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org/est Critical Review

Metal-Based Ionic Liquids in Oxidative Desulfurization: A Critical

Review
Fen Liu, Jiang Yu,* Abdul Basit Qazi, Li Zhang, and Xueke Liu
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ABSTRACT: Ionic liquids (ILs) as novel functional desulfuriza-

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tion materials have attracted increasing attentions. Metal-based

ionic liquids (MILs) are classified into three types of metal chloride
ILs, metal oxide ILs, and metal complex ILs based on the definition
and basic structure of MILs in this critical review. On the basis of
the properties of ILs such as structure designability, super
dissolution performance, good thermal and chemical stability,
nonflammability, and wide electrochemical window, MILs exhibit
unique advantages on hydrophobicity, oxidation performance, and
Brö nsted−Lewis acidity. Therefore, MILs possess both the
absorption and oxidation centers for the intramolecular adsorption
and oxidation to improve the oxidative desulfurization (ODS) process. During the novel nonaqueous wet oxidative desulfurization
process (Nasil), H2S can be oxidized into elemental sulfur with hydrophobic MILs, which can be regenerated by oxygen for recycle,
to solve the problems of low sulfur capacity, low sulfur quality, and severe secondary pollution in the aqueous Lo-Cat wet oxidative
desulfurization process. Another outstanding feature of MILs in ODS is biomimetic catalysis, which has the function of activating
molecular oxygen and improving the oxidation performance. Metal oxide ILs and metal complex ILs are used in combination with
hydrogen peroxide or oxygen with the existing water to generate a Fenton-like reaction to convert hydrophobic organic sulfur or SO2
into hydrophilic sulfoxide/sulfone or sulfur acid, respectively. However, the corrosion of Cl− to the equipment and emulsification
phenomenon in the extraction process of sulfoxide/sulfone separation still need further study. Furthermore, the promising strategies
to construct highly efficient and green desulfurization processes for large-scale applications are provided.

1. INTRODUCTION (e.g., Co/Mo, Ni/Mo).7,8 Moreover, aromatic thiophenes such

Sulfur compounds such as organic sulfide, hydrogen sulfide
(H2S), and sulfur dioxide (SO2) are primarily produced from
natural gas, flue gas, and fuel oil, finally emitted as the form SOx
species.1−3 It is one of the essential origins of acid rain causing
severe damages to the ecological environment and human
health. To date, SOx is still an important pollutant under
common control in most countries. To control the environ-
mental pollution caused by SOx species, almost all countries
have made a great effort to limit the sulfur content in fuel oil.4
For example, in 2016, China explicitly stipulated that the
Chinese national V standard of the sulfur content in oils is below
10 ppm.5 So it is important and necessary to remove sulfur
compounds from either the environmental treatment or the
production process.
The removal approaches of sulfur compounds include
adsorption, absorption, biological methods, and catalysis.6
Catalysis has attracted much attention owing to its mild reaction
conditions and high selectivity, which has been widely used for
desulfurization. Hydrodesulfurization (HDS) is the most
commonly used technology for the desulfurization of organic
sulfide, which must be carried out under severe conditions of
high temperature (300−400 °C) and pressure with H 2
consumption (20−100 atm H2) as well as expensive catalysts
as dibenzothiophene (DBT), benzothiophene (BT), and 4,6-
dimethyldibenzothiophene (4,6-DMDBT) are difficult to be
removed because of the steric hindrance.9 Claus technology is
one of the most widely used technologies for the desulfurization
of H2S.10,11 Because of the thermodynamic limitations, total
sulfur content in the tail gas is about 10,000 ppm which is always
further processed with Superclaus technology.12 A Lo-Cat wet
oxidation process composed of iron-complex compounds such
as the EDTA-Fe (EDTA = ethylenediaminetetraacetate)
aqueous solution as a desulfurizer is another most commonly
used commercial technology for the desulfurization of H2S.13
However, several shortcomings such as pH control, decom-
position of desulfurizer, and secondary pollution limited its
further applications. Regarding the desulfurization of SO2, flue-
gas desulfurization (FGD) processes are the most adopted
Received: August 31, 2020
Revised: December 2, 2020
Accepted: December 30, 2020
Published: January 12, 2021

© 2021 American Chemical Society https://dx.doi.org/10.1021/acs.est.0c05855

1419 Environ. Sci. Technol. 2021, 55, 1419−1435
Environmental Science & Technology
Figure 1. Idea flow of this critical review.
commercial technologies.14,15 Double alkali desulfurization is
one of the widely used FGD processes for SO2 capture, and
afterward, the desulfurizer, for example, NaOH/Na2CO3
aqueous solution, is regenerated by a sodium-alkali reaction.
Although, the poor purity of the side product caused by the high
solubility of sodium sulfite and the generation of solid waste
remains a problem. Alternatively, limestone oxidation with the
redox reaction of SO2 with CaO covers the larger part of the
commercially used FGD process to produce sulfuric acid.
However, catalyst activity and produced acid concentration
need to be promoted.
The catalytic oxidation process not only removes sulfur
compounds but also converts sulfur compounds into valuable
products, and conveniently, products are separated. For
example, organic sulfides can be oxidized to their corresponding
sulfoxides or sulfones that present slightly higher polar
properties than hydrocarbon molecules, which is beneficial to
the sulfur removal from fuel oil.16 H2S and SO2 can be converted
into sulfur and SO3, respectively, which are conducive to
conservation, transportation, and preparing chemical prod-
ucts.13,15 To realize high efficient and selective catalysis, catalyst
and reaction conditions are the key factors.
Ionic liquids (ILs) are mostly room temperature molten salts
composed of organic cations and (in)organic anions.17 ILs
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exhibit several advantages in potential applications, such as
preventing the loss of organic solvents due to low vapor pressure,
nonvolatility, recyclability, no secondary pollution, high
stability, selectivity, and volatile structure design of ILs for
different systems. The specific functional ILs could be designed
and prepared through the appropriate selection and modifica-
tion of the cations and anions. With their good design properties,
high solubility, low vapor pressure, and good thermal stability,
ILs have been widely investigated and applied prominently as
functional liquids.18−20 Electrochemical deposition once was the
main application of ILs as solvents due to its wide electro-
chemical window, which was first prepared from the mixture of
ethylpyridinium bromide and aluminum chloride.21 Ionic
liquids can directly absorb H2S and SO2 as solvents and can
also enhance the absorption of SO2 after modification, such as
guanidine-based ILs.22 Lei et al.19 reported that sulfur
compounds could be absorbed by the interaction with N and
H atoms of cationic groups of ILs to form hydrogen bonds,
greatly influenced by the alkyl chain length, functional groups,
and types of cations of ILs. Additionally, the anions of ILs also
play an important role in determining the solubility of sulfur
compounds in ILs, especially through the hydrogen bonds
between sulfur compounds and halide ions.
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Metal-based ionic liquids (MILs) are a subclass of ILs. They
not only have the general characteristics of ILs but also show the
characteristics of magnetism and catalytic oxidation that
originate from the metal incorporated in the complex ion.23
Therefore, there are absorption reaction centers and catalytic
oxidation reaction centers in MILs molecules, which can greatly
enhance the absorption capacity of ionic liquids with a strong
interaction between absorbed the substance and MILs.24,25 At
first, MIL (MeEtImCl/AlCl3) was used in the field of catalysis
for Friedel−Crafts reactions as a solvent and catalyst.26 The
results showed that MeEtImCl/AlCl3 can promote the reaction
rate through the Lewis acidic species Al2Cl7−. From then on, the
window was opened for the use of MILs in various catalytic
reactions. During the past decades, MILs have been widely used
for desulfurization based on catalytic performance, hydro-
phobicity, high solubility, high thermal and chemical stability,
and reusability, as well as the designability of MILs. In 2001,
MILs were first used for desulfurization as an extractant based on
the Lewis−base interactions between IL/AlCl3 and organic
sulfide.27 However, MILs composed of AlCl3 are air and
moisture sensitive, which limits their application in desulfuriza-
tion. Since then, more and more attention has been focused on
this application of ILs in oxidative desulfurization (ODS). A
series of functionalized ILs containing, for example, Zn, Cu, Fe,
Sn, Mo, V, or W metal ions that are stable exposed to air and
moisture are synthesized to construct highly efficient desulfur-
ization systems.28−30 According to different structures and
properties of the designed functionalized MILs, MILs can be
divided into three categories: metal chloride ILs, metal oxide
ILs, and metal complex ILs.31 Using MILs for desulfurization as
extractants and/or catalysts exhibits several advantages, such as
high activity in a wide temperature range, recyclability, and no
secondary pollution.
Some review papers have been published on the subject of
“desulfurization in ionic liquids” over the past decade.3,8,10,32,33
However, so far, no review papers have concentrated on the
developments of ODS of organic sulfide, H2S, or SO2 by MILs,
even though MILs have had an increasingly significant role in
desulfurization in recent years. Moreover, the regeneration of
MILs during desulfurization has not been reviewed, although it
is important for the recycling of desulfurizer and economic
reasons. Additionally, the design of novel MILs and their
applications have become a highly active and interesting area of
research; for example, MILs have been popular materials in
applications such as separation, electrolytes for batteries,
analytical chemistry, (in)organic synthesis, CO2 conversion,
and desulfurization.25,34−37
ODS in MILs and their industrial applications over the past
decade are systematically discussed in this critical review. The
idea flow of this critical review is shown in Figure 1. Specifically,
we first briefly summarize the shortcomings of the main
commercially used technologies and the purpose of this critical
review in Section 1. The structure and typical physicochemical
properties of metal chloride ILs, metal oxide ILs, and metal
complex ILs are illustrated in Section 2, as well as the discussion
and speculation on the applications of MILs for ODS of organic
sulfide in Section 3, ODS of H2S and the pilot test of the
nonaqueous wet oxidative desulfurization process in Section 4,
and ODS of SO2 in Section 5. Furthermore, the green processes
of ODS in MILs are analyzed in detail from the aspects of MILs
recycling and product separation in Section 6.1. The toxicity of
ILs and the exhibited problems of the current desulfurization
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process with MILs are discussed in Section 6.2, along with future
research challenges and perspectives of ODS in MILs.
2. IDENTIFICATION AND PHYSICOCHEMICAL
PROPERTIES OF MILS
Metal chloride ILs can be produced by the reaction of room
temperature ILs and metal chloride salt, in which metal ions are
mainly presented as the form of MClxn− possessing strong Lewis
acidity.38,39 By adjusting the molar ratio of the metal chloride in
the system, basic (x < 0.5), neutral (x = 0.5), or acidic (x > 0.5)
MILs can be obtained, respectively.40 Additionally, hydro-
phobicity and magnetism are typical physicochemical properties
of metal chloride ILs, such as [C4mim][FeCl4], which facilitates
their reusability (Table 1). However, Lee et al.41 stated that
[Bmim]FeCl4 was partially soluble in water at room temper-
ature, due to the hydrogen bonding interactions between FeCl4−
and water molecules and the hydrophilic imidazolium ring.
Moreover, the solvent effect will greatly decrease the stability of
Fe−Cl bonds in FeCl4− anions,42 which may lead to the
decomposition of FeCl4− anions, owing to the relatively weak
interaction of Fe−Cl bonds (2.225 Å) compared to Fe−N
bonds (2.065 Å).43 By regulating the ligand species, the novel
metal complex ILs containing more stable iron complex ions
such as biomimetic [(Porp)Fe(III)]+ that can activate oxygen
and basic [Fe(EDTA)]− have been prepared.44−46 Unlike metal
chloride ILs and POM-ILs, the metal complex ions can be
incorporated in cations and/or anions in the metal complex ILs
with different ligands, which results in various types of metal
complex ILs with particular properties (Tables S1−S3).
Nevertheless, to design liquid metal complex ILs with low
viscosity has been a challenge and an interesting subject.47
Generally, the metal oxide ILs possess a high redox performance
attributed to the strong redox properties of the rare metal ions
such as molybdenum (Mo), tungsten (W), and vanadium (V) of
polyoxometalate (POM) anions.48 Due to the hydrophilic
performance of POM anions, self-assembly is also an out-
standing property of POM-ILs to form emulsion systems.49,50
However, the relatively high cost of rare metal ions and the
complicated preparation processes limit their industrial
applications.
To characterize the structures of ionic forms and
chemicophysical properties, several characterization methods
have been applied, such as probe-infrared spectra (probe-IR),
Raman spectra, nuclear magnetic resonance (NMR), UV−vis
spectra, electrospray ionization tandem mass spectrometry
(ESI-MS), X-ray photoelectron spectroscopy (XPS), X-ray
diffraction (XRD), thermogravimetry-differential scanning
calorimetry (TG-DSC), and cycle voltammetry (CV). However,
it is difficult to characterize three-dimensional structures and the
coordination of cations and anions of MILs. For example, Wang
et al.51 described that the phase separation varied with the
content of FeCl3·6H2O during the preparation of [C4mim]-
[FeCl4] with [C4mim]Cl and FeCl3·6H2O, but the exact molar
ratio of [C4mim]Cl and FeCl3 in the ionic liquid phase is still
unclear. Although several researches have presented that MILs
show paramagnetic behavior under the application of an external
magnetic field (Table S1), the relationship between the fluid
structure and paramagnetic performance of MILs remains
unknown.
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Table 1. General Formula, Typical Examples, Ionic Formation, Physicochemical Properties and Characterization Methods of Metal Chloride ILs, Metal Oxide ILs, and Metal 3. OXIDATIVE DESULFURIZATION OF ORGANIC

52,
53

57
ref
38,

44,
54
55
50
56

46
SULFIDE IN MILS

FTIR, XRD, XPS, NMR, ESI-MS, SEM, TEM, CV, TG-

To overcome the shortcomings of conventional HDS
Probe-IR, in situ IR titration, Raman, UV−vis, NMR,
ESI-MS, XPS, CV, TG-DSC, Karl Fisher titration,
technology such as severe conditions of high temperature and

FTIR, UV−vis, CV, Karl Fischer, potentiometry

pressure with H2 consumption, expensive catalysts, and poor
removal efficiency of aromatic thiophenes, sulfur compounds
extraction by chemical interactions between acidic ILs and basic
Characterization

sulfur compounds has been proposed.27,53 The ODS technology

exhibited some promising results for highly efficient removal of
DFT, ab-initial calculation

organic sulfide due to the broken equilibrium of extractive

desulfurization. Owing to the properties such as low volatility,
nonflammability, high polarity, good thermal stability, low
toxicity, variability in the types of structure, and immiscibility to
oil as well as the excellent catalytic activity, MILs have attracted
titration

much attention.58 The ODS process with MILs generally

DSC

includes extraction, oxidation, and regeneration stages (Figure

2), and the extraction and oxidation mechanisms are presented
high thermal stability, ionic conductivity,
Lewis acidity, hydrophobicity, magnetism,

thermal stability, self-assembly property

in Figure 3.
conductivity, magnetism, water soluble
O2 activation, redox performance, ionic
Lewis acidity, redox performance, high

3.1. ODS of Organic Sulfide in Metal Chloride ILs. Metal

Physicochemical properties

chloride compounds possess significant Lewis acidity. Bösmann

et al.27 developed a new approach using [Bmim]Cl/AlCl3 as the
extractant for desulfurization of DBT from fuel, indicating that
the Lewis acid−solute base interactions enhanced the extraction
redox performance

performance of the ILs. However, the sensitivity of AlCl3-based

ILs to moisture and the side reaction of polymerization caused
by strong Lewis acidity of Al2Cl7− limited their large-scale
applications.62 Huang et al.62 developed the novel absorbent
with [Bmim]Cl/CuCl that was stable to air and moisture for
ODS of organic sulfide from gasoline due to the strong π-
[C4mim]+, [PMo10V2O40]5−

complexation interaction with thiophene. To resolve the

[C16mim]+, [PW12O40]3−

inherent low fluidity of Lewis acidic ILs containing AlCl4− and

[Emim]+, [Fe(EDTA)]−
[(Porp)Fe(III)]+, Cl−
[C4mim]+, [Et3NH]+,
[P66614]+, [FeCl4]−,

CuCl2− anions, Ko et al.63 prepared Fe-containing ILs for deep

Ionic form

desulfurization of organic sulfide from fuel oil. However, MILs

containing FeCl4− anions were prepared at N2 atmosphere as
[Fe2Cl7]−

AlCl3-based ILs, and until the year of 2004, Hayashi and

Hamaguchi52 synthesized [Bmim][FeCl4] with [Bmim]Cl and
Detailed information can be found in the Supporting Information (Tables S1−S3).

FeCl3·6H2O in air and found the formation of [Bmim][FeCl4]

and water mixture biphasic system. From then on, hydrophobic
[C4mim][PMo10V2O40]
[C16mim][PMo12O40]
Typical examples

[Emim][Fe(EDTA)]

and magnetic [Bmim][FeCl4] has attracted much attention in

[Et3NH][FeCl4]
[P66614][FeCl4]

aromatic sulfur removal. Nevertheless, the extractive desulfur-

[C4mim][FeCl4]

(Porp)Fe(III)Cl

ization efficiency was limited due to the extraction equilibrium of

aromatic sulfur compounds in metal chloride ILs.64
Therefore, introducing oxidant into the above desulfurization
system to convert hydrophobic organic sulfides into the
hydrophilic sulfones or sulfoxides is a promising strategy to
Cnpip, NR4, PR4; M = Al, Fe, Cu, Zn, Mn,

[Cation][PM12‑xVxO40] Cation = Cnmim,

improve sulfur compounds removal. Li et al.65 introduced H2O2

NR4, PR4, CnPy, Cnpip; Anion = Tf2N,
[Cation][Anion] Cation = MLx, Cnmim,
[Cation][MClx] Cation = Cnmim, CnPy,

NR4, PR4, CnPy, Cnpip; M = Mo, W;

into [Bmim]Cl/FeCl3 to form Fenton-like systems for ODS of

organic sulfide with 99.2% removal efficiency of DBT within 30
General formula

min. Organic sulfide such as DBT was first extracted into an ILs
BF4, PF6, Cl, Br, F, MLx

phase and then oxidized into dibenzothiophene sulfonea

(DBTO2) by •OH radicals produced from the reaction of
Fe3+ and H2O2 (Figure 2a). For the recycling of the catalyst,
x = 0, 1, 2, 3, 6

tetrachloromethane (CCl4) was used for the re-extraction of

DBTO2.58 To remove H2O and residue H2O2, vacuum drying is
necessary for the ILs recycling and regeneration process, which
Co

undoubtedly increases the operation complexity.66−68 In

addition, water wash can be also used for the regeneration of
Metal complex ILs
Metal chloride ILs
Complex ILsa

metal chloride ILs.69 The development of ODS of organic

Classification

Metal oxide ILs

sulfide with metal chloride ILs over the past decade is listed in
Table S4.
In the ODS process with metal chloride ILs, the metal
chloride ILs always act as both extractant and catalyst.
a

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Figure 2. Oxidative desulfurization (ODS) of dibenzothiophene (DBT) in different systems with MILs as catalyst, including extraction, oxidation, and
regeneration processes: (a) ODS in MILs−ILs systems with H2O2/O2 as the oxidant, including metal chloride ILs, POM-ILs, and metal complex ILs.
(b) ODS in emulsion systems, solid POM-ILs, and supported MILs with H2O2/NaClO as oxidant. (c) ODS in supported POM-ILs without solvent
and with O2 as oxidant.

Therefore, sulfur compounds are readily extracted through the
π−π interaction, hydrogen bonds between chlorometalate
anions and aromatic sulfur compounds, and π-complexation of
metal ions with S atoms (Figure 3a).70,71 Particularly, Li et al.60
claimed that the extraction mechanism with [Bmim]FeCl4 was
via charge transfer from aromatic sulfur compounds to Lewis
acidic FeCl4− anions. The generation processes of •OH and
•O2− radicals are as the following equations68
Fe3 + + H 2O2 → [FeOOH]2 + + H+
[FeOOH]2 + → Fe2 + + HO2 •
Fe 2 + + H 2O2 + H+ → Fe3 + + •OH + H 2O
•OH + H 2O2 → H 2O + HO2 •
HO2 • ↔ •O2− + H+
Fe3 + + •O2− → Fe 2 + + O2
− −
•O2 + HO2 •+H 2O → O2 + H 2O2 + OH
OH− + H+ → H 2O
Because of the high cost of imidazolium-based ILs, in recent
years, the novel metal chloride ILs were synthesized with
inexpensive materials, such as ammonium-based ILs (e.g.,
(C4H9)4NCl/FeCl3)72 and coordination ILs (e.g., [Hnoc]Cl/
ZnCl2, [HDBN]Cl/ZnCl2, and [Hnmp]Cl/FeCl3).66,68,73
However, H2O2 activity for oxidation of sulfur compounds
needs to be improved to decrease the dosage of H2O2. In
addition, the relatively lower thermal stability and weaker
interaction with sulfur compounds than the imidazolium-based
ILs are non-negligible.66,68 With the increase of water content in
the system, the dissolution of metal chloride ILs in water is also
significant, which will cause the loss of ILs.41 Moreover, the
(1)
dissolution of ILs in fuels and ILs loss during each recycling step
(2)
and regeneration process are problems in ODS of organic sulfide
with metal chloride ILs. Meanwhile, the dissolution of ILs can
(3) cause the contamination of fuels, resulting in the deterioration in
standards of fuels such as the octane value of gasoline and cetane
(4) index of diesel fuel. Therefore, preventing the loss of metal
chloride ILs has been an interesting and important topic.
(5) Wang et al.74 designed novel metal chloride ILs containing
binuclear cations to enhance the magnetic performance,
(6) facilitating the magnetic separation of ILs from fuels. Results
showed that [C4(mim)2]Cl2/2FeCl3 could be easily separated
(7) from the oil phase by an external magnetic field, which greatly
reduced the catalyst loss during the separation of MILs from oil.
(8)
However, the HPLC analysis of the model oil phase showed that
there was still a small amount of MILs dissolved in model oil.
3.2. ODS of Organic Sulfide in Metal Oxide ILs.
Heteropolyoxometalates (HPOMs) have been used as catalysts
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Figure 3. Extraction and oxidation mechanisms during ODS of organic sulfide: (a) Extraction mechanism containing π−π interaction, H−Cl hydrogen
bonds, and M-S bonds.59,60 (b) Fenton-like reaction mechanism in metal chloride ILs.58 (c) Oxidation mechanism in POM-ILs.61 (d) Oxidation
mechanism in POM-ILs with radicals as the oxidant.50
in aqueous solution for ODS of organic sulfide. Akbari et al.75
reported that although HPOMs possessed high catalytic activity
for ODS, the high solubility of HPOMs in polar solvents was one
challenge to be resolved which would lead to the severe loss of
HPOMs. In 2004, Bourlinos et al.76 first synthesized POM-ILs
with H3PW12O40 and surfactant, obtaining hydrophobicity and
high conductivity. Afterward, Huang et al.77 first applied POM-
ILs ([PSPy]3PW12O40·2H2O) to ODS of organic sulfide,
achieving 98.4% ODS efficiency for 4,6-DMDBT which was
difficult to remove owing to the steric hindrance. However, due
to the limits of phase transfer and catalyst activity, the kinetics of
the ODS process with POM-ILs was relatively low.
Molybdenum-based, tungsten-based, phosphomolybdenum-
based, and phosphotungsten-based POM-ILs have been widely
prepared as catalysts with H2O2, O2, or NaClO as oxidants for
ODS of organic sulfide (Table S5). In general, aromatic sulfur
compounds are first extracted into the IL phase/interface from
oil by the strong π−π interaction of sulfur compounds with the
imidazolium ring of ILs, and then, the extracted sulfur
compounds are oxidized by active peroxo species from POM-
ILs (Figure 2a−c).78,79 Taking molybdenum-based POM-ILs as
an example, MoO bonds (I) are first transmitted into active
peroxo species (II) with H2O2, and then, the active peroxo
species (II) transfer its oxygen atom to aromatic sulfur
compounds and is regenerated to MoO simultaneously.
The formed R2SO is continually oxidized to R2SO2 by active
peroxo species (II) and active peroxo species (II) is regenerated
to MoO simultaneously (Figure 3c).61
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Organic solvents, such as acetonitrile,80 toluene,81 and
CH3OH,82 have been used as extractants for ODS of organic
sulfide to dissolve POM-ILs and H2O2 and promote extraction
efficiency. However, these conventional organic solvents are
volatile and flammable which can cause damage to the
environment and human health, as well as the solubility in oil
causing cross contaminantion of the oil.
Hydrophobic conventional ILs, such as [Bmim]BF4, [Bmim]-
PF6, [Omim]BF4, and [Omim]PF6, have been widely used as
extractants with the oxidants H2O2 or O2 for ODS of organic
sulfide (Table S5).78,83−85 To promote the interfacial surface
area and improve the reaction microenvironment, Ding et al.86
used [(C8H17)3NCH3]2W6O19 as the catalyst with the presence
of H2O2 as the oxidant and [Omim][PF6] as the extractant to
form a three-liquid-phase emulsion system as microreactors for
ODS of organic sulfide from fuel oil (Figure 2b). DBT was first
extracted into the interface of emulsion droplets through the
hydrophobic interaction with hydrophobic cations of
[(C8H17)3NCH3]2W6O19. The active peroxo species formed
by active oxygen were transferred from H2O2 to W6O192−, and
the extracted sulfur compounds were oxidized to DBTO2 by the
active peroxo species. Simultaneously, the reduced POM anions
were continually decomposed into the initial structure W6O192−
and transferred into the water phase. Furthermore, P- and V-
substituted POM-ILs have been applied to further enhance the
emulsion stability and interfacial surface area.87,88 Also, a series
of Keggin-type POM-ILs and Anderson-type POM-ILs
containing cobalt (Co), zinc (Zn), nickl (Ni), lanthanum
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(La), or vanadium(V) have been synthesized to form bimetallic
POM-ILs to promote the catalytic activity for oxidative
desulfurization (Table S5).78,89,90 With the use of conventional
ILs as the extractant, the ODS efficiency by improving the phase
transfer of sulfur compounds, the stability of the emulsion
system, and the solubility of POM-ILs could be promoted.
However, the solvents composed of BF4− and PF6− are not eco-
friendly due to the corrosion of halide ions (e.g., F−, Cl−) to the
apparatus.91 Moreover, BF4− and PF6− can be degraded by
chemical oxidation with H2O2.92 Deep eutectic solvents (DES)
exhibit similar properties with ILs containing large and
asymmetric ionic species, but possess wider varieties of ionic
species and low cost, easy preparation, and hypotoxicity.93,94 In
addition, polyethylene glycol dimethyl ether (NHD) is a
commercial commonly used neutral solvent, which exhibits
excellent solubility, nonflammability, and nontoxicity. Zhang et
al.95 have proved that NHD improved the kinetics of Fe-based
ILs in ODS of H2S. Using DESs and NHD as solvent for ODS of
organic sulfide may be potential solvents for constructing a green
ODS process.
Because of the hydrophobic cations and hydrophilic anions of
POM-ILs, pure POM-ILs could form a self-emulsification
system for ODS. For example, [(C6H13)3PC14H29]2W6O19,61
[(n-C8H17)3NCH3]3[PMoO],96 and [C16mim][PyW]97 have
been designed as both the extractant and catalyst to construct
solvent-free ODS of aromatic sulfur compounds with the
presence of H2O2. The ODS process and mechanism are similar
to the three-liquid-phase system, and the ILs loss is largely
reduced. However, the ODS process with these emulsion
systems took 2 h to achieve the highest desulfurization
efficiency. Moreover, it is relatively difficult to separate the
emulsion system from oil.
A solid POM-ILs catalyst, such as [C16mim][PMoO], has
been prepared for ODS of organic sulfide with NaClO as the
oxidant and without extra conventional ILs.50 During the ODS
process, the [C16mim][PMoO] catalyst was well dispersed in oil
and accumulated on the interfacial layer upon resting, resulting
in easy separation from oil. Meanwhile, the product DBTO2 was
precipitated on the surface of POM-ILs (Figure 2b). During the
oxidation process, the [C16mim][PMoO] catalyst was activated
by •OH and •O2− radicals produced from NaClO (Figure 3d).
However, the production of NaCl could lead to secondary
pollution. Developing a novel oxidant or POM-ILs structure to
generate reactive oxygen species (ROS) is a promising strategy
to enhance the kinetics of ODS process.
To increase the stability, active sites, and the specific surface
area of a catalyst, a series of solvent-free supported MILs
combined with oxygen as the oxidant, such as MoOx/MC-600,
CNC@PIL@POM, or [(C 8 H 17 ) 3 NCH 3 ] 3 PMo 12 O 40 @γ-
Fe2O3@SiO2@mSiO2, have been designed for ODS of organic
sulfide in recent years.98−100 During the ODS process, sulfur
compounds are first extracted on the IL interface of supported
MILs and then oxidized by oxygen (Figure 2c). Jiang et al.98
designed a novel MoOx/MC-600 catalyst with polyoxometa-
late-based poly(ionic liquid) as a precursor for aerobic oxidation
of organic sulfide, which can be easily separated by a magnet.
With the presence of low-valence Mo and oxygen vacancies, the
oxidation efficiency could be promoted.
3.3. ODS of Organic Sulfide in Metal Complex ILs. The
metal complex ILs have not received much attention in
desulfurization of organic sulfide in recent years. The Fenton-
like system composed of [C4Py]3Fe(CN)6, [Omim][PF6], and
H2O2 has been constructed for the catalytic oxidative removal of
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DBT, BT, 3-methylbenzothiophene (3-MBT), 4-methyldiben-
zothiophene (4-MDBT), and 4,6-DMDBT (Table S6).101
Results showed the positive effect of excess water on sulfur
removal and the lower sensitivity of [C4Py]3Fe(CN)6 to water
than [FeCl4]−, which led to a higher desulfurization efficiency
with [C4Py]3Fe(CN)6 than MILs containing [FeCl4]−.
Metalloporphyrin such as (Porp)Fe(III)Cl is a type of
biomimetic catalysts which exhibits high capability of O2
activation to produce FeIIIOO− (peroxo), FeIIIOOH (hydro-
peroxo), and FeIVO (oxo) intermediates.44 With the presence of
H2O2 as the oxidant, (Porp)Fe(III)Cl presented the Fenton-like
reaction property and promoted the production of radicals to
oxidize organic sulfur compounds.57
Thus, designing metal complex ILs with low water sensitivity
and relatively low interaction between a center metal and
anionic ligand is significant for ODS of organic sulfur
compounds. Furthermore, acidic metal chloride ILs and
POM-ILs dissolved in oil can not only cause the corrosion of
apparatus but can also decrease the quality of fuel oil. Thus, by
regulating the cationic and anionic structures of metal complex
ILs, novel metal complex ILs possessing relatively low acidity
and low solubility in oil may be developed.
4. OXIDATIVE DESULFURIZATION OF H2S IN MILS
Dry desulfurization is an important method for H2S removal
from industrial process gas, including coal gasification, biogas,
exhaust gas, and so on.102,103 Because of the high chemical
affinity of H2S with metal ions and surface metal sites, metal
oxides, such as Fe2O3, Al2O3, ZnO, and V2O5, have been the
most commonly used sorbents for dry desulfurization. During
the ordinary dry desulfurization process, H2S can be adsorbed
and oxidized into elemental sulfur at low temperatures in the
presence of air.104 This process is easly to operate with relatively
a low operating cost. However, reactor blocking and difficult
separation of catalysts from elemental sulfur are problems for
processing high concentration H2S-containing gas sources,
which may cause severe intractable industrial hazardous waste.
Therefore, it is only suitable for the fine desulfurization stage
containing low H2S concentrations. Claus technology is another
important dry desulfurization process for H2S remove from tail
gas containing high H2S concentration and a molar ratio of 2:1
of H2S to SO2 in the oxidation reactor.10,11 However, the
subsequent fine desulfurization is necessary for the residual
10,000 ppm of H2S in the exhaust of the Claus tail gas treatment
process due to the thermodynamic limitations.
Until now, the Lo-Cat wet oxidation desulfurization process is
the most commonly used technology commercially for the
removal of H2S due to the mild conditions, high conversion
efficiency, and easy operations.13 Nevertheless, there exist some
drawbacks as the following: (1) iron complex needed to confirm
the desulfurization at the range of pH 6−8 to prevent Fe3+
hydrolysis and guarantee high desulfurization efficiency, (2)
decomposition of coordination complex EDTA during the
regeneration of desulfurizer by active oxygen in which the
Fenton-like system can form, (3) overoxidation of sulfur
compounds to inorganic side products such as sulfate, sulfite,
and thiosulfate, and (4) discharge of high-salt organic
wastewater, low purity of the produced sulfur element which
will be treated as solid waste, and severe secondary pollution.
Therefore, the development of a novel desulfurization system is
essential.
However, in the ODS process with MILs, the desulfurization
system is nonaqueous with high thermal and chemical stability,
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Figure 4. Nonaqueous wet oxidation desulfurization process and desulfurization mechanism: (a) Nonaqueous wet oxidation desulfurization process in
Fe-IL and the Fe-IL regenerated by air. (b) ODS mechanism of H2S removal in Fe(III/II)-IL/DMF system.42
benign solubility, and good redox performance, which facilitates
the oxidation of hydrogen sulfide into elemental sulfur and the
dissolution of O2 in the desulfurization system resulting in the
higher regeneration efficiency. Generally, compared with a dry
desulfurization process, high quality sulfur can be formed and
well separated from the desulfurizer due to the surface activity of
ILs, preventing the stick of sulfur and pipe blocking. Moreover,
MILs exhibit a high capacity of oxygen absorption, which results
in the simple regeneration of MILs by aeration even at low
temperature.
4.1. ODS of H2S in Fe-Based ILs. Whether in dry
desulfurization or wet oxidation, Fe-based compounds exhibit
good performance for the oxidation of H2S to elemental sulfur
due to the low cost, abundant sources, and good redox
performance of Fe-based compounds. Hua et al.105 developed
a nonaqueous system FeCl3/95%NMP/5%H2O (NMP = N-
methylpyrrolidinone) for ODS of H2S with a regeneration by
O2. There is no need of special ligands and pH control in the
FeCl3/95%NMP/5%H2O system, while a high desulfurization
efficiency of 99.72% and high quality sulfur product were
achieved. The 11.23% NMP was degraded due to H2O2
produced in FeCl3/95%NMP/5%H2O system. Especially, the
low solubility of ferric chloride in organic solvents limits the
improvement of the desulfurization capacity.
Following this problem, He et al.106 first proposed a novel
nonaqueous oxidation desulfurization system based on Fe-based
ILs. Similar to other ILs, the imidazole organic cations can
absorb H2S, and the partner metal complex anions act as the
oxidation center. The H2S absorption and oxidation was
completed and intensified synchronously in Fe-based ILs
intramolecularly. Thus, the sulfur capacity for H2S removal by
Fe-based IL is far more than the aqueous Lo-Cat system.
Because of the hydrophobicity of [Bmim][FeCl4], the water
produced during the desulfurization of H2S can be separated
spontaneously without desulfurizer loss, which enhances its
recycling efficiency.31 The Fe-based ILs system is different from
the aqueous basic desulfurization system, for the Fe-based ILs
possessing both Lewis and Brönsted acidity which results in the
absorption of CO2 sour gas being prevented.51 Additionally, this
nonaqueous oxidation desulfurization system has several
advantages, including high thermal stability, high desulfurization
selectivity, no side products, high quality sulfur without pH value
control, and wastewater discharge. The development of ODS of
H2S in MILs over the past decade is listed in Table S7. The
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nonaqueous oxidation desulfurization process with Fe-based ILs
is illustrated in Figure 4a. H2S is absorbed and oxidized to sulfur
with Fe-based ILs in an absorption tower, and then, Fe-based IL
is regenerated by bubbling O2 after being separated with
sulfur.107
Nevertheless, the actual sulfur capacity of the developed
nonaqueous wet oxidation desulfurization process with the
[Bmim][FeCl4] ionic liquid is 0.31 g/L, that is far less than
theoretical sulfur capacity.106 Wang and Zhu108 proposed that it
may be attributed to the strong acidity of [Bmim]FeCl4 as well
as its dual function as media and catalyst.
However, the high cost of imidazolium-based ILs is still
hinders their large-scale industrial application. The relatively low
cost amine-based ILs Et3NHCl/FeCl3 has been synthesized for
ODS of H2S.54,109 Results showed that 1.6Et3NHCl/FeCl3 ionic
liquid possessed good thermal stability and high sulfur capacity
of 6.36 g/L that was much higher than that of [Bmim]FeCl4
(0.87 g/L).54 It is ascribed to the strong binding interaction
between H2S and Et3NH+ which is twice as much as the binding
energy of H2S and [Bmim]+. On the other hand, Et3NHCl/
FeCl3 is prone to foaming during the ODS process due to the
high viscosity and surface tension of Et3NHCl/FeCl3, increasing
the residence time of H2S and the sulfur capacity of desulfurizer
Et3NHCl/FeCl3. However, the foaming phenomenon in the
absorption tower not only causes an increase in tower height to
prevent tower flooding but also increases the difficulty of sulfur
separation. An organic solvent such as ethanol has been used for
defoaming in the surfactant system; thus, it plays an active role in
desulfurization efficiency and sulfur quality due to the viscosity
reduction and defoaming functions. Moreover, the TG curve of
Et3NHCl/FeCl3 showed that the initial decomposition temper-
ature was around 200 °C, and 50% mass loss occurred at 300 °C,
while the obvious mass loss of [Bmim]FeCl4 was about 350
°C.110 Therefore, the mass loss of ammonium-based Fe-ILs
during the ODS process of H2S removal is non-negligible.
Water is an important factor influencing the H2S ODS
process. Water accumulated in a desulfurization system could
increase the solubility in the desulfurizer and limit sulfur
precipitation. Wang and Ding111 reported that adjusting water
content from 5.88% to 80% could regulate the acidity of the
[Bmim]FeCl4 system and increase the H2S removal efficiency,
yet it is difficult to prevent the formation of sulfur blockage at vol
% (H2O) ≥ 80%. Lee et al.41 stated that high water content in
[Bmim]FeCl4 can react with Fe2+ and O2 to produce •OH
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Figure 5. General schematic of pilot test of H2S ODS by Fe-based ILs.
radicals, leading to the decomposition of Fe-based ILs organic
cations. However, water takes part in the regeneration reaction
as a reactant during the regeneration process by O2 (Figure 4a).
Therefore, keeping a certain amount of water in the Fe-based ILs
desulfurization system is necessary to improve the desulfuriza-
tion performance. The formation of radicals should be
terminated to decrease the decomposition of the desulfurizer
due to too much water in Fe-based ILs, which can be achieved by
the hydrophobic properties of Fe-based ILs and pretreatment to
reduce the water vapor carried by raw materials.
Therefore, low water content in the ODS process of the H2S
by Fe-based IL system is inevitable. Organic solvents as
scavengers can be used to eliminate the influence of radicals
produced by the reaction of H{[Bmim]Fe(II)xCly}, O2, and
H2O. N,N-Dimethylformamide (DMF), 1,3-dimethyl-2-imida-
zolidinone (DMI), polyethylene glycol dimethyl ether (NHD),
and N-methylpyrrolidinone (NMP) can be used as additives to
decrease the viscosity and acidity of a desulfurization system to
improve the adsorption capacities of H2S.42,95,112,113 Guo et al.42
reported that DMF could interact with Fe(III/II)-IL to produce
intermediates such as DMF···FeCl3···HS···Fe(III/II)-IL, result-
ing in the decrease of Fe−Cl bonds stability and easy oxidation
into sulfur (Figure 4b). Wang and Zhang51 found the release of
HCl gas from the BmimFeCl4 desulfurization solution during
the ODS process. Therefore, using these aprotic and basic/
neutral solvents as additives in a nonaqueous wet ODS process
may bind HCl to prevent its escape for keeping the
desulfurization system working well.
Alternatively, the supported MILs materials such as
5%[Bmim]Cl·CuCl2@silica and Et3NHCl·CuCl2@cyclodex-
trins modified zeolite have been designed to overcome the
mass transfer limited by the high viscosity of ILs.114,115
As to the regeneration process of the Fe-based ILs, O2
regeneration is the most commonly used technology to convert
Fe(II)-ILs into Fe(III)-ILs due to the environmentally friendly
property and low cost of oxygen. To achieve the complete
regeneration of [Bmim]Fe(II)Cl4 to [Bmim]Fe(III)Cl4, it can
be realized by air at room temperature for 80 h and at 50 °C for
20 h but at room temperature for 7 h and at 50 °C for 3 h
regeneration by oxygen.107 Jet-flow technology combined with a
jet-flow agent has been used to intensify the dissolution
performance of O2 in aqueous solution.116 However, cavitation
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and strong oxidation species •OH or •O2− are difficult to
generate by jet-flow technology in Fe-based ILs, preventing
further oxidation of sulfur. In addition, Zhang and Tong117
developed a novel process for H2S desulfurization on an Fe/Cu
catalyst, in which cupric ions reacted with S2− to produce CuS,
and then, the generated CuS converted Fe3+ into Fe2+, which
greatly enhanced the sulfur capacity for H2S removal. However,
how the addition of cupric ions into an Fe catalyst affected the
regeneration process of Fe2+ is unknown. Our research group
has investigated the regeneration of Fe(II)-IL in a Cu−Fe−ILs
system with bubbling oxygen, and results showed that the
addition of Cu2+ could significantly enhance the regeneration
efficiency by the reduction of reaction activation energy.
However, it is unclear whether the ODS process of H2S can
be promoted in the Cu−Fe−ILs system compared to Fe-ILs,
and the regeneration mechanism remains unclear.
4.2. ODS of H2S in Metal Oxide ILs. To avoid the water
loss in H2S desulfurization with aqueous protonated polyox-
ometalates, expand the range of temperature and improve the
desulfurization efficiency, POM-ILs have been designed by
dissolving protonated polyoxometalates in ILs for H2S oxidation
desulfurization.56,118,119 Wang and co-workers56,120 found that
both [Bmim]PMo10V2O40/BmimCl solutions at 200 °C and
[CH 3 (CH 2 ) 15 N(CH 3 ) 3 ] 3 {PO 4 [MoO(O 2 ) 2 ] 4 }/[Bmim]-
[HCO3] solutions at 95 °C showed great H2S desulfurization
performance, and they were ready to be regenerated by air. The
oxygen of [Bmim]PMo10V2O40 could be replaced by S2− of H2S,
and then, S2− was oxidized to sulfur during the regeneration of
[Bmim]PMo10V2O40. However, the H2S removal process in
[Bmim]PMo10V2O40/BmimCl solutions is predominated by
H2S absorption rather than oxidation. Ma et al.119 reported that
Cl− of BmimCl which has strong interactions with H2S can be
included into the cavity of PMo12O403− to enhance the sulfur
capacity of ILs. Therefore, reducing the viscosity of ILs by using
MILs with lower viscosity or adding aprotic solvents to enhance
the mass transfer of H2S into a POM-based ILs/ILs system is
necessary to promote the desulfurization efficiency and recycling
times.
4.3. ODS of H2S in Metal Complex ILs. As mentioned
above, Wang et al.51 reported on HCl emission during the
desulfurization of H2S with [Bmim][FeCl4], which implied that
H+ was easily combined with a Cl atom of an Fe-based IL to form
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HCl to escape with the oxidation of H2S to elemental sulfur in
the absorption stage. Moreover, HCl can be also evacuated in
the regeneration stage accompanied by aeration, leading to air
pollution and the structural change of the Fe-based IL.
Two ways have been proposed to solve this problem. Guo et
al.42 and Zhang et al.113 proved that the addition of aprotic
solvents, for example, DMF and NMP, acted as an “acid-binding
agent” to prevent the evacuation of HCl to some extent.
However, it is still difficult for total control of the HCl emission
with the treatment of high sulfur gas. Actually, if Cl elements are
substituted by strong complex ligands, both the corrosion of Cl
and the HCl emission can be avoided. Wang et al.120 prepared a
basic iron-based IL [Bmim][Fe(EDTA)] through the sub-
stitution of Cl in [Bmim][FeCl4] with EDTA and used it for
ODS of H2S. Results showed that 4.2980 mg/(mL h) of sulfur
production could be achieved with 25 mL/min of O2 and 10
mL/min of H2S for 7 h in a [Bmim][Fe(EDTA)]/NHD
complex system.
4.4. Pilot Test. The pilot test aims to verify the stability of a
desulfurization solution and the manipulation of the desulfuriza-
tion process. Figure 5 describes a general schematic of H2S ODS
by Fe-based ILs. It can be applied in the purification of industrial
process gas such as coke oven gas, sour water stripping tail gas,
and Claus hydrogenation tail gas.121,122 The novel desulfuriza-
tion process called Nasil (nonaqueous phase system of ionic
liquid) is similar to the traditional aqueous wet oxidation
desulfurization process with Lo-Cat. Even so, based on the
organic surface activity of Fe-based ILs, there are significant
differences between them:
(1) The gas absorption capacity in ILs is significantly
influenced by pressure and temperature. The more the
gas absorption capacity increases with increasing feed gas
pressure, the faster the reaction rate rises. Thus, the
absorption of H2S in Fe-based ILs can be run in a smaller
size tower at higher pressure. For example, natural gas
(ca.0.5 MPa) can be treated in an absorber with a volume
of only one-fifth of the absorber at atmospheric pressure.
The regeneration process can also be operated in the same
way with higher pressure air. All are beneficial to promote
the treatment and regeneration performance with lower
cost.
(2) Due to the surfactant characteristics of ILs, the primary
sulfur particles are easily self-aggregated and precipitated
without sulfur plug in pipes and apparatus, which has been
a big problem in the traditional aqueous wet oxidation
desulfurization process. In the pilot test of Claus
hydrogenation tail gas with 5000m3/d, the sulfur paste
obtained by centrifugation with a solid content of 70% can
be directly melted at 130−140 °C without loss of
desulfurizing agents. The liquid sulfur with purity up to
99.5% can be collected directly from the lower layer
through liquid/liquid separation. This is great progress to
avoid solid waste or hazardous waste. Meanwhile, the
supernatant can be recycled as a desulfurization lean
liquid. Therefore, the Nasil process based on MILs can be
applied in a wider temperature range and is not limited by
the evaporation of water in the Lo-Cat process at higher
temperature.
(3) Owing to the hydrophobicity of Fe-based ILs, the water in
the raw gas and produced in the ODS process is dispersed
in the desulfurization solution. For example, the water in
the desulfurization system of biogas easily escapes with
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the raw gas and air for regeneration. Another key point is
that this new process does not require a continuous
chemical supplement to maintain stable operation of the
desulfurization system. Finally, no refractory organic
wastewater was discharged.
(4) However, the strong corrosion behavior of Cl in Fe-based
ILs brings new challenges to the selection and use of
equipment. It is significant to develop a novel desulfurizer
of nonhalide-based MILs to reduce the corrosion of a
desulfurizer, such as [Bmim][Fe(EDTA)] with ligand
EDTA in replace of Cl−.
Although [Bmim]FeCl4 was found to be hydrophobic,52 Koo
et al. reported that 20% (v/v) of [Bmim]FeCl4 was fully miscible
with water, and [Bmim]FeCl4 can be recovered by adding
acid.123 As for the recovery of [Bmim]FeCl4 from the solvents
with low boiling point such as ethanol, it can be conducted by
evaporation to remove ethanol.124 After several recycles of MILs
for ODS, impurities in raw gas such as coal tar and other
aromatic compounds in coke oven gas may be accumulated in
MILs which need to be removed to improve the recyclable
capacity of MILs. The purification and discard routes of
[Bmim]FeCl4 in the ODS system, taking coal tar as an example,
are presented in Figure 6.125 The [Bmim]FeCl4/NHD complex
Figure 6. Purification and discard routes of [Bmim]FeCl4 for ODS of
coke oven gas.125
desulfurizer can be separated from coal tar by adding water and
then is purified for recycle by the evaporation of water. For those
discharged [Bmim]FeCl4, FeCl4− ions are hydrolyzed in water
to form a Fe(OH)3 colloidal precipitation which can be used as a
water treatment agent, and the biodegradable imidazole
materials can be used as new effective antimicrobial agents or
could be directly treated by biochemical wastewater treatment.
5. OXIDATIVE DESULFURIZATION OF SO2 IN
FE-BASED ILS
Wet flue-gas desulfurization catalyzed by metal ions with strong
oxidation ability to convert S(IV) to S(VI) is one of the most
important approaches for SO2 removal and H2SO4/CaSO4·
2H2O recovery.15,126,127 However, this process is usually carried
out in an aqueous homogeneous phase, and it is difficult to
separate the desulfurization product and reuse the catalysts.
The absorption of SO2 by ILs was reported more than 10
years ago,22,128 and so far, there have been few reports on the
oxidation of SO2 to sulfuric acid using ionic liquids. When SO2
was blown into [Bmim][FeCl4], neither absorption nor
oxidation of SO2 occurred with/without O2 atmosphere.
However, as long as the [Bmim][FeCl4] system contains
water,a Fenton-like reaction initiates in the aqueous phase with
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Table 2. ODS Process in MILs, Including Operating Conditions, Sulfur Capacity, Merits, and Shortcomings
ODS conditions Sulfur capacity
MILs Organic sulfide H2S SO2 Organic sulfide H2S SO2 Merits Shortcomings
Metal refs 58, 129, 66 refs 42, 54, 131 ref 124
chloride
ILs
T = 25−90 °C, t = T = 25−180 °C, t = T = 40 °C, t = ∼2.5 mg/g 0.31−14.48 g/L 24.4 g/L Easy synthesis Partially loss of
10−120 min, 15−360 min, Cinitial 250 min, Cinitial = and regenera- MILs in water
Cinitial = = 1%−99.9%, Fflow 32.5 g/m3, tion, simple or oil, relatively
500−1000 ppm, = 15−80 mL/min, VFe‑IL:Vwater:Vethanol regulation of low regenera-
n(O)/n(S) = without pH control = 1:1.5:3,pH 2.0 acidity, high tion efficiency,
3.5:1−8:1, absorption and Cl− corrosion
m(oil):m(MIL) oxidation effi- to the equip-
= 3:1−5:1, ciency, hydro- ment
without pH phobicity
control, 4−8 re-
cycles

Metal refs 49, 50, 82 refs 56, 118, 119

oxide ILs
T = 25−100 °C, t T = 80−200 °C, t = ∼10−100 mol/mol 166−648 g/mol High catalytic High cost and
= 2−180 min, 120−360 min, activity, rela- complicate
Cinitial = Cinitial = tively high re- synthesis, mass
250−1000 ppm, 690−2000 mg/m3, cycling ca- transfer limita-
n(O)/n(S) = Fflow = pacity tion, emulsifi-
3:1−6:1, 100−200 mL/min, cation, addi-
n(S):n(MIL) = without pH control tional solvents
8:1−100:1,
without pH
control, 6−10
recycles

Metal refs 57, 130

complex
ILs
T = 60 °C, t = ∼100 mol/mol O2 activation, Relatively low
240 min,Cinitial = metal complex thermal stabil-
500 ppm,, ILs containing ity, most are
n(O)/n(S) = metal cations solid state
3:1−6:1, or metal anions
n(S):n(MIL) = prepared, as
100:1, without well as basic
pH control MILs

O2 bubbling due to the dissolution of Fe-based ILs in water. The
reactive oxygen species, for example, hydroxyl radicals, promote
the oxidation of SO2 into acid at room temperature. Xie et al.124
constructed a ternary system containing Fe-based ILs, ethanol,
and water for wet oxidative flue-gas desulfurization for the first
time, in which a homogeneous solution of Fe-based ILs/
ethanol/water can be obtained, and SO2 is oxidized and
recovered as sulfuric acid. With introduction of ethanol to form a
homogeneous phase, it is conducive to gas−liquid contacts,
leading to high reaction efficiency. The product sulfur acid
solution could be easily stripped from Fe-based ILs by removing
ethanol, and the catalyst (Fe-based ILs) could also be recovered
from water simultaneously. Results showed that the best
desulfurization efficiency was greater than 90%. However,
ethanol as a radical scavenger is not a suitable solvent to achieve
highly efficient desulfurization. Therefore, developing a new
desulfurization system with novel water-soluble solvents such as
acetone is expected to be an effective strategy to enhance the
desulfurization efficiency by radical reactions.
6. FUTURE RESEARCH AND CONCLUSIONS
6.1. Green Process. On the basis of the structure and
properties of MILs, MILs are divided into three types in this
critical review: metal chloride ILs, metal oxide ILs, and metal
complex ILs. MILs can exhibit strong oxidation performance or
biomimetic catalysis performance according to the ODS
mechanism. During ODS of H2S, H2S is absorbed and oxidized
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into elemental sulfur with Fe-based ILs as catalysts based on a
strong oxidation performance. Metal oxide ILs and metal
complex ILs mainly exhibit biomimetic catalysis performance,
activating oxygen or hydrogen peroxide in the ODS process to
oxidize sulfur compounds. The ODS conditions of organic
sulfide, H2S, and SO2 removal in MILs, including temperature,
desulfurization and regeneration times, pH, and dosage of MILs,
are summarized in Table 2, as well as the merits and
shortcomings with different types of MILs. ODS processes
with MILs generally possess mild conditions, high desulfuriza-
tion efficiency, easy recycling, and no secondary pollution.
Especially for metal complex ILs, the structure can be well
regulated for specific purposes, containing O2 activation capacity
and more stable complex ions. However, there still exists some
shortcomings, such as the loss of MILs in water or oil, relatively
low regeneration efficiency, and high cost. Therefore, develop-
ing more green ODS processes with MILs is urgent for their
further industrial applications.
6.1.1. ODS of Organic Sulfide. In conclusion, the main
problems in ODS of an organic sulfide system usually with H2O2
as the oxidant are the limit of mass transfer and the emulsion
phenomenon between the aqueous phase and oil phase in the
ODS system. Magnetic MILs with strong magnetic perform-
ance, for example, [C4(mim)2]Cl2/2FeCl3, has been inves-
tigated to realize the recovery under the strong magnetic field
with 97.1% desulfurization efficiency and five recycles.74
However, the dissolution of the MILs in oil was still non-
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Environ. Sci. Technol. 2021, 55, 1419−1435
Environmental Science & Technology
negligible. The supported MILs containing multinuclear cations
or magnetic carriers such as magnetic mesoporous silica may be
promising catalysts for efficient ODS of aromatic sulfur
compounds with high efficient separation and regenera-
tion.132,133
As reported, a Schiff base complex and PorpFe(III)-based
complex are biomimetic catalysts for oxygen molecule activation
to regenerate ROS with strong oxidation performance.44,45,134 It
is a good strategy to develop the supported PorpFe(III)-based
complex ILs for ODS of organic sulfide with oxygen as the
oxidant to obtain high ODS efficiency and easy regeneration. Yu
et al.135 has developed NaY sieve loading with a Schiff base Cu−
Co complex for heterogeneous ODS of aromatic sulfur
compounds with oxygen as the oxidant. Therefore, a bubbling
oxygen fluid bed could be designed for ODS of organic sulfide
with the supported PorpFe(III)-based complex ILs, as like the
fluid-bed reactor of HDS technology in industrial applications,
which gives us low energy consumption and high mass transfer
efficiency.
6.1.2. ODS of H2S. A pilot test has fully presented the green
technology of H2S ODS by Fe-based ILs. However, the H
elements from H2S are converted into H2O rather than
hydrogen as a clean energy. Currently, hydrogen is mainly
produced from coal gasification or petroleum cracking at high
temperature and high pressure with a great production cost.136 It
is an attractive idea to recycle the H element as hydrogen clean
energy by electrolysis. The Puguang Gas Field (Sichuan
Province, China) produces the highest H2S concentration
(about 20%) in Asia. There are sulfur productions of 6000−
7000 t/d which is equivalent to 500 t/d H2 production.
Electrolysis can be operated at ambient temperature and
pressure and driven with solar energy with low energy
consumption and no secondary pollution.137
ILs possess good stability and few side reactions during the
electrolytic reaction due to its wide electrochemical window,
good stability, and high conductivity.138,139 Guo et al.42 found
that Fe(II) in Fe(III/II)-IL/DMF could be successfully
regenerated by electrolysis technology with 36% current
efficiency at the Pt electrode simultaneously with the production
of hydrogen from the desulfurization lean solution. Additionally,
carbon emission reduction is one of the important tasks for the
petrochemical industry and coal chemical industry. The trapped
CO2 can be introduced into the cathode of an electrolyzer to
react with H from the desulfurization lean solution to produce
syngas (CO + H2) or hydrocarbon chemicals (CH4/HCOOH).
A stable and highly efficient electrolysis regeneration and
resource process can be designed as shown in Figure 7. Ma et
al.137 have constructed a solar-driven electrochemical approach
for the simultaneous conversion of CO2 to CO on a ZnO@
graphene cathode catalyst and H2S to sulfur on a graphene
anode catalyst mediated by an Fe3+/Fe2+-EDTA redox reaction
with high activity and stability. Owing to the large surface area, a
plate electrolytic cell for electrolysis with a flowing electrolyte is
able to promote the electrode reaction efficiency.
6.2. Summary and Prospects. In this critical review, we
summarized and criticized the most important developments of
ODS with MILs over the past decade. In conclusion, MILs are
eco-friendly catalysts with nonvolatility, high catalytic activity,
and recyclability. With the incorporation of metal ions into ILs,
MILs always act as both the absorber and catalytic center. The
particular physicochemical properties of MILs provide essential
preconditions to construct a green ODS process for organic
sulfide, H2S, and SO2 in the future, which can provide a new idea
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pubs.acs.org/est Critical Review
Figure 7. Electrolysis regeneration of ODS-rich liquid of MILs with
bubbling CO2 in the anodic area.
to resolve the bottleneck problems of the traditional aqueous
ODS process at basic pH.
Due to the water solubility of MILs to some extent,
investigating the effect of MILs on the water environment and
the eco(toxicity) of ILs is important. Many new models have
been developed to evaluate the toxicity of ILs to human health
and the environment, but there is no exact verdict until now.
However, according to the practical experience of H2S ODS
with [Bmim]FeCl4, [Bmim]FeCl4 exhibits good recycling
capability ascribed to its hydrophobicity and high thermochem-
ical stability, which will greatly reduce the negative effect on the
environment. Moreover, [Bmim]FeCl4 can be purified with the
water-soluble property, and [Bmim]FeCl4 dissolved in water is
hydrolyzed to Fe(OH)3 colloidal particles that can be used as
water treatment agents and biodegradable imidazole materials
that can be used as medicine sources. However, the
emulsification during the regeneration process of MILs in
ODS of organic sulfide is still a problem, which may lead to the
contamination of oil and low recovery efficiency of MILs.
Therefore, developing a highly efficient recovery technology is
urgent for the large-scale of MILs in ODS processes.
Additionally, developing novel MILs such as metal complex
ILs with biodegradable ligands and ILs is also necessary.
Further research needs carried out as follows:
(1) In view of functional materials, the three types of MILs
belong to the complex-based MILs. Their multifunctional
properties, including chemical and thermal stability,
oxidation performance, selective gas absorption, hydro-
phobicity, and surface activity, can be obtained by
adjusting the types of cationic and anionic ions in MILs,
especially the types of metal complex ions. MILs are
sensitive to the change of pressure and temperature and
expected to intensify their selective absorption or
extraction of sulfur compounds. Their paramagnetic
performance and hydrophobic characteristics will be
conducive to the construction of a rapid and efficient
separation and recovery process.
(2) In view of desulfurization technology, the mechanism and
species of activated molecular oxygen induced by
organometallic complexes and O2 can be regulated by
water and organic solvents. A green desulfurization
process of moderate oxidation and resource utilization
of sulfide can be constructed without excessive oxidation
of sulfide to lots of inorganic salts and refractory industrial
wastewater.
https://dx.doi.org/10.1021/acs.est.0c05855
Environ. Sci. Technol. 2021, 55, 1419−1435
Environmental Science & Technology pubs.acs.org/est Critical Review

(3) In view of ecological environmental protection, the
organic ligands of MILs or conventional ILs used to
prepare MILs should be biodegradable to avoid a great
negative impact on the environment due to the loss or
discharge during the process of ODS. Therefore,
designing nontoxic hydrophobic metal complex ILs
containing biodegradable amino acids, choline, DES,
and more is urgent for the sake of the environment and
economy. Especially, it is very important to reduce the risk
of halogen corrosion to equipment, which can reduce
equipment investment, and operating costs and risks.
(4) In view of scaleup, the high viscosity of ILs is one of the
problems in the industrial application of ILs. But it is
meaningless to pursue the perfluorinated ILs with low
viscosity for industrial scaleup application due to high-
cost and poor environment compatibility. The aprotic
industrial organic solvents with low viscosity and high
boiling point can be directly used to make MILs
desulfurization solutions for industrial applications.
(5) In view of recycling and resources, the solution to sulfide
pollution must be eco-friendly and recyclable without
secondary pollution. Therefore, MILs that are used for
ODS must be easy to separate from desulfurization
systems and products (e.g., sulfone, sulfur, and sulfuric
acid) and easy to recycle, which will also result in
improving the purity of MILs during ODS and reducing
the negative effect of MILs on the environment. The
hydrophilicity, oxidation, thermal stability, and phase
transfer characteristics of MILs are essential factors for the
construction of novel desulfurization processes.
Abdul Basit Qazi − Research Group of Environmental Catalysis
and Separation Process, Beijing Key Laboratory of Energy
Environmental Catalysis, College of Chemical Engineering,
Beijing University of Chemical Technology, Beijing 100029,
China
Li Zhang − Research Group of Environmental Catalysis and
Separation Process, Beijing Key Laboratory of Energy
Environmental Catalysis, College of Chemical Engineering,
Beijing University of Chemical Technology, Beijing 100029,
China
Xueke Liu − Research Group of Environmental Catalysis and
Separation Process, Beijing Key Laboratory of Energy
Environmental Catalysis, College of Chemical Engineering,
Beijing University of Chemical Technology, Beijing 100029,
China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.est.0c05855
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work is funded by the National Science and Technology
Major Project (No. 2016ZX05017-004), National Natural
Science Foundation of China (No. 21076019, No. 90610007),

■
*
ASSOCIATED CONTENT
sı Supporting Information
National Ministry of Science and Technology Program of China
(863 Program) (No. 2007AA06Z115), and Ph.D. Programs
Foundation of Ministry of Education of China (No.
The Supporting Information is available free of charge at 20090010110003).

■
https://pubs.acs.org/doi/10.1021/acs.est.0c05855.
Table S1: Characterization of properties and structure of ABBREVIATIONS
metal chloride ILs. Table S2: Characterization of IL, ionic liquid
properties and structure of metal oxide ILs. Table S3: MILs, metal-based ionic liquids
Characterization of properties and structure of metal POM, polyoxometalate
complex ILs. Table S4: Oxidative desulfurization of HPOM, heteropolyoxometalate
organic sulfide in metal chloride ILs over the past decade. Porp, porphyrins
Table S5: Oxidative desulfurization of organic sulfide in ODS, oxidative desulfurization
metal oxide ILs over the past decade. Table S6: Oxidative HDS, hydrodesulfurization
desulfurization of organic sulfide in metal complex ILs FGD, flue-gas desulfurization
over the past decade. Table S7: Oxidative desulfurization DBT, dibenzothiophene
of H2S in MILs over the past decade. (PDF) BT, benzothiophene

■ AUTHOR INFORMATION
Corresponding Author
4,6-DMDBT, 4,6-dimethyldibenzothiophene
3-MBT, 3-methylbenzothiophene
4-MDBT, 4-methyldibenzothiophene
Jiang Yu − Research Group of Environmental Catalysis and ROS, reactive oxidation species
Separation Process, Beijing Key Laboratory of Energy [Bmim]=[C4mim], 1-butyl-3-methyl imidazolium
Environmental Catalysis, College of Chemical Engineering, [Omim]=[C8mim], 1-octyl-3-methyl imidazolium
Beijing University of Chemical Technology, Beijing 100029, CnPy, N-alkylpyridine
China; orcid.org/0000-0002-5762-4143; CnPip, N-alkyl piperidinium
Email: yujiang@mail.buct.edu.cn CnPyr, N-alkylpyridinium
CnPyrr, N-alkyl pyrrolidinium
Authors EDTA, ethylenediaminetetraacetate
Fen Liu − Research Group of Environmental Catalysis and DES, deep eutectic solvent
Separation Process, Beijing Key Laboratory of Energy NHD, polyethylene glycol dimethyl ether
Environmental Catalysis, College of Chemical Engineering, DMI, 1,3-dimethyl-2-imidazolidinone
Beijing University of Chemical Technology, Beijing 100029, DMF, N,N-dimethylformamide
China NMP, N-methylpyrrolidinone
1431 https://dx.doi.org/10.1021/acs.est.0c05855
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Environmental Science & Technology
■
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