You are on page 1of 56

Green Chemistry

Oxidative Desulphurization of Fuel Oils Using Ionic Liquids:


A Review

Journal:
Manuscript ID:
Article Type:
Date Submitted by the Author:
Complete List of Authors:

Green Chemistry
GC-TRV-05-2015-001114
Tutorial Review
25-May-2015
Bhutto, Abdul Waheed; Beijing University of Chemical Technology, ,
College of Chemical Engineering Beijing, China; Dawood College of
Engineering and Technology, Department of Chemical Engineering
Abro, Rashid; Beijing university Of Chemical Technology, Beijing Key
Laboratory of Membrane Science and Technology & College of Chemical
Engineering, Beijing University of Chemical Technology, Beijing 100029, P.
R. China
abbas, tauqeer; Universiti Teknologi Petronas, Malaysia, Petronas Ionic
Liquid Center, Department of Chemical Engineering
Chen, Xiaochun; Beijing University of Chemical Technology, College of
Chemical Engineering
Yu, Guangren; Beijing University of Chemical Technology, College of
Chemical Engineering

Page 1 of 55

Green Chemistry

Green Chemistry Guidelines for Referees


Green Chemistry publishes high quality research and reviews
demonstrating a significant advance in green and sustainable
chemistry.
To warrant publication in Green Chemistry, manuscripts must demonstrate:
1. Innovative, high quality research with high scientific integrity.
2. Significant novelty and advance with respect to green and sustainable
chemistry.
Please ensure that your report comments on both of these aspects

Green Chemistry has a 2013 impact factor of 6.85 and publishes only the highest quality research,
therefore, routine and incremental work however competently researched and reported should
not be recommended for publication.
If you believe that a paper would be better suited to a more specialised journal, please state so in
your report. Please note that the rejection rate for Green Chemistry is currently about 75% of
submitted manuscripts.
Thank you for your assistance in evaluating this manuscript your help and guidance is greatly appreciated.
General Guidance
Journal Scope: Details regarding the journal scope of Green Chemistry can be found here. All manuscripts must be written so as to be
widely accessible (conceptually) to chemists and technologists. Green Chemistry does not publish research associated with 'end-ofpipe' or remediation issues.
Please note that the same quality standards which apply for the Royal Society of Chemistrys specialised journals must apply to
papers submitted to Green Chemistry. This includes characterisation of new compounds or materials. It is the responsibility of
authors to provide fully convincing evidence for the homogeneity, purity and identity of all compounds they claim as new. Please
consult the relevant specialised journal documentation for further guidance.

Organic Chemistry, please see Organic & Biomolecular Chemistry guidelines

Materials Chemistry, please see Materials Horizons guidelines

Physical Chemistry, please see PCCP guidelines

Inorganic Chemistry, please see Dalton Transactions guidelines.


Referees have the responsibility to treat the manuscript as confidential. Please be aware of our Refereeing Procedure and Policy, which
contains full information on the responsibilities of referees and authors, and our Ethical Guidelines.
When preparing your report, please:

Comment on the originality, significance, impact and scientific reliability of the work;

State clearly whether you would like to see the article accepted or rejected and give detailed
comments (with references, as appropriate) that will both help the Editor to make a decision on the article and the authors to
improve it.
Please inform the Editor if:

There is a conflict of interest;

There is a significant part of the work which you are not able to referee with confidence;

The work, or a significant part of the work, has previously been published;

You believe the work, or a significant part of the work, is currently submitted elsewhere;

The work represents part of an unduly fragmented investigation.


When submitting your report, please:

Provide your report rapidly and within the specified deadline, or inform the Editor immediately if you cannot do so. We
welcome suggestions of alternative referees.
If you have any questions about reviewing this manuscript, please contact the Editorial Office at green@rsc.org

Green Chemistry

Page 2 of 55

Dear Editor,
We highly appreciate your efforts to improve our manuscript.
Following those pretty helpful comments, we have significantly revised our
manuscript. The responses are as follows.
Referee 1
Q1. The authors summarized the oxidative desulfurization of fuel using ionic liquids.
However, this manuscript is a routine work. The authors only summarized the results
from the literatures, and did not put forward their own views deeply.
Re. In the revised version, we have deep discussed and put forward our own views, as
the highlighted text in yellow. In addition, we have added one new section 3.4.
Challenge and Perspective of ODS using ILs, to address the challenge and perspective
of ODS using ILs.
Q.2. In addition, at times it is difficult to understand in whole or in parts. The manuscript
requires proper writing.
Re. We have improved and polished the text, especially the writing.
Q.3. The literatures about oxidative desulfurization of fuel using ionic liquids are not
cited completely. According to the Web of Science, the number of literatures is about
70.
Re. We have re-carried out the literature survey. Now the number of literatures cited in
the manuscript is about 74.
Referee 2
Q1. The authors present an interesting review of the literature about the ODS with the
use ionic liquids. The manuscript concisely describes all aspects of the use of ionic
liquids in the ODS processes. From this point of view, this manuscript is eligible for
publication in Green Chemistry. However, the manuscript was very carelessly prepared.
In text can find numerous errors that absolutely must be removed. In current form, this
manuscript should not be submitted to Green Chemistry. Authors must make very
careful adjustment of the whole manuscript and remove many unacceptable errors:
Re. We really feel sorry for such errors. We have carefully checked and made the
manuscript free of writing mistakes, especially type errors. The sections have been also
1

Page 3 of 55

Green Chemistry

re-arranged, and a new section 3.4. Challenge and Perspective of ODS using ILs was
added. Please read it again, and any further suggestions will be very welcome.
Q2. citation [12] and [13] is the same
Re. Correction has been made.
Q3.citation [31] is incomplete
Re. Correction has been made.
Q4. Tables 2,3 and 4 (numbered as 3!!!) must by reedited
Re. Correction has been made.
Q5. Figures 5 and 9 are have been taken from the cited papers and inserted into the
manuscript very carelessly. Both figures are far from original and must be reedited
Re. Correction has been made.
Q6. In chemical abbreviations of ionic liquids indexes must be used in the correct form
(eg. PF4)
Re. Correction has been made.
Q7. All abbreviations of ionic liquids must be used in uniform format (eg. bmim or BMIM)
Re. Correction has been made.
Q8. In my opinion, based on common definition well described in literature, the
IL/POM/SiO2 compound isnt amphiphilic.
Re. Correction has been made.
Q9. p. 16 [Otbim]Ac isnt correct, should be [Omim]Ac.
Re. Correction has been made.
Q10.Citation [41] must by checked, probably is incorrect
Re. Correction has been made.

Green Chemistry

Page 4 of 55

Oxidative Desulphurization of Fuel Oils Using Ionic Liquids: A Review


Abdul Waheed Bhuttoa,b, Rashid Abroa, Tauqeer Abbasc,d , Xiaochun Chena and Guangren Yua,*
a

Beijing Key Laboratory of Membrane Science and Technology & College of Chemical Engineering,
Beijing University of Chemical Technology, Beijing 100029, P. R. China
b

Department of Chemical Engineering, Dawood University of Engineering and Technology, Karachi,


Pakistan.
c

Petronas Ionic Liquid Center, Department of Chemical Engineering, Universiti Teknologi Petronas,
Malaysia
d

Department of Chemical Engineering, COMSATS Institute of Information Technology, Lahore,


Pakistan
*Authors to whom correspondence should be addressed; E-mail:gryu@mail.buct.edu.cn.
Tel./Fax: +86-10-6443-3570.
Abstract
Due to sterically-hindered adsorption of some thiophenic sulphur compounds (S-compounds) such as
thiophene, dibenzothiophene and their derivatives on catalyst surface, hydrodesulphurization (HDS) is not
effective to remove such thiophenic S-compounds in fuel oils. To produce clean fuel oils with lower S-content
(e.g., S<10ppm), severe conditions such as high temperature, high pressure, active catalyst and complex process
are required in HDS, which, however, results into higher cost, more olefin loss, and lower oil yield. Although
some alternative methods such as extraction (EDS), oxidation (ODS), adsorption (ADS) and bio desulfurization
(BDS) have been studied, no one is widely used in commercial scale due to some respective problems. In the
past few decades, ODS of fuel oils using ionic liquids (ILs) has drawn increasing attentions, and many works
have been published. In this new method, instead of traditional organic solvents, ILs are employed as
extractants or/and catalysts, where S-compounds are extracted into ILs phase and oxidized to their sulfone
products, and these more polar sulfones are removed easily. ILs have some advantages such as non-volatility,
wide liquid range, high thermal and chemical stability, regenerability and reusability, which make this new ILsbased method avoid the problems such as solvent loss/contamination and difficult separation and regeneration
in tradition ODS with organic solvents. It is worth noting that the numerous species and the designability of ILs
produce a very huge candidate pool for selecting one suitable IL for oxidative desulfurization. Recently, many
1

Page 5 of 55

Green Chemistry

scientific findings about ODS using ILs have shown its good future. Here, we give a review for these interesting
results to illustrate the novelty, problem and perspective of such a new method.

1. Introduction
Desulphurization of fuel oils such as gasoline, jet fuel, kerosene, diesel and heating oil is an
important process in oil refining. Sulphur compounds (S-compounds) in fuel Oils are
undesirable as they create problems during refining as well as during their commercial use.
During refining, S-compounds tend to deactivate some catalysts used in crude oil processing
and cause corrosion problems in pipeline, pumping, and refining equipment. During the
commercial use of fuel oils, S-compounds are transferred to sulfur oxides in combustion, and
then to sulfates, acid rain, or other particulates which are harmful to the environment.
Furthermore, the S-compounds in the exhaust gases of diesel engines can significantly impair
the emission control technology designed to meet NOx and suspended particulate matter (SPM)
emission standards. With increasing environmental concerns, governments all over the world
are implementing stringent standards to limit the S-content in fuel oil, as shown in Figs. 1 and 2.
Fulfilling the required lower S-compounds specifications, represents a major operational and
economic challenge for the petroleum refining industry1. Therefore, intensively studied are
going to find new economically viable deep desulphurization technologies.
Hydrodesulphurization (HDS) is a widely used commercial method to remove S-compounds
in fuel oils. In HDS, S-compounds are catalytically converted into H2S and corresponding
hydrocarbons at elevated temperatures (300 to 340C) and pressures (20 to 100 atm of H2)
with Co-Mo/Al2O3 or Ni-Mo/Al2O3 catalyst, and H2S is subsequently separated from oils and
catalytically oxidized into elemental sulfur in the Claus process. HDS process is efficient in
removing thiols, sulfides, and disulfides but is less effective for heterocyclic S-compounds

Green Chemistry

Page 6 of 55

such as thiophene (TS), dibenzothiophene (DBT) and their derivatives, especially 4, 6dimethyldibenzothiophene (4, 6-DMDBT) because of the ineffective adsorption of these
heterocyclic S-compounds on catalyst surface. Some typical S-compounds in fuel oils are
shown in Fig.3. To remove these heterocyclic S-compounds in HSD, the reactor size unit needs
to be increased by factors of 5 to 15 and the pressure and temperature have to be elevated
further more with more active catalysts. These steps result into significantly increase in the
operational and capital costs and also leads to undesired side reactions bringing saturation of
olefins and loss of octane number. To overcome drawbacks of HDS in deep desulphurization,
some alternative methods such as extraction (EDS), oxidation (ODS), adsorption (ADS) (Tab.1
shows different adsorbents used in ADS at optimized conditions), and bio desulphurization
(Tab.2 shows bio-desulfurization by different microorganisms) are under considerations.
Since refractory heterocyclic S-compounds such as TS, DBT and their derivatives are easily
removed by the oxidative desulphurization (ODS)2, 3, therefore ODS is currently being
explored as a promising strategy to achieve an ultra-low S-level in fuel oil because it is simple
in processing and high efficiency4. No use of expensive hydrogen is another advantage of ODS.
In subsequent operation, oxidized compounds can be extracted from fuel oils through
contacting oxidized fuel oils with non-miscible polar solvents. Many solvents have been
explored such as N,N-dimethylformamide, acetonitrile, methanol and dimethylsulfoxide.
However, these solvents are volatile which result in not only solvent volatile loss and
contamination but also make the solvent recovery difficult.
Ionic liquids (ILs), just emerging in the past few decades, are a class of new solvents, which
are promising alternatives to traditional volatile solvents used in ODS. ILs, composed entirely
of organic cation and inorganic or organic anion, have been explored as green reaction media,

Page 7 of 55

Green Chemistry

owing to their unique properties such as negligible volatility, excellent thermal and chemical
stability, good solubility characteristics, and the variety of structures available.
ILs has been investigated as extractive reagents in extractive desulfurization, as has been
reviewed in our recent publication5. Recently, researchers have been attempting to use ILs as
solvents in ODS as well as both catalysts and extractive reagents in coupled extractiveoxidative desulfurization6. Such ODS with ILs shows very positive results and also eliminates
the loss of volatile solvent and contamination/pollution. ODS with ILs also ensure easy
regeneration and good stability. In addition to this, it also ensure that those heterocyclic Scompounds unreactive to HDS are efficiently removed in only single stage to obtain clean fuel
oils with S<10 ppm.
Besides homogeneous catalytic ODS, many research groups have committed to
heterogeneous catalysis system of supported ILs, ILs emulsion, and ILs photocatalysis. This
work reviews recent progress and developments to purify the fuel oil to S-free or S-ultralow
fuels by ODS with ILs technology, also the issues of traditional ODS.
2. Oxidative Desulphurization (ODS)
ODS has been considered as a promising technology for deep desulphurization of light oil3.
As shown in following reactions, in ODS the S-compounds are oxidized to sulfones by
chemical reaction using an oxidant. The sulfone compounds are then easily extracted from the
fuel oil by a solvent taking advantage of due their higher polarity5. Thus, ODS process
comprises of two stages: (i) oxidation; (ii) followed by separation operations.


        

Green Chemistry

Page 8 of 55

Oxidization brings dramatic changes in physical properties of S-compounds. For example


methyl sulfide (CH3SCH3) is a light ( = 0.846 g/mL), water-insoluble, low boiling liquid (bp
= 36oC), whereas methyl sulfoxide (CHSOCH3) is a heavy ( = 1.481g/mL), high boiler
(189oC) and water-miscible liquid7.
2.1. Oxidant in ODS
The oxidation of S-compounds with organic hydroperoxides occurs in the presence of
catalysts. The oxidants that can be used include peroxy organic acids, hydroperoxides, nitrogen
oxides, peroxy salts and ozone, etc. These oxidants donate oxygen atoms to the S-compounds
in mercaptans (thiols), sulfides, disulfides and thiophenes to form sulfoxides or sulfones.
Tab.3 gives the list of some common oxidants and their active oxygen content.
Among different chemical oxidants, the best option is H2O2. Table 3 indicates that H2O2 gives
the highest percentage of active oxygen. The other advantages for the use of H2O2 are: (1) low
cost, (2) non-polluting, (3) non-strongly corrosive, and (4) commercial availability8. The main
challenge using H2O2 as an ODS oxidant is the slow reaction rate because of mass-transfer
limitation in the biphasic oxidation reaction and the subsequent energy-consuming biphasic
separation process.
2.2. Catalyst in ODS
Oxidation reactions are effective in the catalysis of organic acids or transition metal salts.
Most studies have been focused on molybdenum (Mo) catalysts, and they usually employ
heterogeneous Mo/Al2O3 catalysts. Mo catalyst supported on Al2O3 presented higher catalytic

Page 9 of 55

Green Chemistry

activity compared with Mo catalyst supported on TiO2 and SiO29. However, molybdenum
tends to leach into the reaction medium, where the catalysts are not very stable and the main
part of the catalytic activity is due to the solubilized molybdenum. The oxidation activity of
each S-compound increased with the increasing O/S molar ratio up to the O/S molar ratio of 3
and then leveled off beyond this value. The oxidative reaction of S-compound can be treated as
a first-order reaction and apparent activation energies of oxidative reaction are 281 kJ/mol9.
The polyaromatic S-compounds show higher reactivity in ODS than TSs and BTs, in the
reverse reactivity order of HDS10. In the oxidation of S-compounds catalyzed by
polyoxometalates, the mass transfer across the interface of aqueous phase and oil phase is the
rate-limiting step. Consequently, a phase transfer agent (PTA) is usually added to the reaction
system in order to enhance the mass transfer. 100% oxidation of DBT in a gas oil was achieved
with

H2O2 as

oxidation

agent

using

phosphotungstic

acid

as

the

catalyst

and

tetraoctylammonium bromide as the phase transfer agent, at optimal conditions11. Zhang and
co-workers12 suggested that [C4mim]3PMo12O40/SiO2 could effectively catalyze the oxidation
of BT, DBT, and 4,6-DMDBT using H2O2 as the oxidant under mild conditions. Complete
DBT conversion was obtained at 60C, an O/S molar ratio of 3.0, and thermal equilibrium in
100 min. The oxidation reactivity decreased in the order: DBT > 4,6-DMDBT > BT.
[C4mim]3PMo12O40/SiO2 and water phase were easily separated together from the oil phase by
centrifugation, and no deactivation was observed after seven runs if the spent catalyst was
dried to remove the H2O retained on the catalyst surface. Carbazole and quinoline had positive
effects on DBT oxidation, probably because they help to slow down the thermal decomposition
of H2O2. The presence of indole inhibited DBT oxidation due to the strong adsorption of
indigo generated by indole oxidation. The [C4mim]3 PMo12O40/SiO2-H2O2 oxidation system is
effective in removing bulky S-compounds from diesel fuels.
6

Green Chemistry

Page 10 of 55

2.3. Separation Operations


The second step in ODS is the removal of the oxidized compounds from fuel oil. The
oxidized S-compounds can be extracted from the light oil by contacting oxidized light oil with
non-miscible polar solvents. Depending on the solvents used for extraction, the oxidized
compounds and solvent are separated from the light oil by gravity separation or centrifugation.
Sulfones are extracted by polar solvents such as N-methyl pyrrolidone (NMP)13, methanol

13

Dimethylformamide (DMF) , dimethyl sulfoxide (DMSO), and acetonitrile in a simple process


under milder conditions with low equipment and operation costs. The most attractive solvent
for the extraction of oxidized organic S-compounds is DMSO14. However these polar solvent
are volatile and harmful to environment and human health15.
Fig 4 shows the flowchart of biphasic simultaneous oxidation/extraction ODS unit.
Oxidation is accomplished by contacting an oxidant with fuel oil under optimum conditions
and continuing the reaction until the oxidized S-compounds are formed. The reaction
conditions are selected in such a way that reaction is stopped before the oxidant attacks other,
less reactive, fuel oil components. Down the reaction, oxidants are regenerated for re-use.
Washing, extraction and chemical post-treatment can remove any unused oxidant that remains
in the light oil.
The oxidized compounds are then extracted from the light oil by contacting oxidized light oil
with a non-miscible solvent. This solvent is selective for the relatively polar oxidized Scompounds. The oxidized compounds and solvent are separated from the light oil by
decantation. The light oil is water washed to recover any traces of dissolved extraction solvent
and polished using other methods, such as by absorption using silica gel and alumina. The
oxidized compounds and solvent are separated from each other by a simple distillation for

Page 11 of 55

Green Chemistry

recycling. The desulphurization efficiency for light oils lies in the order straight-run light gas
oil > commercial light oil > light cycle oil and demonstrates that high-aromatic-content light
oil is difficult to desulfurize.
2.4. Oxidative Reaction Mechanism
Generally, in the ODS reactions, the divalent sulfur atom of S-compounds undergoes
electrophilic addition of oxygen atoms from the hydrogen peroxide to form the sulfone, i.e., a
hexavalent sulfur9, 16-18. Fig. 5 shows the overall ODS reaction and a schematic diagram of the
process.
Several

mechanisms

of

ODS

reactions

have

been

previously

proposed17-19. The

homogeneous biphasic ODS system is simple and uses no PTA. Fig. 6 presents a detailed
reaction mechanism. Once the catalyst mixes with the H2O2 and the diesel fuel in acetic acid,
the biphasic catalyst system starts to form at room temperature. Farhan Al et.al

20

suggested

that WO42 anion reacts in two steps with two molecules of H2O2 in sequential substitution
reactions and in each step a W = O group is replaced by a W(O2) group and H2O is displaced.
The resulting peroxotungstate [(O)2WO2)2] anion then reacts by sequential oxygen atom
transfer to the sulfur of R2S to form sulfoxide (R2SO) then the sulfone (R2SO2), which can be
extracted with the aqueous phase. The peroxotungstate can be regenerated on the interface
between the two layers or in the aqueous phase in presence of adequate supply of H2O2.
Sulfones are known to be slightly more polar than S-compounds; so they will form a white
precipitate. The whole process will result in a biphasic solution by which the upper layer
becomes almost S-free diesel20.
2.5. Kinetics Study of Catalytic Oxidation on S-Compounds

Green Chemistry

Page 12 of 55

Zhu et al,21 investigated ODS using surfactant-type polyoxometalate-based ILs, such as


[(nC8H17)3NCH3]3{PO4[MoO(O2)2]4},[(n-C12H25)3NCH3]3{PO4[MoO(O2)2]4},
C8H17)3NCH3]3{PO4[WO(O2)2]4}

and

[(n-C12H25)3NCH3]3{PO4[WO(O2)2]4} .

[(nThe

study

proposed overall mechanism of catalytic desulfurization in four steps as shown in Fig. 7,


which are; (1) the active peroxo species (II) (abbreviated as Mo(O2)) is regenerated from the
reaction of (I), when surfactant-type polyoxometalate-based ionic liquids (SPILs), reacting
with excess H2O2. (2) An oxygen transfers from the active Mo-peroxo species (II) to the
sulfide; then there is a formation of the transition state. (3) A complete O-transfer to the sulfide
takes place, which yields the sulfoxide and the Mo(O) species (I). (4) The active species (II)
takes part in the ODS, which leads to the corresponding sulfone and the regeneration of the
Mo(O) species (I).
The reaction sequence that may be involved in this oxidation as proposed by Zhu et al21is
shown in Fig 8.The first step of the reactions (1) must be reversible to regenerate the catalyst,
followed by other oxidation steps which lead to the R2SO and R2SO2. Furthermore, k2 is the
rate constant of the rate determining step, which was given on the basis of the concentration of
the active species. So the rate of the formation of sulfoxide can be expressed by Eq. (1):
r=

 


 


= k MoO R S

= k H O MoO k  MoO  k MoO R S k MoO R SO=0

MoT = MoO + MnO 


r=

(1)

 


=$

$% $ & '(   )


*% +$% (  +$  +$,  

(2)

(3)
(4)

The initial rate can be obtained as the following Eq. (5):

Page 13 of 55

Green Chemistry

r- =

 /


$% $ & '(   / )

(5)

$*% +$% (  / +$  /

According to the experimental condition, k-1 + k1[H2O2]> > k2[R2S] is reasonable for the
stability of [MoO2]. In this case, the oxidation rate is the first-order. So Eqs. (6) and (7) were
obtained from Eq. (5).
r=
K=

 


= KR S

$% $ & (  
$*% +$% (  

(6)
(7)

Eq. (6) suggests that there is a straight linear relation between the plot of [R2S] and t, which
goes through the origin point. Therefore, the catalytic oxidative desulfurization can be treated
as the pseudo-rst-order rate with SPILs catalysts.
Reaction kinetics was great important parameters to explain the oxidation of DBT.
Experiments were performed using SPIL A to obtain kinetic parameters of the oxidation of Scompounds. The rate constant for the apparent consumption of S-compound was obtained from
the pseudo-first-order Eq. (6) as follow 22.
1

 = kC
1

(8)

In 14 = kt

(9)

t/ = 0.693/k

(10)

Where Co and Ct were the S-concentrations at time zero and time t (min) and k was the rstorder rate constant (min1). The plot of ln(Co/Ct) against t, a straight line with slope k was
obtained (Fig 9). Half-life was calculated by Eq. (9), which was derived from Eq. (8) by
replacing Ct with Co/2.
The apparent rate constant k of DBT was 0.0408 min1 and the half-life was 17.0 min. The
kinetic data of the DBT oxidation were in accordance with an apparent rst-order kinetic rate21.
10

Green Chemistry

Page 14 of 55

The kinetics for oxidative desulfurization of DBT and BT by [C63MPy]Cl/FeCl3 is given in


Fig.10. It shows that the rate constant was 1.0161 and 0.3147 min1 for DBT and BT at 298 K,
respectively23. It is observed that the rate constant values of bulkier S-compounds is higher in
ODS when compared to the rate constant for the same compounds in HDS process24.
3. ODS using Ionic Liquids
3.1. Ionic Liquids (ILs)
ILs, termed as green solvents, can be used for desulfurization of liquid fuel due to their very
low vapor pressure and wide range of applications with unique physical and chemical
properties as mentioned above25. Their ability to be recycled without any impact on the
environment provides impressive advantage in the present era of environmental concern34. In
the past few years, significant literatures have become available in the area of preparation,
characterization and application of ILs for synthesis, catalysis and separation.
Commonly used ILs consist of inorganic anions and organic cations with alkyl side chains
and aromatic moieties26. Different ILs can be synthesized having a wide range of physical and
chemical properties that can be fine-tuned by using different cations and anions to meet the
requirement of specific applications. ILs are good solvents for a wide range of both inorganic
and organic materials, and unusual combinations of reagents can be brought into the same
phase. They are often composed of poorly coordinating ions, so they are highly polar yet noncoordinating solvents. They are immiscible with a number of organic solvents and provide a
non-aqueous, polar alternative for two-phase systems. Hydrophobic ILs can also be used as
immiscible polar phases with water. ILs are nonvolatile, hence they may be used in highvacuum systems and eliminate many contaminant problems27. Well-known cations are

11

Page 15 of 55

Green Chemistry

imidazolium, pyridiniuim, isoquinolonium, ammonium, phosphonium and sulfonium as shown


in Fig 11.
3.2. ODS using ILs
Lo et al28 were first to combine chemical oxidation and solvent extraction using ILs in a onepot operation for deep desulfurization of light oils. Simultaneous extraction and oxidation of Scompounds from light oil in ILs increases the desulfurization yield by about an order of
magnitude relative to that of merely extracting with ILs28. The ILs acts as both extraction
media for the S-compounds and provide the oxidation environments for the conversion of Scompounds to sulfones. An organic acid or a transition metal is needed as catalyst in the ODS
process. The same study found water-immiscible IL [C4mim]PF6 more-effective solvent than
the water-soluble [C4mim]BF4 for providing an environment that results in a higher rate of
chemical oxidation28. Xu et al have carried out a detailed theoretical study to better understand
the mechanism of oxidative-extractive desulfurization of DBT from fuels by [C6mim]BF4 IL in
the presence of H2O229. These ILs containing halogen atoms such as the anion BF4- and PF6easily yield white fumes of hydrogen fluoride or hydrate precipitates, which will lead to
potential environmental and safety problems.
Some other ODS processes using H2O2 as oxidant and ILs as both solvent and extractant
were reported30-33. Nie et al used Iron-containing ILs used as extractant in ODS process to
remove 100% S and reached reaction equilibrium fast34with an apparent rate constant of
0.9951 min-1 at 298 K. Cooper and co-workers 35 observed that when a coordination compound
is generated between H2O2 and an amide, such as urea; then the H2O2 on the coordination
compound decomposes to produce hydroxyl radicals that are strong oxidizing agents.More
than 95% S-removal could be obtained by carrying out the extraction with [C4mquin]N(CN)2
12

Green Chemistry

Page 16 of 55

at 30oC at 500 rpm with 1:5 IL:diesel weight ratio and 20 minutes of extraction time36. Zhao et
al37 reported that the S-contents of DBT dissolved in n-octane could be dramatically reduced
using H2O2formic acid as an oxidant and pyridinium-based ILs as phase-transfer catalysts
(PTCs). Jiang et al38 showed that [C8bim]CH3COO containing eight-carbon side chain has of
best catalytic activity for ODS. 87.5% of TS in the model oil was removed under the optimal
conditions of oxidation temperature at 70 C, oxidation time of 180 min, simulated oil dosage
of 10 ml, and ILs/H2O2 volume ratio of 1:1.1. When acetic acid-based ILs were used as both
PTCs and extractants, which showed good oxidative ability31.
Jiang et al38 achieved high desulfurization efficiency of DBT both in hydrophilic IL
[C4mim]BF4 (94.9%) as well as in hydrophobic IL [C8mim]BF4 (97.2%) by using ChFeCl4 as a
catalyst under mild conditions. Electron spin resonance measurements suggested that the active
oxygen species generated by ChFeCl4 and H2O2 in IL were involved in the catalytic oxidation
of DBT. Wilfred et al36 achieved desulfurization efficiency up to 99.9% through catalytic
oxidation using 1- butyl-6-methylquinolinium dicyanamide [C4mquin]N(CN)2.
Kulkarni and co-workers39 also applied this oxidation/extraction system to actual light oil
containing a S-content of 8040 ppm. After 10 h, in the C4MIM+PF6 extraction/oxidation
system, the decrease of S-content was observed from 8040 to 1300 ppm. The Bronsted acid IL
[Hnmp]BF4 is effective on the ODS of actual diesel fuel. The results show that 99.4% sulfurcontaining compounds which are present in the actual diesel fuel can be removed40.
Use of acidic ILs have led to very good results in ODS of fuels without the need of addition
of an external catalyst to the medium41. The intrinsic acidic character of the ILs allows them to
act as both catalysts and solvents. It also eliminates the requirement of additional catalyst. The
acidity of protons is mainly determined by their solvation. The acetic acid-based ILs act as

13

Page 17 of 55

Green Chemistry

both phase-transfer catalysts and extractants with good oxidative ability. In this regard, study
by Thomazeau et al42 has proposed an acidity scale that correlations the catalytic activities
measured in various acidic reactions. Fanget al43 suggests that with imidazolium as the cation,
the desulfurization capability of ILs decrease in the following order, TFA> HSO4>
COO>AlCl4> AcO. The study also shows that when the acidity of IL is much stronger, the
catalytic and extractive capability is better.When the anion is HSO4, the order of the
desulfurization capacity of different cationtypes is [C5mim]+> [C3Py]+>[C4mim]+> [C3mim]+>
[HSO3C3 mim]+> [HSO4C3EA]+> [HSO3C5Py]+. It shows that ILs with cation
[Cnmim]+(including [C2mim], [C3mim], [C4mim], and [C5mim]) have better extraction
capability than those with [HSO3C3mim]+, [HSO4C3EA]+, and [HSO3C5Py]+43. Zhao et al44
optimized ODS of DBT in the model oil with Brnsted acidic ILs N-methyl-pyrrolidonium
phosphate [C6nmp]H2PO4 as catalytic solvent and H2O2 as oxidant. 99.8% DBT in the model
oil was removed under the optimal conditions of molar ratio of H2O2 to sulfur of 16:1, reaction
temperature of 60oC, reaction time of 5 h, and volume ratio of model oil to ILs of 1:1. The
desulfurization efficiency of actual diesel was 64.3% under the optimized conditions. The
Brnsted acidic IL [C6nmp]H2PO4 can be recycled six times without a significant decrease in
activity.
There are very few examples of the use of Fenton-like reagents in oxidative desulfurization38.
Fenton-like ILs [(C8H17)3CH3N]Cl/FeCl3H2O2 system showed that the S-removal of DBTcontaining model oil reached 97.9% and that the S-level of FCC gasoline could be reduced
from 360 ppm to 110 ppm45.
Dong el al

23

studied the activity of [C63mpy]Cl/ FeCl3 on BT and DBT. The results suggest

S-removal followed the order of DBT> BT. Xiong el al46 investigated the catalytic
performance of Fenton-like IL supported on meso-porous material MCM-4,1 with BT, DT,
14

Green Chemistry

Page 18 of 55

DBT, and 4,6-DMDBT.The results shown in Fig. 12 suggest that the S-removal decreased in
following order: DBT>DT>BT>4,6-DMDBT.
The difference in removal efficiency mainly came from aromatic -electron density of Scompounds. The electron density on the sulfur atom of DBT, BT, and 4,6 DMDBT is 5.758,
5.739, and 5.760, respectively

49.

The relatively lower electron density of TS made ILs

extraction after ODS process ineffective when attempting to desulphurize gasoline. Sextraction is not the only parameter to take into account. Co-extraction of (un)desired
compounds, integration of the process in the refinery, and life cycle analyses, among others,
are further aspects to take into account in the decision-making prior to implementation of the
proposed alternatives.
3.2.1. Effect of Reaction Temperature on S-Removal
The influence of reaction temperature on removal of DBT by [C63mpy]Cl/FeCl3 in the
presence of H2O2 is shown in Fig. 12 and 13. It can be seen that when the reaction temperature
for [C63mpy]Cl/FeCl3 increases S-removal increases. However, when the temperature increases
above 308K, the S-removal decreases sharply. DBT is easier to remove than BT at 298 K by
[C63mpy]Cl/FeCl323. For [C4mim]Cl/3ZnCl2, the highest S-removal efficiency of 99.9% is
obtained at 45C after 7h, but only 65.7% at 30C and 89%at 60C; whats more, the Sremoval is 99.9% after 3h at 45C, 47.4% at 30Cand 62.1% at 60C

47

. According to

Sachdeva and Pant48 the formation of peroxide becomes more rapid at higher temperature,
leading to increased conversion of S-compounds to sulfones.
Zhao, et al44 found out the optimal temperature at 60C, for ODS of DBT in n-octane as
model oil with Brnsted acidic IL [C6nmp]H2PO4 as catalytic solvent and H2O2 as oxidant.
Zhang, et al49 used [C4mim]HSO4 in ODS of DBT in model oil. In their work complete
15

Page 19 of 55

Green Chemistry

conversion at 60C was realized in 30 min. When temperature was raised to 70 or 80C, the
desulfurization decreased to 99% and 96%, respectively. These studies suggest a high
temperature is not beneficial for the removal of DBT. This might be because the
decomposition of H2O2 was accelerated at high temperatures50. Therefore, ODS using ILs
could be easily carried out at moderate (40-600C) temperature. The optimal temperatures
depends upon nature of ILs33. Mostly, low viscous ILs follow a slight decreasing or no
effecting trend for S-removal efficiency with increasing temperature from ~ 400C. On the other
hand, the trend becomes reversed for high viscosity ILs, such as [C4mim]Cl/3ZnCl2,
[C6nmp]H2PO4 and [C4min][PF6], where an increase in temperature from ~ 400C corresponds
to a slight or high increase in the efficiency. The reason for these variations between high and
low viscosity ILs can be understood from the variation in the viscosity of ILs with increasing
temperature. With an increase of temperature for high viscosity ILs, the viscosity of ILs is
decreased, and as a result, the ILs and the S-content of the oil have more opportunities to
interact with each other, leading to the high S removal efficiency.
3.2.2. Mass Ratio of IL to Model Fuel
The ILoil mass ratio is one important factor for the selectivity of ILs for ODS
desulfurization. As the cost of ILs is high, it is preferred that a minimum quantity is utilized in
fuel desulfurization, but it is observed from the literature that the S-removal efficiency
decreases with a decreasing ILoil mass ratio. For instance, the mass ratios of
[C4mim]Cl/3ZnCl2 to oil were tested at 60 minutes and the order of S extraction in ODS
efficiency follows the order 1 : 5 < 1 : 4 < 1 : 3 < 1 : 2 < 1 : 1 < 2 : 1 (w/w) ILoil. Tab.45
indicates that, with the increase of IL/oil mass ratio, the S-removal efficiency increases both
for [C4mim]Cl/2ZnCl2 and [SO3H_C4mim]HSO4. Compared with the molar ratio of O/S, the
16

Green Chemistry

Page 20 of 55

effect of mass ratio of IL/oil is limited; for example, when the mass ratio of IL/ oil is increased
from 1:5 to 1:1, the S-removal is increased from 92.2% to 100% for [C4mim]Cl/2ZnCl2 and
from 93.9%to 98.1% for [SO3H_C4mim]HSO4. Meanwhile, Similar results were obtained
when a series of [BF4] and [MeSO4]-based ILs were used to investigate the influence of the
mass ratio. Despite the increasing efficiency with an increasing ILoil mass ratio, it is found
that the increase does not have the same rate for all ILs. This typically depends on how the
individual chemical natures of ILs are related to their extraction abilities. According to the
study by Mochizuki and Sugawara51 the extraction yield of DBT increased linearly with an
increase in the length of alkyl chains and the mass ratio of the IL to the model fuel.
Apart from the positive effects of increasing the ILoil mass ratio, the ILoil mass ratio has
to be carefully selected based on a compromise between S removal and oil recovery. Moreover,
the regeneration of ILs may also be considered for the process as this highly affects the overall
process cost.
3.2.3. Regeneration of used ILs
After each ODS process finished, the IL is recovered and reused without significant loss of activity.
Regeneration of ILs is an important feature for selection of ILs. It can compensate for the high cost of
ILs. The methods of regeneration of S-loaded ILs may vary on the basis of the nature of the ILs and Scompounds. The regeneration of used hydrophilic ILs is carried out by dilution with water followed by
simple distillation41. According to the study by Zhang et al

49

[C4mim]HSO4 can be recycled five

times with a slight loss in activity, e.g., DBT removal dropped from 100% to 95% under the same
experimental conditions. The study by Zhao et al40 suggest that IL [C6nmp]BF4 can be recycled 7
times without a significant decrease in activity. [CH2COOHPy]HSO4 can be recycled 9 times without
a significant decrease in the sulfur removal52.
17

Page 21 of 55

Green Chemistry

Wang et al53 suggested that during the recycling some IL was wasted when IL was separated
and regenerated which result in little drop in DBT removal from the oil phase with the increase
of the cycle. Zhang et al54 attributes the decrease of S-removal to the increase of oxidation
product DBTO2 that accumulates in the IL phase.
The desulfurization activity of [C63mpy]Cl/FeCl3 decreased from 100% to 94.5% after five
cycles. Dong et al23 investigated the recycling of the used IL phase with and without
distillation. Results are shown in Tab. 5 which suggest that the used IL [C63mpy]Cl/FeCl3 with
distillation has a better recycling performance than[C63mpy]Cl/FeCl3 without distillation in the
ODS process. Presence of white solid DBTO2 also affects the performance of recycled ILs23.
3.2.4. Concentration of H2O2 as Oxidant
The concentration of H2O2 has a significant influence on desulfurization efficiency. Mostly, the Sremoval efficiency increases with oxidant to S- compound (O/S) molar ratio. The effect of O/S molar
ratio on desulfurization for [C4mim]Cl/3ZnCl2 was determined by Chen et al47, the S-removal
efficiency increases from 18.6% when the molar ratio of O/S is 2, to the maximum value of 99.9%
when the molar ratio of O/S is 8; but exceeding the O/S molar ratio of 8, the S-removal efficiency
decreases with increasing O/S molar ratio, e.g., the value is reduced to 49.3% when the molar ratio of
O/S is 9. According to the stoichiometry of the ODS reaction, 2 mol of H2O2 is consumed for every 1
mol of DBT to give the corresponding sulfone, i.e., DBT-sulfone (DBTO2), thus the molar ratio of O/S
is 2; however, the highest S-removal of 99.9% is obtained at the O/S molar ratio of 8, instead of 2, as
shown in Fig.14, i.e., the stoichiometric H2O2 is not enough to oxidize all the DBT extracted into the
IL phase; this is because of the fact that the decomposition of some H2O2 occurs in ODS process and
excess H2O2 is required to ensure the DBT oxidization, which are also indicated in several papers in
literature.53 At the same time, it is neither desirable when the amount of H2O2 solution is too much,
18

Green Chemistry

Page 22 of 55

because excessive H2O2 solution will dilute the IL and influence the extraction of DBT from diesel
fuel41. This is consistent with the result in Fig.14, where the S-removal efficiency is reduced from 99.9%
to 49.3% when the O/S molar ratio increases from 8 to 9.
In the study by Jiang et al55 the S-removal was 76.3% with 30 wt % H2O2 which increased to
97.9% with 7.5 wt % H2O2.In the above study [C4mim]3Fe(CN)6was used as catalyst and
[C4mim]BF4 as an extractant. The results of the ODS of model oil catalyzed by Fenton-like ILs
at room temperature by Jiang, Y., et al 45 are shown in Tab.6.
3.2.5. Influence of Molar Ratio of ILs on S-removal.
Chen, et al 47 investigated the effect of IL/oil mass ratio on S-removal. Their results are given
in Fig.15 which indicates that the quantity of IL has an important effect on the removal of DBT.
The S-removal efficiency was increased from 49.1% to 99.9% when the mass ratio of IL/oil
was increased from 1:5 to 1:2. However, the S-removal efficiency came down to 87.8% when
mass ratio of IL/oil was further increased to 1:1. The reason being that when O/S molar ratio
was reduced with the increase in IL/oil mass ratio, the IL get capacity to extract more DBT56,
but the amount of H2O2 was kept constant so the O/S molar ratio is reduced, less S-compounds
were oxidized. Similar results were obtained by both Zhang et.al 57 and Chen, X., et al41.
3.2.6. Influence of viscosity of ILs on S-removal.
ILs are prepared from two solid materials, which would lead to the high dynamic viscosity
of the obtained ILs which limits their extraction ability58. Due to the much higher viscosity of
ILs59, the overall sulfur removal rate is limited by the mass transfer between phases with very
active catalysts. For this reason, an increase in the mass transfer clearly improves the overall
sulfur removal rate. With viscous IL, the overall sulfur removal rate is limited by the mass

19

Page 23 of 55

Green Chemistry

transfer between two phases which led to reduction in reaction rates and may also causes
competitive unimolecular side reactions. Viscous IL also causes handling difficulties during
filtration, decantation, and dissolution.ODS process can be more effective if the shortcomings
of ILs on high cost and viscosity are overcome31-33. Ionic liquids incorporating the
bis(trifluoromethanesulfonyl)imide, [NTf2], anion are favoured for their low viscosities59.
According

to

Li,

et

al

C5H9NO0.3FeCl3shows

remarkable

extraction

ability

for

dibenzothiophene (DBT) with Nernst partition coefficients (kN) above 7.560. Low viscosity IL
allows extraction of oxidized sulphur compound in relatively short timeat room temperature58.
Increasing temperature reduces the viscosity of IL which increases the catalytic performance of
IL. However, the decomposition of H2O2 accelerates at higher temperatures, leading to reduced
desulfurization efficiency61.
3.3. Other Pattern of ODS with ILs
3.3.1. Supported ILs as Catalytic Solvent
Processes that focused on homogeneous catalytic systems need large amount of ILs that are
costly and may affect the economic viability of a potential process. The recovery of the ILs is
another problem. Many groups have committed to heterogeneous catalysis system and turned
to studying supported ILs. Immobilizing a certain amount of ILs on solid carriers could obtain
ILs supported catalysts. The obtained catalysts combined the advantages of ILs with the easy
separation and recovery performances of the supported materials. Xun et al 62 in their study of
the synthesis of metal-based IL supported catalyst and its application in catalytic oxidative
desulphurization of fuels prepared the heterogeneous catalyst by embedding [C4mim]FeCl4 IL
in silica gel. Scheme given in Fig. 16was followed to synthesize the [C4mim]FeCl4/silica gel

20

Green Chemistry

Page 24 of 55

catalysts. The amount of [C4mim]FeCl4 decreased sharply to reach deep desulphurization and
solved the problems of recycle. The catalytic oxidation reaction of different S-containing
compounds decreased in the order of DBT > BT > 4,6-DMDBT62.
Although heterogeneous catalysts showed excellent performance in catalyst recovery and
reuse, the catalytic sites were lower exposure to the reactants. Thus, their activities were
usually lower than those of homogeneous catalysts. Additionally, heterogeneous catalyst also
required relative long reaction time and easily leached of active species into the reaction
medium63.
3.3.2. Catalytic ODS using IL Emulsion System
Ge et al64have developed a catalytic oxidation IL emulsion desulphurization system, which
composed of water-immiscible IL ([C4mim]PF6), 30 wt % H2O2, and an amphiphilic catalyst
[C18H37N(CH3)3]7[PW11O39]. Here [C18H37N(CH3)3]7[PW11O39] behaves both an emulsifying
agent and a catalyst instead of only a surfactant. This kind of catalyst not only maintains the
emulsion droplets stable but also provides higher interfacial surface area where the oxidation
of S-compounds takes place. During the reaction, the IL emulsion functions as highly
dispersed microreactors. The S-compounds in the model oil were first extracted into the IL
emulsion

phase

and

then

oxidized

to

their

corresponding

sulfones

by

[C18H37N(CH3)3]7[PW11O39] in the H2O2/[C4mim]PF6 interface. The sulfones accumulated in


the [C4mim]PF6 phase. After reaction, the desulphurization system quickly divided into two
layers; the deep desulphurization can be achieved in this way. After the reaction, the reaction
system was still a biphasic system, so the oil could be separated by simple decantation from the
biphasic system of the IL easily. The used ILs, whose structure does not change and the
recovered IL can be reused for further emulsion catalytic oxidation cycles. For example
21

Page 25 of 55

Green Chemistry

[C4mim]PF6 emulsion desulphurization system could be recycled five times with an


unnoticeable decrease in catalytic activity.
The milky-white IL emulsions are formed when H2O2 and [C18H37N(CH3)3]7[PW11O39] were
added into [C4mim]PF6. The catalyst is distributed in the interface of H2O2 and waterimmiscible ILs. In this emulsion reaction system, the catalyst molecule acts as an emulsifying
agent, could be uniformly distributed in the interface of H2O2IL, and forms a film around the
dispersed IL droplets (Fig 17). Consequently, the lipo philic quaternary ammonium cations of
the amphiphilic catalyst would lie on the oil side and the hydrophilic hetero poly anions would
lie on the H2O2 side. Since

hetero poly anions ([PW11O39]7-) depolymerized into several

smaller active species including [(PO4)(WO(O2)2)4]3-(PW4), [(PO4)(WO(O2)2)2(WO(O2)2


(H2O))]3-(PW3), and [(PO3(OH)) (WO(O2)2)2]2-(PW2) in the presence of H2O2, because the IL
emulsion was immiscible with n-octane and formed a biphasic system. The S-compounds in
the model oil were first extracted from oil phase into IL phase and oxidized to their
corresponding sulfones by the active species simultaneously; the sulfones accumulated in IL
phase. After reaction, the desulphurization system quickly divided into two layers. In this way,
the catalyst in the emulsion droplets can be readily separated from the oil and recycled, and the
IL emulsion system could be recycled five times without an obvious decrease in activity65.
3.3.3. Photo-catalytic ODS using ILs
Photo-catalytic ODS (PODS) is also considered as aneective alternative method. In the
PODS process, S-compounds in nonpolaroil phase were extracted to polar extractant phases,
such as water, acetonitrile, or ILs, in which they were photo-oxidized to the corresponding
sulfones in the presence of O2, H2O2, or photosensitizers66-68. With the development of photocatalysis, TiO2 become the most used photo-catalyst due to its nontoxicity, chemical stability,
22

Green Chemistry

low cost, and high photo-catalytic ability. TiO2 was also used in PODS69,

Page 26 of 55

70

.Xiao et.al71

prepared Nano-TiO2 in [C4mim]BF4 IL via microwave radiation. In this process, IL was used
not only as microwave absorption medium for preparation of TiO2 but also as extractant for
DBT. The eect of microwave time on the photo-catalytic desulfurization ability of prepared
TiO2 in the presence of O2 was investigated. 98.2% and 94.3% sulfur could be removed from
model oil and actual diesel oil, respectively, in 10 h UV irradiation under the conditions that
V(IL)/V(oil) = 1:5, air flow = 200 mL/min. The [C4mim]BF4 IL was recycled five times with a
slight decrease in desulfurization eciency.
The in situ photo-catalytic oxidation process for DBT was proposed by Xiao et.al71 as shown
in Fig 18. TiO2 was prepared from titanium tetraisopropoxide (TTIP) in [C4mim]BF4 IL. When
[C4mim]BF4 IL containing TiO2 was mixed with model oil that contained DBT, DBT was
extracted from oil phase to the IL phase. When the TiO2 in the IL was irradiated by UV light,
the photogenerated holes reacted with water or hydroxyl groups on the surface of TiO2 to form

OH radicals, which oxidized DBT to DBTO2. Then, the DBT was transferred from oil to IL

and was degraded continuously.


Mohd Zaid et al72 studied the Photo-oxidativeextractive deep desulfurization of diesel
using CuFe/TiO2 and eutectic ionic liquid. First they synthesized series of bimetallic Cu
Fe/TiO2 photo-catalysts using solgel hydrothermal method and then photo-catalysts were
evaluated for photo-oxidative extractive deep desulfurization of model oil. The study
identified that 2.0 wt% CuFe/TiO2 photo-catalyst can efficiently oxidize sulphur species
under mild conditions in the presence of hydrogen peroxide (H2O2:S molar ratio of 4) as
oxidant and eutectic based ionic liquid as extractant.
3.4. Challenge and Perspective of ODS using ILs

23

Page 27 of 55

Green Chemistry

Aiming at the replacement or supplement of the present inefficient and expensive HDS, to
remove those heterocyclic S-compounds to produce clean ultra-low S or S-free fuel oils, ODS
using ILs have been intensively studied recently. The research results presented and discussed
above indicate a good perspective for such a new method, though some problems accompanied,
the advantages and possible limitations are listed in Tab. 7.
Temperature, reaction/extraction time, molar ratio of O/S, mass ratio of IL/oil, etc., have
been thoroughly investigated, showing exciting results. Those heterocyclic S-compounds in
fuel oils, which are unreactive to traditional HDS, can be expected to be removed completely
at mild conditions such as lower temperature (e.g., room temperature) and atmospheric
pressure after few minutes of contacting. Using ILs instead of traditional volatile organic
solvents in ODS excludes the loss and contamination of solvents and possible safety issue,
makes the regeneration and separation of solvents or ILs easier, and the regenerated ILs can be
recycled without any noticeable activity loss. It is worthy of noting that the properties of ILs
vary enormously as a function of their molecular structure, that is to say that the property of
ILs can be tailored through elaborately selecting the paring of cation and anion or modifying
the structure of cation or anion. Therefore, there is still a very enormous room left to optimize
the ILs in their specific application in ODS.
Compared with the ODS using ILs as solvent and extractive reagent where one acidic
catalyst is required generally, the ODS using some functional acidic ILs as both extractive
reagent and catalyst where no additional catalyst is required is a better option, because there
does not exist some problems such as difficult regeneration and recycling of catalyst in
homogeneous catalysis and possible contamination of oils by catalyst. Some other options such
as supported ILs as catalytic solvent, ILs emulsion and ILs photo-catalysis are also worthy of
being investigated.
24

Green Chemistry

Page 28 of 55

There are some issues to be considered such as treatment of waste sulphones as oxidation
product of S-compounds, cost of ILs and selectivity of ODS. In addition, most studies
performed currently are focused on the investigation of model fuel oils, and researchers are
encouraged to investigate the desulfurization of real feedstock such as gasoline and diesel fuels.
Compared with many studies on desulfurization experiments, the desulfurization mechanism
are rather scarce, and some computer simulations coupled with spectrum characterization
studies will favor uncovering the mechanism. In near future, to promote the final pilot test or
industrial application of such a new technology, some studies are desired, e.g., development of
cheaper and more active ILs; set-up of kilogram/ton-scale of desulfurization process;
optimization of operation conditions; investigations of loss, lifetime/stability, regeneration and
reusability of ILs; evaluations on oil yield and oil quality.
Concluding Remarks
S-compounds are the major harmful impurity in fuel oils, which result into the severe
environmental issues in the combustion of fuel oils. Desulfurization of fuel oils is a key
process in oil refining. Traditional HDS, due to its ineffectiveness to remove some heterocyclic
S-compounds in fuel oils, is facing some challenges in producing clean ultra-low S or S-free
fuel oils. Alternative methods are desired, among which ODS using ILs has been intensively
studied recently. In this work, we reviewed these research results of ODS using ILs since 2003
when Loet al reported the first results, also the traditional ODS. This review clearly indicates
that ODS using ILs can effectively remove those heterocyclic S-compounds in fuel oils and
reduce the S-content to < 10 ppm under mild conditions with a very good perspective for the
application in future, although some issues have to be also addressed in future such as

25

Page 29 of 55

Green Chemistry

treatment of waste sulphones, cost of ILs, selectivity of ODS and economic-technological


evaluations at large scale of process.
The development of functional ILs and the ODS using such functional ILs as both extractive
reagent and catalyst, also supported ILs as catalytic solvent, ILs emulsion and ILs
photocatalysis, are expected to be studied further in future.
Acknowledgements
This work was financially supported by National Natural Science Foundation of China
(21176021, 21276020). We extend our appreciation to the Deanship of Scientific Research at
King Saud University for funding the work, through Research Group Project No. RG-1436026.
References
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.

B. Cooper and K. Knudsen, in Practical Advances in Petroleum Processing, eds. C. Hsu and P. Robinson, Springer New York, 2006, DOI:
10.1007/978-0-387-25789-1_10, ch. 10, pp. 297-316.
W. Zhu, P. Wu, Y. Chao, H. Li, F. Zou, S. Xun, F. Zhu and Z. Zhao, Industrial & Engineering Chemistry Research, 2013, 52, 17399-17406.
J. M. Campos-Martin, M. C. Capel-Sanchez, P. Perez-Presas and J. L. G. Fierro, Journal of Chemical Technology & Biotechnology, 2010, 85,
879-890.
M. Shakirullah, W. Ahmad, I. Ahmad and M. Ishaq, Fuel Processing Technology, 2010, 91, 1736-1741.
R. Abro, A. A. Ahmed, S. S. Al-deyab, G. Yu, A. B. Qazi, S. Gao and X. Chen, RSC Advances, 2014, DOI: 10.1039/C4RA03478C.
X. Chen, H. Guo, A. A. Abdeltawab, Y. Guan, S. S. Al-Deyab, G. Yu and L. Yu, Energy & Fuels, 2015, DOI:
10.1021/acs.energyfuels.5b00172.
J. B. Green, S. K. T. Yu, C. D. Pearson and J. W. Reynolds, Energy & Fuels, 1993, 7, 119-126.
A. M. Dehkordi, Z. Kiaei and M. A. Sobati, Fuel Processing Technology, 2009, 90, 435-445.
D. Wang, E. W. Qian, H. Amano, K. Okata, A. Ishihara and T. Kabe, Applied Catalysis A: General, 2003, 253, 91-99.
X. Jiang, H. Li, W. Zhu, L. He, H. Shu and J. Lu, Fuel, 2009, 88, 431-436.
F. M. Collins, A. R. Lucy and C. Sharp, Journal of Molecular Catalysis A: Chemical, 1997, 117, 397-403.
J. Zhang, A. Wang, X. Li and X. Ma, Journal of Catalysis, 2011, 279, 269-275.
F. Zannikos, E. Lois and S. Stournas, Fuel Processing Technology, 1995, 42, 35-45.
M. Te, C. Fairbridge and Z. Ring, Applied Catalysis A: General, 2001, 219, 267-280.
M. Zhang, W. Zhu, S. Xun, H. Li, Q. Gu, Z. Zhao and Q. Wang, Chemical Engineering Journal, 2013, 220, 328-336.
J. L. Garca-Gutirrez, G. A. Fuentes, M. E. Hernndez-Tern, F. Murrieta, J. Navarrete and F. Jimnez-Cruz, Applied Catalysis A: General,
2006, 305, 15-20.
B. Yu, P. Xu, Q. Shi and C. Ma, Applied and environmental microbiology, 2006, 72, 54-58.
C. Song and X. Ma, Applied Catalysis B: Environmental, 2003, 41, 207-238.
N. L. Klyachko and A. M. Klibanov, Applied biochemistry and biotechnology, 1992, 37, 53-68.
T. X. a. M. L. H. Farhan M. Al-Shahrani, Oil and Gas Journal, 2010.
W. Zhu, G. Zhu, H. Li, Y. Chao, M. Zhang, D. Du, Q. Wang and Z. Zhao, Fuel Processing Technology, 2013, 106, 70-76.
W. Zhu, H. Li, Q. Gu, P. Wu, G. Zhu, Y. Yan and G. Chen, Journal of Molecular Catalysis A: Chemical, 2011, 336, 16-22.
Y. Dong, Y. Nie and Q. Zhou, Chemical Engineering & Technology, 2013, 36, 435-442.
V. Selvavathi, A. Meenakshisundaram, B. Sairam and B. Sivasankar, Petroleum Science and Technology, 2008, 26, 208-216.
L. A. Blanchard, D. Hancu, E. J. Beckman and J. F. Brennecke, Nature, 1999, 399, 28-29.
S. Zahn and B. Kirchner, in Chemical Modelling: Applications and Theory Volume 9, The Royal Society of Chemistry, 2012, vol. 9, pp. 1-24.
T. Welton, Chemical reviews, 1999, 99, 2071-2084.
W.-H. Lo, H.-Y. Yang and G.-T. Wei, Green Chemistry, 2003, 5, 639-642.
H. Xu, Z. Han, D. Zhang and C. Liu, Journal of Molecular Catalysis A: Chemical, 2015, 398, 297303.
D. Liu, J. Gui, D. Liu, X. Peng, S. Yang and Z. Sun, Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, 2012, 35, 1-8.
W. Liang, S. Zhang, H. Li and G. Zhang, Fuel Processing Technology, 2013, 109, 27-31.
L. Lu, S. Cheng, J. Gao, G. Gao and M.-y. He, Energy & fuels, 2007, 21, 383-384.
G. Yu, J. Zhao, D. Song, C. Asumana, X. Zhang and X. Chen, Industrial & Engineering Chemistry Research, 2011, 50, 11690-11697.
Y. Nie, Y. Dong, L. Bai, H. Dong and X. Zhang, Fuel, 2013, 103, 997-1002.

26

Green Chemistry

35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.
67.
68.
69.
70.
71.
72.
73.
74.

Page 30 of 55

M. S. Cooper, H. Heaney, A. J. Newbold and W. R. Sanderson, Synlett 1990, 9, 533-535.


C. Devi Wilfred, M. Z. M. Salleh and M. I. B. M. Mutalib, Separation Science and Technology, 2014, 50, 159-163.
D. Zhao, Y. Wang, E. Duan and J. Zhang, Fuel Processing Technology, 2010, 91, 1803-1806.
W. Jiang, W. Zhu, H. Li, Y. Chao, S. Xun, Y. Chang, H. Liu and Z. Zhao, Journal of Molecular Catalysis A: Chemical, 2014, 382, 8-14.
P. S. Kulkarni and C. A. M. Afonso, Green Chemistry, 2010, 12, 1139-1149.
D. Zhao, J. Wang and E. Zhou, Green Chemistry, 2007, 9, 1219-1222.
X. Chen, Y. Guan, A. A. Abdeltawab, S. S. Al-Deyab, X. Yuan, C. Wang and G. Yu, Fuel, 2015, 146, 6-12.
C. Thomazeau, H. Olivier-Bourbigou, L. Magna, S. Luts and B. Gilbert, Journal of the American Chemical Society, 2003, 125, 5264-5265.
D. Fang, Q. Wang, Y. Liu, L. Xia and S. Zang, Energy & Fuels, 2014, 28, 6677-6682.
D.-s. Zhao, Z.-m. Sun, F.-t. Li and H.-d. Shan, Journal of Fuel Chemistry and Technology, 2009, 37, 194-198.
Y. Jiang, W. Zhu, H. Li, S. Yin, H. Liu and Q. Xie, ChemSusChem, 2011, 4, 399-403.
J. Xiong, W. Zhu, H. Li, Y. Xu, W. Jiang, S. Xun, H. Liu and Z. Zhao, AIChE Journal, 2013, 59, 4696-4704.
X. Chen, D. Song, C. Asumana and G. Yu, Journal of Molecular Catalysis A: Chemical, 2012, 359, 8-13.
T. O. Sachdeva and K. K. Pant, Fuel Processing Technology, 2010, 91, 1133-1138.
W. Zhang, K. Xu, Q. Zhang, D. Liu, S. Wu, F. Verpoort and X.-M. Song, Industrial & Engineering Chemistry Research, 2010, 49, 1176011763.
L. Lu, S. Cheng, J. Gao, G. Gao and M.-y. He, Energy & Fuels, 2006, 21, 383-384.
Y. Mochizuki and K. Sugawara, Energy & Fuels, 2008, 22, 3303-3307.
C. Zhang, X. Pan, F. Wang and X. Liu, Fuel, 2012, 102, 580-584.
J. Wang, D. Zhao and K. Li, Energy & Fuels, 2009, 23, 3831-3834.
J. Zhang, W. Zhu, H. Li, W. Jiang, Y. Jiang, W. Huang and Y. Yan, Green Chemistry, 2009, 11, 1801-1807.
W. Jiang, W. Zhu, Y. Chang, H. Li, Y. Chao, J. Xiong, H. Liu and S. Yin, Energy & Fuels, 2014, 28, 2754-2760.
D. Liu, J. Gui, L. Song, X. Zhang and Z. Sun, Petroleum Science and Technology, 2008, 26, 973-982.
W. Zhang, K. Xu, Q. Zhang, D. Liu, S. Wu, F. Verpoort and X. M. Song, Industrial and Engineering Chemistry Research, 2010, 49, 1176011763.
C. Asumana, G. Yu, X. Li, J. Zhao, G. Liu and X. Chen, Green Chemistry, 2010, 12, 2030-2037.
N. E. A. Cousens, L. J. Taylor Kearney, M. T. Clough, K. R. J. Lovelock, R. G. Palgrave and S. Perkin, Dalton Transactions, 2014, 43,
10910-10919.
F.-t. Li, B. Wu, R.-h. Liu, X.-j. Wang, L.-j. Chen and D.-s. Zhao, Chemical Engineering Journal, 2015, 274, 192-199.
C. Yansheng, L. Changping, J. Qingzhu, L. Qingshan, Y. Peifang, L. Xiumei and U. Welz-Biermann, Green Chemistry, 2011, 13, 1224-1229.
S. Xun, W. Zhu, D. Zheng, L. Zhang, H. Liu, S. Yin, M. Zhang and H. Li, Fuel, 2014, 136, 358-365.
J. Xiong, W. Zhu, W. Ding, L. Yang, Y. Chao, H. Li, F. Zhu and H. Li, Industrial & Engineering Chemistry Research, 2014, DOI:
10.1021/ie503322a.
J. Ge, Y. Zhou, Y. Yang and M. Xue, Industrial & Engineering Chemistry Research, 2011, 50, 13686-13692.
E. Ito and J. A. R. van Veen, Catalysis Today, 2006, 116, 446-460.
Y. Shiraishi, K. Tachibana, T. Hirai and I. Komasawa, Industrial & engineering chemistry research, 2002, 41, 4362-4375.
F. Lin, D. Wang, Z. Jiang, Y. Ma, J. Li, R. Li and C. Li, Energy & Environmental Science, 2012, 5, 6400-6406.
D. Zhao, R. Liu, J. Wang and B. Liu, Energy & Fuels, 2008, 22, 1100-1103.
R. Vargas and O. Nez, Journal of Molecular Catalysis A: Chemical, 2008, 294, 74-81.
Y. Shiraishi, T. Hirai and I. Komasawa, Journal of chemical engineering of Japan, 2002, 35, 489-492.
X.-j. Wang, F.-t. Li, J.-x. Liu, C.-g. Kou, Y. Zhao, Y.-j. Hao and D. Zhao, Energy & Fuels, 2012, 26, 6777-6782.
H. F. Mohd Zaid, F. K. Chong and M. I. Abdul Mutalib, Fuel, 2015, 156, 54-62.
OPEC, 2014 World Oil Outlook, Organization of the Petroleum Exporting Countries (OPEC), Vienna, Austria, 2014.
J.-M. Bregeault, Dalton Transactions, 2003, DOI: 10.1039/B303073N, 3289-3302.

27

Page 31 of 55

Fig.1.

Green Chemistry

Maximum diesel sulfur limits, January 201473.

28

Green Chemistry

Fig.2.

Page 32 of 55

Maximum gasoline sulfur limits, January 201473.

29

Page 33 of 55

Fig.3.

Green Chemistry

S-compounds in fuel oils.

30

Green Chemistry

Fig.4.

Page 34 of 55

Flow chart of biphasic simultaneous oxidation/extraction ODS unit.

31

Page 35 of 55

Green Chemistry

Fig.5. ODS reaction, biphasic system31.

32

Green Chemistry

Page 36 of 55

Non-polar phase

Polar Phase

Fig.6. Homogeneous biphasic ODS system without PTA.20

33

Page 37 of 55

Green Chemistry

Fig.7. Mechanism proposed for oxidation of S-compound to sulfone over the active species21.

34

Green Chemistry

k1
H2O2 + Mo=O
O
Mo

O
O

Mo

Fig.8.

O
Mo

k2
+ R2S

+ H2O

Mo=O

+ R2S

Mo=O +

R2SO

k3
+ R2SO

Page 38 of 55

Sequence involved in the oxidation reaction21.

35

Page 39 of 55

Fig.9.

Green Chemistry

Time-course variation of DBT removal and ln(C0/Ct)21.

36

Green Chemistry

Page 40 of 55

Fig.10. Kinetics for oxidative desulfurization of DBT and BT by [C63MPy]Cl/ FeCl3. Conditions: moil=9g, mIL=
3 g, O/S molar ratio = 4, T = 298 K23.

37

Page 41 of 55

Green Chemistry

CH3
3HC
N+

CH3

3HC

N+

CH3

CH3

3HC

CH3

CH3

Imidazolium

Pyridiniuim

CH3
S+
3HC

3HC

P+ CH3
CH3

Fig.11.

CH3

CH3

CH3

Sulfonium

Pyrrolidinium

Phosphonium

3HC

N+ CH3
CH3

Ammonium

Different structures for IL cations.

38

Sulfur removal efficiency (%)

Green Chemistry

100
90
80
70
60
50
40
30
20
10
0

Page 42 of 55

4,6DMDBT
BT
DT
DBT

20

40

60

80

100

120

Time (min)
Fig.12. The effect of different S-compounds on S-removal efficiency. Experimental conditions: 5-mL model oil,
n(H2O2) 0.39mmol, m([pmim]FeCl4-MCM-41)50.06 g, V([Omim]BF4)51 mL, T=30oCat 30oC, time =1 h46.

39

Sulfur rem oval efficiency (% )

Page 43 of 55

Green Chemistry

100
90
80

DBT
BT

70
60
50
40
0

10 12 14 16 18 20 22

Time (min)
Fig.13. Effect of different S-compounds on S-removal by [C63MPy]Cl/FeCl3. Conditions: initial S-content 1000
ppm, moil=9g,mIL= 3 g, O/S molar ratio = 4, T = 298 K 23.

40

Green Chemistry

Page 44 of 55

S-removal efficiency (%)

100
80
60
40
20
0
2:1

4:1

6:1

7:1

8:1

8.5: 1

9:1

Molar ratio of O/S


Fig.14. Influence of the molar ratio of O/S on S-removal efficiency by [C4mim]Cl/3ZnCl2-H2O2(temperature,45C; time,
3h; initial S-content, 505ppm; mass ratio of IL/oil, 1/2)47.

41

Page 45 of 55

Green Chemistry

Fig.15. Influence of the mass ratio of IL/oil on S-removal efficiency by [C4mim]Cl/3ZnCl2-H2O2 (temperature, 45
C; time, 3 h; initial S-content, 505 ppm; molar ratio of O/S, 8)47.

42

Green Chemistry

Page 46 of 55

Fig.16. The synthesis process of [C4mim]FeCl4/silica gel catalyst62.

43

Page 47 of 55

Green Chemistry

Fig.17. Catalytic Oxidation of DBT in IL Emulsion System64.

44

Green Chemistry

Page 48 of 55

Fig.18. In Situ Photo-catalytic Oxidative Desulfurization Process of DBT71.

45

Page 49 of 55

Green Chemistry

Table.1. Different adsorbents used in ADS at optimized conditions5.


Adsorbents

Activated carbon

Model

S-

Initial S: (ppm)

Temp. (K)

Pressure

S-removal

oil

comp.

gas oil

DBT

178

198

95%

(atm)

gas oil

TS

300

243

1.5

88%

Alumina

gas oil

DBT

700

393

n/a

30%

Zeolites from coal

hexane

TS, BT

500

303

63%

NiMoP/Al2O3

hexane

DBT

450

600

40

56%

Gallium +Y -zeolite

nonane

DBT

500

333

n/a

97%

Cu-zirconia

octane

TS

2000

180

n/a

99%

Ruthenium complexes

hexane

DBT

40

298

55%

46

Green Chemistry

Page 50 of 55

Table.2. Bio-desulfurization by different microorganisms5.


Microorganism

Model oil

Initial S: (ppm)

Temp (K)

S-removal

Gordoniaalkanivorans RIPI90A

hexadecane

320

303

90%

Mycobacterium sp. ZD-19

hexadecane

92

303

100%

Mycobacterium goodii X7B

tertradecane

200

313

99%

Rhodococcuserythropolis IGTS8

hexadecane

100

303

80%

Gordoniaalkanivorans strain 1B

heptane

100

308

63%

Bacillus subtilis WU-S2B

tridecane

100

323

50%

Pseudomonas stutzeri UP-1

hexadecane

500

304

74%

Sphingomonassubarctica T7b

gas oil

280

300

94%

Bacterium, strain RIPI-22

hexadecane

100

303

77%

Pseudomonas delafieldii R-8

diesel oil

591

303

47%

47

Page 51 of 55

Green Chemistry

Table.3. List of some common oxidants and their active oxygen content 74.
Oxidant

Active oxygen (wt %)

By-product

H2 O 2

47.1

H2 O

t-BuOOH

17.8

t-BuOH

HNO3

25.0

NOx, N2O, N2

N2 O

36.4

N2

NaClO

21.6

NaCl

NaClO2

35.6

NaCl

NaBrO

13.4

NaBr

13.7

C5H11NO

10.5

KHSO4

NaIO4

29.9c

NaI

PhIO

7.3

PhI

H2 O 2

47.1

H2 O

C5H11NO2a
KHSO5

a N-Methylmorpholine N-oxide (NMO).


b Stabilized and commercialized as the triple salt: 2KHSO5KHSO4K2SO4.
c Assuming all 4 oxygen atoms are used.

48

Green Chemistry

Page 52 of 55

Table.4. S-removal efficiency vs mass ratio of IL/oil for [C4mim]Cl/ 2ZnCl2 and [SO3H_C4mim] HSO447.
ILs

Oil

O/S

Time

Temp.

ODS efficiency for IL-oil mass ratio

Ratio

(h)

(K)

1:5

1:3

1:2

1:1

2:1

[C4mim]Cl/ 2ZnCl2

Model

8:1

363

92.2

97

98.5

100

n/a

[SO3H_C4mim]HSO4

diesel

8:1

333

93.9

95

96

98.1

n/a

49

Page 53 of 55

Green Chemistry

Table.5. Recycling of [C63MPy]Cl/FeCl3 in desulfurization of model oil23.


Cycle

Cycle S-removal [%](by ILs

S-removal [%](by ILs without

with distillation)

distillation)

100

100.0

100

99.8

100

97.4

97.8

92.9

94.5

85.4

Conditions: initial sulfur (as DBT) content 1000 ppm, moil = 9 g,


mIL= 3 g, O/S molar ratio = 4, t = 20 min, T = 298 K.

50

Green Chemistry

Page 54 of 55

Table.6. Variation of types of ILs in the desulfurization system45.


Entry

ILs

S-removal [%]
Without H2O2[a]

With H2O2[b]

[(C8H17)3CH3N]Cl/FeCl3

30.6

97.9

[(C8H17)3CH3N]Cl/CuCl2

18.6

26.2

[(C8H17)3CH3N]Cl/SnCl2

22.1

25.8

[(C8H17)3CH3N]Cl/ZnCl2

20.5

19.8

[(C4H9)3CH3N]Cl/FeCl3

15.3

95.8

[C10H21(CH3)3N]Cl/FeCl3

17.2

93.4

[(C10H21)2(CH3)2N]Cl/FeCl3

29.0

98.7

[a] Experimental conditions: model oil (5 mL), IL (0.702 mmol), T=25C, t=1 h.
[b] Experimental conditions: model oil (5 mL), IL (0.702 mmol), T=25C, t=1 h, n(H2O2)/n(S)=14:1.

51

Page 55 of 55

Green Chemistry

Table.7. Advantages and limitations of ODS using ILs.


Advantages

Limitations

mild conditions such as room temperature and atmospheric

waste treatment of S-compound oxidized product of

pressure withconventional reaction and separation refinery

sulfones

equipment

cost of ILs

no consumption of expensive hydrogen or noble catalyst (in

possible side reaction in ODS

some cases, functional ILs can act as solvent and catalyst)

quantity and yield of fuel oil

high efficiency to remove heterocyclic S-compounds


immune to HDS
easy regeneration, recycling, separation of solvent or ILs
excluding of solvent loss and contamination
enormous room left to design and prepare functional ILs
with better desulfurization performances
other advantages such as low-cost and high selectivity

52