Journal of Chemical Technology and Biotechnology J Chem Technol Biotechnol 80:1089–1096 (2005)

DOI: 10.1002/jctb.1333

Review
Use of ionic liquids as ‘green’ solvents
for extractions
Hua Zhao,1∗ Shuqian Xia2 and Peisheng Ma2
1 Chemistry Program, Department of Natural Sciences and Mathematics, Savannah State University, Savannah, GA 31404, USA
2 School of Chemical Engineering, Tianjin University, Tianjin, China

Abstract: This review summarizes recent applications of ionic liquids (ILs) as ‘green’ solvents in
extractions of a variety of substances, including metal ions, organic and bio- molecules, organosulfur from
fuels, and gases. ILs could also be used along with another ‘green’ technology, supercritical fluid extraction
(SFE), for a more effective separation of products from ILs. In addition to their environmentally-benign
feature, ILs have other favorable properties over organic solvents used for extraction, such as adjustable
hydrophobicity, polarity and selectivity.
 2005 Society of Chemical Industry

Keywords: ionic liquid; extraction; green technology; industrial application; supercritical fluid

INTRODUCTION summarize the IL extractions of metal ions, organic

Ionic liquids (ILs) are a group of new organic
salts that exist as liquids at a low temperature
(<100 ◦ C). An important feature of ILs is their
immeasurably low vapor pressure. For this reason, they
are called ‘green’ solvents, in contrast to traditional
volatile organic compounds (VOCs). ILs have many
attractive properties, such as chemical and thermal
stability, nonflammability, high ionic conductivity,
and a wide electrochemical potential window.1 – 3
Therefore, they have been extensively investigated
as solvents or co-catalysts in various reactions
including organic catalysis,1,2,4 – 8 inorganic synthesis,9
biocatalysis,8,10 – 14 and polymerization.15,16
As a favorable separation technique for engineers,
extraction is an energy-efficient technology using
two immiscible phases (conventionally an organic
phase and an aqueous phase). Many organic solvents
involved, however, are toxic and flammable VOCs.
To improve the safety and environmental friendliness
of this conventional separation technique, ILs can be
used as ideal substitutes because of their stability,
nonvolatility and adjustable miscibility and polarity.
ILs can be hydrophilic and hydrophobic depending
on the structures of cations and anions.1,17 The
anion seems more important in determining the water
miscibility of ILs.17 Those ILs based on [PF6 ]−
and [Tf2 N]− {= bis[(trifluoromethyl)sulfonyl]amide}
are normally water immiscible, therefore, they are the
solvents of choice for forming biphasic systems in most
IL extraction applications. The following sections will
and bio-molecules, organosulfur from fuels, and gases,
as well the combined use of ILs with supercritical
fluids.
IL EXTRACTIONS OF METAL IONS
The hydrophobic character of some ILs allows
them to extract hydrophobic compounds in biphasic
separations. Metal cations tend to stay in the aqueous
solution being hydrated. Therefore, in order to remove
metal ions from the aqueous phase into hydrophobic
ILs, extractants (or chelators, ligands) are normally
needed to form complexes to increase the metal’s
hydrophobicity.18 – 20 The solvation of crown-ether
complexes in ILs is more thermodynamically favored
than conventional organic solvents.19 This is a key
advantage of using ILs for extractions of metal
ions.
Table 1 summarizes some representative examples
of IL extractions of metal ions, including alkali,
alkaline earth, heavy, and radioactive metals. To
achieve optimal extraction efficiency, there are several
controlling factors:
(1) Varying the structure of an IL (especially the side
chain of its cation) to change its hydrophobicity
can improve the partition coefficients of metal
ions.18,21
(2) Types of extractants (such as crown ethers) can
be modified to achieve optimal selectivity for a
specific application.22

∗ Correspondence to: Hua Zhao, Chemistry Program, Department of Natural Sciences and Mathematics, Savannah State University,
Savannah, GA 31404, USA
E-mail: zhaoh@savstate.edu
(Received 10 February 2005; revised version received 30 March 2005; accepted 7 April 2005)
Published online 26 May 2005
 2005 Society of Chemical Industry. J Chem Technol Biotechnol 0268–2575/2005/$30.00 1089
H Zhao, S Xia, P Ma

Table 1. Examples of IL extractions of metal ions

Extractant/ligand/
Substances IL metal chelator Reference

Alkali metals Li+ , Na+ , K+ , Rb+ , Cs+ [Cn MIM][PF6 ] (n = 4–9) DC18C6 21,37
Na+ , Cs+ [Cn MIM][PF6 ] (n = 4, 6, 8) 18C6, DC18C6, Dtb18C6 18
Cs+ [Cn MIM][Tf2 N] (n = 2, 3, 4, 6, 8) BOBCalixC6 38
Na+ , K+ , Cs+ [Cn MIM][Tf2 N] (n = 2, 4, 6, 8) DC18C6, N-alkyl 39
aza-18-crown-6 ethers
Alkaline earth metals Mg2+ , Ca2+ , Sr2+ , Ba2+ [Cn MIM][PF6 ] (n = 4–9) DC18C6 37
Sr2+ [Cn MIM][PF6 ] (n = 4, 6, 8) 18C6, DC18C6, Dtb18C6 18
Sr2+ [R1 R2 MeIM][PF6 ], [R1 R2 MeIM][Tf2 N] DC18C6 19
Sr2+ [Cn MIM][Tf2 N] (n = 2, 4, 6, 8) DC18C6, N-alkyl 39
aza-18-crown-6 ethers
Heavy and radioactive Pb2+ [Cn MIM][PF6 ] (n = 4–9) DC18C6 37
metals
Cu2+ , Ag+ , Pb2+ , Zn2+ , [C4 MIM][PF6 ] Dithizone 23
Cd2+ , Hg2+
Cd2+ , Co2+ , Ni2+ , Fe3+ , [C4 MIM][PF6 ], [C6 MIM][PF6 ] PAN, TAN 20
Hg2+
Ag+ [Cn MIM][PF6 ] (n = 4, 6, 8) Calyx[4]arene-bearing 40
pyridine
Cu2+ , Cr6+ , Zn2+ [Cn MIM][BF4 ] (n = 1, 3, 6, 8, 10) None 41
[Cn MIM][PF6 ] (n = 6, 10)
Hg2+ , Cd2+ TSILs None 28,35
Lanthanides (Nd3+ , La3+ , [C4 MIM][PF6 ] CMPO 32
Er3+ , Ce3+ , Sm3+ , Eu3+ ,
Gd3+ , Ho3+ )
Actinides (Th4+ , U2+ , Pu4+ ) [C4 MIM][PF6 ], [C4 MIM][NO3 ], Dtb18C6, CMPO, TBP 29,34
Others Al3+ [C4 MIM][Tf2 N], [C6 MIM][PF6 ] n/a 42,43
[C8 MIM][PF6 ]

Note: Cn MIM = 1-alkyl-3-methylimidazolium; DC18C6 = dicyclohexano-18-crown-6; 18C6 = 18-crown-6; Dtb18C6 = 4,4 -(5 )-di-(tert-butylcyc-
lohexano)-18-crown-6; BOBCalixC6 = calix[4]arene-bis(tert-octylbenzo-crown-6); Tf2 N = bis[(trifluoromethyl)sulfonyl]amide; R1 R2 MeIM = 1-R1 -2-
R2 -3-methylimidazolium (R1 = Bu, Et, or Pr; R2 = H, or Me); PAN = 1-(2-pyridylazo)-2-naphthol; TAN = 1-(2-thiazolylazo)-2-naphthol; CMPO =
octyl(phenyl)-N,N-diisobutylcarbamoylmethyl phosphine oxide; TBP = tri-n-butylphosphate.

(3) The extraction efficiency of metal complexes can
also be controlled by the pH of the system.23
Among IL extractions of metal ions, the extraction
of radioactive metals (lanthanides and actinides) has
particular industrial significance for the handling of
nuclear materials. Earlier studies in the area included
the behavior of uranium species in various ILs includ-
ing mixtures of chloroaluminate ILs and butylpyri-
dinium chloride,24,25 mixtures of chloroaluminate ILs
and [C2 MIM]Cl,26 chloroaluminate ILs,27 and sev-
eral RTILs.18,19,28 Recent work primarily focused on
two aspects: (1) the fundamental understanding of
ILs in nuclear chemistry such as radiochemical sta-
bility of ILs,29 superoxide ion electrochemistry in
ILs,30 and electrochemical properties of actinides in
ILs;31 (2) applications of ILs in nuclear extractions of
lanthanides32 and actinides (Table 1).29,33,34
However, the disadvantages of using extractants
are the difficulty of separating them from ILs and
the complexity of the system.28 As a new concept
introduced in the late 1990s, Task-Specific ILs
(TSILs) are designed to have targeted functionality
and, in this case, TSILs are those ILs containing metal
ion-ligating functional groups. Therefore, TSILs serve
as the hydrophobic solvent and the extractant at the
same time. TSILs containing side-chains of thiourea
derivatives and urea derivatives could dramatically
increase the partitioning of Hg2+ and Cd2+ ions from
aqueous solutions.28,35 Moreover, as indicated in a
recent review,36 TSILs are not limited to the extraction
processes; they are also versatile solvents/catalysts used
in organic catalysis, solid phase synthesis, and even
production of ‘liquid Teflon’ and emulsions.
IL EXTRACTIONS OF ORGANIC/BIO/BIOFUEL
MOLECULES
The high solubility of charged organic molecules in
ILs has stimulated the development of organic prod-
uct recovery by these ‘green’ media. As illustrated
in Table 2, phase partitions of many phenolic com-
pounds are investigated in the IL–water biphasic sys-
tems. The distribution coefficient is highly influenced
by the pH value which determines the existing form of
a phenolic compound as a conjugated acid or base.41,44
The same principle applied to the extraction of amino
acids through [BMIM][PF6 ] where the concentration
of the crown ether (DC18C6) also played an impor-
tant role on the amino acid recovery (Table 2).45
Meanwhile, IL biphasic systems were also used to
separate many other biologically important molecules

1090 J Chem Technol Biotechnol 80:1089–1096 (2005)

 Use of ionic liquids as ‘green’ solvents for extractions

Table 2. Examples of IL extractions of organic/bio/biofuel molecules

Substances IL Extractant Reference

Phenolic compounds phthalic acid, aniline, 4-hydroxybenzoic [BMIM][PF6 ] None 44

acid, benzoic acid, p-toluic acid,
benzene, chlorobenzene,
1,2,4-trichlorobenzene,
1,4-dichlorobenzene,
4,4 -dichlorobiphenyl
Phenol, tyrosol, p-hydroxybenzoic acid [Cn MIM][BF4 ] (n = 1, 3, 6, 8, 10) None 41
[Cn MIM][PF6 ] (n = 6, 10)
Chlorophenols [C4 MIM][PF6 ], [EMIM][Beti] None 58
Amino acids Tryptophan, glycine, alanine, leucine, [BMIM][PF6 ] DC18C6 45
lysine, arginine
Carbohydrates Xylose, fructose, glucose, sucrose [Cn MIM][X] (n = 4, 6, 8, 10; None 46
X = Cl− , PF6 − , BF4 − )
Glucose, sucrose, lactose, cyclodextrin [BMIM][dca] (carbohydrate solubility None 47
is approximately 200 g l−1 )
Cellulose [Cn MIM]X (n = 4, 6, 8) None 59
Organic acids Lactic acid, acetic acid, glycolic acid, [Cn MIM][PF6 ] (n = 4, 6, 8) TBP (in some 48
propionic acid, pyruvic acid, butyric cases)
acid
Biofuels Butyl alcohol (from fermentation broth) [BMIM][PF6 ], [C8 MIM][PF6 ] Pervaporation 49
was used
Antibiotic Erythromycin-A [BMIM][PF6 ] None 50
Hydrocarbons Olefins (such as ethylene, propylene, [Cn MIM][X], [HPy][X] (n = 4, 6; None 54,55
and butanes) from paraffins X = BF4 − , PF6 − )
C4 – 8 diolefin (such as butadiene) from [BMIM][BF4 ] None 56
C1 – 18 paraffins

Note: BMIM (or C4 MIM) = 1-butyl-3-methylimidazolium; EMIM = 1-ethyl-3-methylimidazolium; Beti = bis(perfluoroethylsulfonyl)imide; HPy = N-
hexylpyridinium; dca = dicyanamide.

such as carbohydrates,46,47 organic acids including
lactic acid,48 butyl alcohol (from the fermentation
broth to produce biofuels),49 and polyketide antibiotic
erythromycin-A.50 It is important to notice that car-
bohydrates are renewable and inexpensive resources
for the chemical industry. The underivatized carbohy-
drates are soluble in water but not in almost any other
solvents, which presents quite a challenge to transform
the carbohydrates. Their high solubility in ILs enables
the possibilities of transformations.47,51,52
Interestingly, an aqueous biphasic system (ABS)
was formed by contacting the hydrophilic [BMIM]Cl
with concentrated solutions of K3 PO4 (or other
kosmotropic salts such as KOH, K2 CO3 , Na2 HPO4 ,
and Na2 S2 O3 ).53 This finding of being able to control
the aqueous miscibility of hydrophilic ILs is very
valuable to the separation technology, because it
enables the recycling of hydrophilic ILs, the metathesis
formation of new ILs, and even reactive separations.
These ABSs have sufficient chemical potentials to
allow the separation of organic molecules into two
phases. The partition of several short chain alcohols
(eg methanol, propanol, butanol and pentanol) in
these ABSs was found to be a strong function of the
tie line lengths.53
Hydrocarbon separation through IL extractions was
also proved possible. One method for separating
olefins (such as ethylene, propylene, and butanes)
from paraffins involved several steps:54,55 (1) salts
(such as silver) were used to form complex olefins;
(2) the olefin-containing mixture was extracted by
the ionic liquid/salt solution, and the olefins were
adsorbed; (3) the olefins were separated by desorption
after the paraffins were removed. Another process
was developed to separate C4 – 8 diolefin hydrocarbons
(such as butadiene) from at least one diolefin and
at least one C1 – 18 paraffin using ILs (such as
[BMIM][BF4 ]).56 A continuous extraction process
using IL to separate C6 – 9 -aromatic hydrocarbons, and
higher hydrocarbons, from benzene-rich petroleum
streams has also been developed.57 These results
presented alternative ‘green’ methods for separation of
hydrocarbon molecules, which is extremely valuable
to the petroleum industry and polymer-processing
industry.
IL DESULFURIZATION OF FUELS
To reduce the impact of SOx emission from fuel
burning on human health and the environment,
tighter regulations are being imposed by EPA on
oil refineries to reduce the statutory sulfur contents
of fuels.60 Conventional desulfurization of diesel
was achieved through hydroprocessing catalysts.
However, further or deep hydrodesulfurization (HDS)
requires high consumption of energy and hydrogen.
Meanwhile, the HDS process is normally only effective
for removing organosulfur compounds of aliphatic
and alicyclic types. The aromatic sulfur molecules
including thiophenes, dibenzothiophenes (DBT), and

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H Zhao, S Xia, P Ma
their alkylated derivatives are very difficult to convert
to H2 S through HDS catalysts.61,62 Alternative
methods (including reactive adsorption63 ) of deep
desulfurization are highly demanded. One alternative
called extractive desulfurization (EDS) seems very
attractive for this purpose because of its low energy
cost, the elimination of hydrogen usage, the retaining
of the chemical structures of fuels and no requirements
of special equipment.
However, EDS through ILs seems particularly
favorable over organic solvents64 because of the use of
environmentally-benign solvents. Current research for
this purpose includes:
(1) EDS of organosulfur compounds: Bosmann
et al investigated various imidazolium- and
chloroaluminate-based ILs and found multistage
extraction was very effective in removing
sulfur;65 several ILs (eg [EMIM][BF4 ],
[BMIM][PF6 ], [BMIM][PF6 ]) exhibited high
selectivity in extracting aromatic sulfur and
nitrogen compounds;66 an ultra-low level of sulfur
(<10 ppm) was obtained when desulfurizating
gasoline and diesel fuel by halogen-free
ILs such as [BMIM][(Me(CH2 )7 OSO3 ] and
[EMIM][EtOSO3 ];67 CuCl-based imidazolium
ILs were prepared and demonstrated ‘remarkable’
ability in removing sulfur from gasoline;68 removal
of mercaptants (compounds containing the thiol
group, –SH) from hydrocarbons streams (eg
crude oil and natural gas) was achieved by reacting
basic metal salts with mercaptans, and adsorbing
the resulting mercaptides into ILs.69
(2) Removal of sulfur through the combination of chemical
oxidation and IL extraction: Lo et al 70 proposed a
‘one-pot’ operation where the sulfur compounds
in light oils were extracted by ILs and were further
oxidized by H2 O2 –acetic acid to form sulfones.
This process was reported to have a higher yield
by an order of magnitude compared with the
extraction alone process by ILs. Another example
is the electrochemical oxidation of polymerizable
sulfur compounds in naphtha followed by the
IL extraction.71 These EDS methods using ILs
have shown high energy-efficiency and high
effectiveness in getting rid of the low level of
sulfur from fuels.
IL/scCO2 EXTRACTIONS
The low volatility of ILs is the advantage that makes
them ‘green’. However, this advantage also creates
challenges for product separation and recovery. If the
product is volatile, a so-called back-distillation may be
used to remove the product from ILs.72 If a hydrophilic
product is obtained in a hydrophobic IL, water may be
used to remove the product from the IL.44 The biggest
problem is to recover nonvolatile or thermo-sensitive
products from ILs. Even though organic solvents (such
as diethyl ether,73 hexane73 and ethyl acetate74,75 ) can
1092
be effective in extracting the product, this approach
obviously compromises the ultimate goal of ‘green’
technologies. To overcome this limitation, another
type of ‘green’ solvent, supercritical fluids (SCFs), has
been adapted for product recovery from ILs.
Among SCFs, supercritical CO2 (scCO2 ) is readily
available and has been a mature technology for
decaffeination, extraction of natural products and dry
cleaning.76 The volatile and nonpolar scCO2 forms
interesting two-phase systems with nonvolatile and
polar ILs. The principle of product recovery by these
biphasic systems is based on the solubility of scCO2
in the IL (controlled by pressure) to transfer organic
products to the scCO2 -rich phase, and the insolubility
of the IL in scCO2 . For example, after extracting
naphthalene from [BMIM][PF6 ] with scCO2 ,77
the same research group successfully recovered a
variety of aromatic and aliphatic compounds from
the same IL with scCO2 .78 The phase behavior
of IL/scCO2 systems was further established.79 It
has also been demonstrated that by using low-
pressure CO2 (<5.2 MPa) both hydrophobic and
hydrophilic ILs can be separated from aqueous
solution.80 This finding is important for the effective
separation of water from IL aqueous solutions
after reactions or other processes complete. Even,
fascinatingly, a three-phase system was formed
by [BMIM][PF6 ]–MeOH–scCO2 , which allows the
solute separation from ILs, even under dilute
conditions (Fig 1).81
The solubility of ILs in pure scCO2 is normally
very low.82,83 However, when scCO2 contained high
contents (>10 mol%) of polar solutes (eg ethanol,
acetone), the solubility of [BMIM][PF6 ] in scCO2 was
quite high.82 This finding presented a challenge when
trying to remove a high concentration of polar organics
from ILs. Fortunately, organic solutes can also be
recovered through the pervaporation using nonporous
membranes with the selective layer consisting of
hydrophilic or hydrophobic polymers.84,85
More recently, the biphasic IL/scCO2 systems
have been used in metal-catalyzed and enzyme-
catalyzed reactions. This unique combination of
reaction and separation offers unique advantages:
(a) organometallic and enzymatic catalysts are soluble
and stable in ILs, but have low solubility in scCO2 ;
Figure 1. Phase behavior of IL/H2 O/CO2 mixture at room
temperature.81
J Chem Technol Biotechnol 80:1089–1096 (2005)

(b) many organic compounds are soluble in scCO2 ,
enabling easy separation of products from ILs; (c) this
process can be designed as batchwise or continuous
operations. Examples of metal-catalyzed organic reac-
tions include batchwise asymmetric hydrogenation of
tiglic acid,86 batchwise hydrogenation of alkenes and
carbon dioxide,87 continuous flow hydroformylation
of oct-1-ene catalyzed by rhodium complexes,88,89
continuous flow hydrovinylation of styrene by immo-
bilized organometallic (Ni-based) catalysts.90
A number of biocatalysis reactions were achieved
successfully in ILs (see reviews, Refs6,11 – 14 ), or
in scCO2 (see reviews, Refs91 – 93 ). The compari-
son study of imidazolium-based ILs, scCO2 and
n-hexane for the biocatalysis of a transesterification
reaction by immobilized enzymes has shown that
the enzyme activity is strongly influenced by the
water activity.94 Recently, the combination of IL and
scCO2 to form biphasic systems has attracted a lot
of attention for biocatalysis. For example, continu-
ous processes of Candida antarctica lipase B-catalyzed
butyl butyrate synthesis and the kinetic resolution
of 1-phenylethanol processes by transesterification;95
batchwise and continuous flow processes of acyla-
tion of octan-1-ol by vinyl acetate and the reso-
lution of 1-phenylethanol both catalyzed by lipase
from Candida antarctica;96 the transesterification reac-
tion of N-acetyl-L-phenylalanine ethyl ester with 1-
propanol catalyzed by immobilized α-chymotrypsin
was conducted in scCO2 containing [C4 MIM][PF6 ]
or [C8 MIM][PF6 ]).97 This research concluded that
these ILs provided a rather polar environment, but
it was adjustable by nonpolar scCO2 to improve the
enzyme activity.
GAS SEPARATIONS BY ILS
ILs can selectively dissolve gases. This makes them
potential solvents for gas separations.98 CO2 has rel-
atively high solubility in imidazolium-based ILs (eg
[BMIM][PF6 ]) as illustrated by recent experiments
and molecular modeling.99,100 A TSIL consisting of
an imidazolium ion to which a primary amine moi-
ety is covalently bonded was specifically designed
for CO2 ‘capture’.101 Ethylene and ethane have
medium solubility in [BMIM][PF6 ], while methane,
argon, oxygen, hydrogen, nitrogen, carbon monox-
ide have low solubility.99,102 Molecular dynamics
calculations were also consistent with experimen-
tal results that, for a given anion, the solubility
of CO2 in different ILs showed no large differ-
ence between the two cations. Another theoretical
study of gas solubility in [BMIM][PF6 ] was con-
ducted through the Monte Carlo simulations.103 In
this study, a molecular mechanics force field was
established to predict the thermophysical proper-
ties such as molar volumes as a function of tem-
perature. The Henry’s constants for water, car-
bon dioxide and argon were also reported in this
study.
J Chem Technol Biotechnol 80:1089–1096 (2005)
Use of ionic liquids as ‘green’ solvents for extractions
Because ILs are nonvolatile, they do not contami-
nate the gas stream during gas separation. The non-
volatility and selectivity of ILs allow them to be used in
conventional absorbers, scrubbers or supported liquid
membranes.104
SUMMARY
The first commercial process was established by BASF
AG (Ludwigshafen, Germany) to scavenge acids using
ILs.105 Several other processes developed by the same
company are in the pilot phase.104 More commercial
process developments involving ILs were presented
in a recent review.104 In summary, ILs are unique
and promising solvents for extractions because of their
non-volatility, adjustable hydrophobicity and polarity,
dissolution ability, and selectivity of gases. There is
a fundamental answer to these favorable properties:
ionic liquids are organic molecules and ionic salts at
the same time. And, they are liquids.
ACKNOWLEDGEMENTS
This project was partially supported by SSU/NIH-
EARDA grant No. 5 G11 HD 32861-07 and by an
NIH-MBRS grant.
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