Journal of Chemical Technology and Biotechnology

J Chem Technol Biotechnol 80:10891096 (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 2 School

Program, Department of Natural Sciences and Mathematics, Savannah State University, Savannah, GA 31404, USA 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 uid 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 uid

INTRODUCTION 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, nonammability, 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-efcient technology using two immiscible phases (conventionally an organic phase and an aqueous phase). Many organic solvents involved, however, are toxic and ammable 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[(triuoromethyl)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

summarize the IL extractions of metal ions, organic and bio-molecules, organosulfur from fuels, and gases, as well the combined use of ILs with supercritical uids.

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 metals 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 efciency, 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 coefcients of metal ions.18,21 (2) Types of extractants (such as crown ethers) can be modied to achieve optimal selectivity for a specic 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 02682575/2005/$30.00

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Table 1. Examples of IL extractions of metal ions

Substances Alkali metals Li+ , Na+ , K+ , Rb+ , Cs+ Na+ , Cs+ Cs+ Na+ , K+ , Cs+ Mg2+ , Ca2+ , Sr2+ , Ba2+ Sr2+ Sr2+ Sr2+ Pb2+ Cu2+ , Ag+ , Pb2+ , Zn2+ , Cd2+ , Hg2+ Cd2+ , Co2+ , Ni2+ , Fe3+ , Hg2+ Ag+ Cu2+ , Cr6+ , Zn2+ Hg2+ , Cd2+ Lanthanides (Nd3+ , La3+ , Er3+ , Ce3+ , Sm3+ , Eu3+ , Gd3+ , Ho3+ ) Actinides (Th4+ , U2+ , Pu4+ ) Al3+

IL [Cn MIM][PF6 ] (n = 49) [Cn MIM][PF6 ] (n = 4, 6, 8) [Cn MIM][Tf2 N] (n = 2, 3, 4, 6, 8) [Cn MIM][Tf2 N] (n = 2, 4, 6, 8) [Cn MIM][PF6 ] (n = 49) [Cn MIM][PF6 ] (n = 4, 6, 8) [R1 R2 MeIM][PF6 ], [R1 R2 MeIM][Tf2 N] [Cn MIM][Tf2 N] (n = 2, 4, 6, 8) [Cn MIM][PF6 ] (n = 49) [C4 MIM][PF6 ] [C4 MIM][PF6 ], [C6 MIM][PF6 ] [Cn MIM][PF6 ] (n = 4, 6, 8) [Cn MIM][BF4 ] (n = 1, 3, 6, 8, 10) [Cn MIM][PF6 ] (n = 6, 10) TSILs [C4 MIM][PF6 ]

Extractant/ligand/ metal chelator DC18C6 18C6, DC18C6, Dtb18C6 BOBCalixC6 DC18C6, N-alkyl aza-18-crown-6 ethers DC18C6 18C6, DC18C6, Dtb18C6 DC18C6 DC18C6, N-alkyl aza-18-crown-6 ethers DC18C6 Dithizone PAN, TAN Calyx[4]arene-bearing pyridine None None CMPO

Reference 21,37 18 38 39 37 18 19 39 37 23 20 40 41 28,35 32

Alkaline earth metals

Heavy and radioactive metals

Others

[C4 MIM][PF6 ], [C4 MIM][NO3 ], [C4 MIM][Tf2 N], [C6 MIM][PF6 ] [C8 MIM][PF6 ]

Dtb18C6, CMPO, TBP n/a

29,34 42,43

Note: Cn MIM = 1-alkyl-3-methylimidazolium; DC18C6 = dicyclohexano-18-crown-6; 18C6 = 18-crown-6; Dtb18C6 = 4,4 -(5 )-di-(tert-butylcyclohexano)-18-crown-6; BOBCalixC6 = calix[4]arene-bis(tert-octylbenzo-crown-6); Tf2 N = bis[(triuoromethyl)sulfonyl]amide; R1 R2 MeIM = 1-R1 -2R2 -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 efciency 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 signicance for the handling of nuclear materials. Earlier studies in the area included the behavior of uranium species in various ILs including mixtures of chloroaluminate ILs and butylpyridinium chloride,24,25 mixtures of chloroaluminate ILs and [C2 MIM]Cl,26 chloroaluminate ILs,27 and several RTILs.18,19,28 Recent work primarily focused on two aspects: (1) the fundamental understanding of ILs in nuclear chemistry such as radiochemical stability 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 difculty of separating them from ILs and the complexity of the system.28 As a new concept introduced in the late 1990s, Task-Specic 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
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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 Teon and emulsions.

IL EXTRACTIONS OF ORGANIC/BIO/BIOFUEL MOLECULES The high solubility of charged organic molecules in ILs has stimulated the development of organic product recovery by these green media. As illustrated in Table 2, phase partitions of many phenolic compounds are investigated in the ILwater biphasic systems. The distribution coefcient is highly inuenced 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 important role on the amino acid recovery (Table 2).45 Meanwhile, IL biphasic systems were also used to separate many other biologically important molecules
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Use of ionic liquids as green solvents for extractions

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

Substances Phenolic compounds phthalic acid, aniline, 4-hydroxybenzoic acid, benzoic acid, p-toluic acid, benzene, chlorobenzene, 1,2,4-trichlorobenzene, 1,4-dichlorobenzene, 4,4 -dichlorobiphenyl Phenol, tyrosol, p-hydroxybenzoic acid Chlorophenols Tryptophan, glycine, alanine, leucine, lysine, arginine Xylose, fructose, glucose, sucrose Glucose, sucrose, lactose, cyclodextrin Cellulose Lactic acid, acetic acid, glycolic acid, propionic acid, pyruvic acid, butyric acid Butyl alcohol (from fermentation broth) Erythromycin-A Olens (such as ethylene, propylene, and butanes) from parafns C4 8 diolen (such as butadiene) from C1 18 parafns [BMIM][PF6 ]

IL

Extractant None

Reference 44

Amino acids Carbohydrates

[Cn MIM][BF4 ] (n = 1, 3, 6, 8, 10) [Cn MIM][PF6 ] (n = 6, 10) [C4 MIM][PF6 ], [EMIM][Beti] [BMIM][PF6 ] [Cn MIM][X] (n = 4, 6, 8, 10; X = Cl , PF6 , BF4 ) [BMIM][dca] (carbohydrate solubility is approximately 200 g l1 ) [Cn MIM]X (n = 4, 6, 8) [Cn MIM][PF6 ] (n = 4, 6, 8)

None None DC18C6 None None None TBP (in some cases) Pervaporation was used None None None

41 58 45 46 47 59 48

Organic acids

Biofuels Antibiotic Hydrocarbons

[BMIM][PF6 ], [C8 MIM][PF6 ] [BMIM][PF6 ] [Cn MIM][X], [HPy][X] (n = 4, 6; X = BF4 , PF6 ) [BMIM][BF4 ]

49 50 54,55 56

Note: BMIM (or C4 MIM) = 1-butyl-3-methylimidazolium; EMIM = 1-ethyl-3-methylimidazolium; Beti = bis(peruoroethylsulfonyl)imide; HPy = Nhexylpyridinium; 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 carbohydrates are renewable and inexpensive resources for the chemical industry. The underivatized carbohydrates 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 nding 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 sufcient 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 olens (such as ethylene, propylene, and butanes) from parafns involved several steps:54,55 (1) salts (such as silver) were used to form complex olens;
J Chem Technol Biotechnol 80:10891096 (2005)

(2) the olen-containing mixture was extracted by the ionic liquid/salt solution, and the olens were adsorbed; (3) the olens were separated by desorption after the parafns were removed. Another process was developed to separate C4 8 diolen hydrocarbons (such as butadiene) from at least one diolen and at least one C1 18 parafn 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 reneries 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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their alkylated derivatives are very difcult 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-efciency and high effectiveness in getting rid of the low level of sulfur from fuels.

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 uids (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 lowpressure CO2 (<5.2 MPa) both hydrophobic and hydrophilic ILs can be separated from aqueous solution.80 This nding 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 ]MeOHscCO2 , 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 nding 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 enzymecatalyzed 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 ;

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
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Figure 1. Phase behavior of IL/H2 O/CO2 mixture at room temperature.81

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Use of ionic liquids as green solvents for extractions

(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 reactions include batchwise asymmetric hydrogenation of tiglic acid,86 batchwise hydrogenation of alkenes and carbon dioxide,87 continuous ow hydroformylation of oct-1-ene catalyzed by rhodium complexes,88,89 continuous ow hydrovinylation of styrene by immobilized 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 comparison study of imidazolium-based ILs, scCO2 and n-hexane for the biocatalysis of a transesterication reaction by immobilized enzymes has shown that the enzyme activity is strongly inuenced 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, continuous processes of Candida antarctica lipase B-catalyzed butyl butyrate synthesis and the kinetic resolution of 1-phenylethanol processes by transesterication;95 batchwise and continuous ow processes of acylation of octan-1-ol by vinyl acetate and the resolution of 1-phenylethanol both catalyzed by lipase from Candida antarctica;96 the transesterication reaction of N -acetyl-L-phenylalanine ethyl ester with 1propanol catalyzed by immobilized -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.

Because ILs are nonvolatile, they do not contaminate the gas stream during gas separation. The nonvolatility and selectivity of ILs allow them to be used in conventional absorbers, scrubbers or supported liquid membranes.104

SUMMARY The rst 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/NIHEARDA grant No. 5 G11 HD 32861-07 and by an NIH-MBRS grant. REFERENCES
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