Review

Received: 1 June 2012 Revised: 15 August 2012 Accepted: 29 August 2012 Published online in Wiley Online Library: 14 November 2012

(wileyonlinelibrary.com) DOI 10.1002/jctb.3935

Ionic liquids and deep eutectic solvents for biodiesel synthesis: a review
Hua Zhaoa and Gary A. Bakerb
Abstract
During the past decade, ionic liquids (ILs) have gained tremendous attention in nearly every branch of the chemical and physical sciences as designer (task-driven) and budding green solvent alternatives to conventional volatile organics. In particular, with a more in-depth understanding of their physicochemical properties, the active exploration of ILs as alternative solvents and/or catalysts in the chemical or enzymatic (biocatalytic) production of biodiesel has gained momentum. Most excitingly, very recent developments in the science of deep eutectic solvents (DESs) have initiated potentially more cost-effective approaches to biodiesel synthesis. At this stage, there is sufcient research completed to provide an important opportunity to stand back and assess the progress in the eld, critically examining the strengths and limitations for IL and DES technology in biodiesel synthesis. No such comprehensive evaluation exists. This work, therefore, seeks to bridge this gap by systematically reviewing the reported methods for biodiesel production which make use of ILs, either as (co)solvent components or catalysts, highlighting existing problems and limitations, with an emphasis placed on the future research required to bypass the hurdles to employing ILs in commercial biodiesel production. c 2012 Society of Chemical Industry Keywords: Biodiesel; ionic liquid; transesterication; triglyceride; alcoholysis; microalgae

INTRODUCTION
In the face of diminishing oil supplies, national security issues arising from reliance on imported crude oil, and the climate implications of the continued burning of fossil fuels (coal, oil, and natural gas), there has been global demand for the development of renewable energy sources that are not based on crude petroleum oil. This demand becomes more urgent with the environmental hazards of drilling and the risk of severe environmental disasters such as the recent Gulf of Mexico BP blowout/leak. As one of the alternative biological sources, biodiesel is becoming an attractive, renewable, CO2 neutral, and biodegradable fuel for diesel engines and heating systems. Biodiesel refers to an oil-based diesel fuel consisting of long-chain alkyl esters and is typically made by chemically reacting lipids with an alcohol to produce fatty acid monoesters. The National Biodiesel Board (USA) also has a technical denition of biodiesel as a mono-alkyl ester. Biodiesel can be prepared from abundant vegetable oils or animal fats (tallow),1 3 as well as other renewable sources of lipids including oleaginous microbial biomass (i.e. molds, yeasts, algae),4,5 soybean oil deodorizer distillate (SODD),6 and pine trees.7 It is important to point out that not all biodiesel is sustainable, particularly those relying on resources imported from other areas and using rain forestlands. Biodiesel has a comparable fuel economy as petroleum-based diesel, and can also reduce the emissions of polluting substances, such as particulate matter (PM), carbon monoxide, and hydrocarbon.8 Conventional chemical methods for preparing biodiesel have a number of limitations such as corrosion and emulsication problems, saponication of fatty acids, energy intensive operations, and high waste treatment. Therefore, because of these limitations, there is a lack of a commercially viable, efcient means for biodiesel production to
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make it a long-term viable substitute for crude oil energy sources in the quantities required to sustain our 21st century energy needs. As an alternative method to conventional chemical routes to biodiesel synthesis, the enzymatic approach seems very attractive due to its mild conditions, the use of green catalysts (mostly lipases), and low waste treatment. However, the enzymatic synthesis of biodiesel has itself been challenged by a number of difculties, one of which is the lack of lipase-compatible non-aqueous solvents. Now, fast-growing research on a new type of non-volatile solvent, named ionic liquids (ILs), has demonstrated their potential for effective enzyme stabilization and activation.9,10 There promises to be great benet from the development of low-cost ILs as alternative solvents for biodiesel synthesis. Despite numerous studies focusing on the application of ILs in the preparation of biodiesel and limited discussion on the subject,11 no in-depth review on this viable alternative technique exists to date. Many review articles on the subject of biodiesel have been published recently, including general reviews on chemical and enzymatic methods,12 16 and biodiesel production from different biomass feedstock17,18 (particularly from microalgae5,19 22 ). Therefore, to minimize the redundancy, we only briey outline some advantages and disadvantages of current technologies for biodiesel production.

Correspondence to: Hua Zhao, Chemistry Program, Savannah State University, Savannah, GA 31404, USA. Email: huazhao98@gmail.com; zhaoh@savannahstate.edu

a Chemistry Program, Savannah State University, Savannah, GA 31404, USA b Department of Chemistry, University of Missouri-Columbia, Columbia, MO 65211, USA

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www.soci.org A common synthetic route to biodiesel production is the transesterication (alcoholysis) of vegetable oils (or animal fats) with a primary aliphatic alcohol (methanol or ethanol). Typically, biodiesel comprises long-chain fatty acid methyl esters (FAMEs) obtained by the methanolysis of triacylglycerides (e.g. triolein), as summarized in Scheme 1. This reaction can be catalyzed by acids, alkaline metal hydroxides, alkoxides, and non-ionic bases (such as amines and amidines).23 However, these methods have several drawbacks: (1) acid/base processes are often related to corrosion and emulsication problems; (2) acid-catalyzed reactions are usually much slower than base-catalyzed processes,24,25 and may require a large excess of alcohol and high pressure (such as 170180 kPa);17 (3) the base-catalysis technology may cause unnecessary saponication of fatty acids,26 thus requiring a low content of free fatty acids in feedstock;17,27 (4) a large excess of alcohol is required to drive the equilibrium to the ester formation and to achieve the facile separation of biodiesel from the glycerol; furthermore, it creates recycling problems (such as the cost and the recovery of methanol); (5) practically, oils and fats are not soluble in alcohols, resulting in barriers for triglyceride conversions; and (6) other issues such as being energy intensive, alkaline waste-water treatment, and interference of free fatty acids and water.1 Therefore, a number of new approaches have been vigorously pursued to circumvent these problems, such as heterogeneous catalysis,28 34 alcoholysis in supercritical methanol,35 38 ILs-catalyzed transesterication,39 41 and lipasecatalyzed transesterication.1,6,42,43 By contrast, the enzymatic transesterication method offers many advantages over the chemical methods. The advantages include mild reaction conditions, low energy demand, low waste treatment, the reusability of enzymes (lipases in most cases), exibility in choosing different enzymes for different substrates, and allowing a small amount of water in substrates, etc.42,44 Therefore, the enzymatic synthesis of biodiesel is a greener alternative to chemical methods. However, the current lipase-catalyzed methods have some downsides that prevent this promising approach from being commercialized. These disadvantages include the high cost of enzymes, lipase inactivation by acyl acceptors such as methanol, and lipase inactivation by impurities in crude and waste oils.42 In addition, due to the poor miscibility between oils/fats and methanol, many enzymatic transesterication reactions are heterogeneous systems involving a complicated liquidliquid interface.42 To address the issue of methanol inhibition of lipases, a number of approaches have been studied, for example, a stepwise addition of methanol during the reaction,45 the use of other acyl acceptors such as methyl and ethyl acetate,46,47 enzyme immobilization,42,48 the use of other organic solvents such as t-butanol, hexane, n-heptane and 1,4dioxane,42,48,49 the use of fatty acid-containing feedstock,6 and the genetic modication of lipases for higher methanol tolerance.42 In addition to causing possible enzyme inactivation, the use of volatile organic solvents in biodiesel production creates potential environmental concerns and safety issues. Therefore, there is a great need for developing an alternative solvent for biodiesel production, such as ionic liquids (ILs). ILs consist of ions and remain liquid at temperatures lower than 100 C. Typical IL cations are nitrogen-containing (such as alkylammonium, N, N -dialkylimidazolium, N-alkylpyridinium and pyrrolidinium), or phosphorous containing (such as alkylphosphonium). The common choices of anions include halides, BF4 , PF6 , CH3 CO2 , CF3 CO2 , NO3 , Tf2 N [i.e., (CF3 SO2 )2 N] , [RSO4 ] , and [R2 PO4 ] . Some typical cations and

H Zhao, GA Baker

anions are illustrated in Scheme 2. As a new generation of nonaqueous solvents, ILs have many favorable properties such as low vapor pressure, a wide liquid range, low ammability, high ionic conductivity, high thermal conductivity, high dissolution capability toward many substrates, high thermal and chemical stability, and a wide electrochemical potential window.50 Because of these unique properties, ILs have been widely recognized as solvents or (co-)catalysts in a variety of applications including organic catalysis,50 53 inorganic synthesis,54 biocatalysis,9,10,53 polymerization,55 and engineering uids.56,57 More importantly, physical properties of ILs (such as polarity, hydrophobicity and hydrogen-bond basicity) can be nely tuned through the judicious selection of cations and anions. All these adjustable properties are crucial to the enzyme stabilization and activation; therefore, numerous enzymatic reactions have been investigated in different types of ILs.9,10,58,59 This review focuses on the reaction medium role of ILs for chemical and enzymatic preparation of biodiesel, the catalyst role of ILs in acid/base-catalyzed transesterication of triglycerides, and the extraction solvent role of ILs for biodiesel production processes. We also discuss the use of deep eutectic solvents for biodiesel synthesis since these solvents share some common properties with regular ILs. Finally, we lay out the challenges of employing ionic solvents in biodiesel preparation.

ILS AS (CO-)SOLVENTS FOR CHEMICAL AND ENZYMATIC PREPARATIONS OF BIODIESEL

There are only limited studies involving ILs as co-solvents for chemical preparation of biodiesel. DaSilveira Neto et al.33 used a tin-based catalyst [Sn(3-hydroxy-2-methyl-4-pyrone)2 (H2 O)2 ] for the methanolysis of soybean oil to biodiesel in [BMIM][InCl4 ], achieving a biodiesel yield of 83% in 4 h under reux condition. ESI-MS measurements suggest a cationic species is formed during the reaction via the substitution of pyrone ligand by alcohol, followed by the coordination of carboxylate compound to tin. Lapis et al.34 carried out the transesterication of soybean oil to prepare biodiesel using [BMIM][Tf2 N] as the co-solvent under acidic or basic conditions: acid catalysis with H2 SO4 resulted in >93% biodiesel yields; base catalysis with K2 CO3 (40 mol%) led to >98% biodiesel yields. Both types of reactions proceeded as multiphase systems where biodiesel formed the top layer and glycerol accumulated in the alcohol-IL-acid/base phase. The phase separation not only favorably drives the reaction equilibrium to the product side, but also simplies the biodiesel purication and glycerol recovery. The enzymatic transesterication of vegetable oils in ILs has been demonstrated by many groups in producing biodiesel.60 Ha et al.61 screened 23 different ILs for the methanolysis of soybean oil catalyzed by the immobilized Candida antarctica lipase (Novozym 435), and identied the hydrophilic ionic liquid (i.e. [EMIM][OTf]) as the best solvent for achieving the highest yield (80%) of fatty acid methyl esters at 12 h. On the other hand, Sunitha et al.62 obtained 9899% yields of fatty acid methyl esters within 10 h of methanolysis of sunower oil in hydrophobic [BMIM][PF6 ] and [EMIM][PF6 ] when catalyzed by Novozym 435; however, the same reaction in hydrophilic BF4 - based ILs gave very poor yields. Gamba et al.63 also utilized several ILs (i.e. [BMIM][Tf2 N], [BMIM][BF4 ] and
EMIM+ = 1-ethyl-3-methylimidazolium; BMIM+ = 1-butyl-3-methylimidazolium.

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Ionic liquids for biodiesel synthesis

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Scheme 1. Schematic illustration of the chemo- or bio-catalyzed synthesis of biodiesel by methanolysis of triolein (glyceryl trioleate).

Cation R1 + R4 N R2 R3 alkylammonium R1 + R4 P R2 R3 alkylphosphonium NC N

Anion O Cl O BF4O PF6CF3 S O O O _ O F3C S N S CF3 O O O R1O P O

CN

R1

+ N R2 N R pyridinium

imidazolium

N R1 R2 R1

+ N R2

O RO S O O

pyrrolidinium

piperidinium

OR2

Scheme 2. Structures of representative cations and anions in ILs.

[BMIM][PF6 ]) as solvents for the enzymatic transesterication of soybean oil, achieving over 90% biodiesel yields in 48 h. Arai et al.64 investigated the fungus whole-cell catalyzed production of biodiesel from soybean oil in two ILs ([EMIM][BF4 ] and [BMIM][BF4 ]), and observed that ionic solvents enabled the lipase to be more tolerant to methanol inhibition and allowed quantitative synthesis of biodiesel under optimized conditions. Yang et al.65 carried out the methanolysis of corn oil in [BMIM][PF6 ] catalyzed by Penicillium expansum lipase and obtained a 69.7% yield in 25 h. The Zhao group66 demonstrated that ether-functionalized ILs based on acetate (Scheme 3) were capable of dissolving oils and afforded high enzymatic activities in biodiesel synthesis. Ruzich and Bassi67 studied the Novozym 435-catalyzed transesterication of triolein with methyl acetate in [BMIM][PF6 ], and achieved 80% biodiesel yield under optimal conditions (i.e. 1:1 volume ratio of IL/oil, 14:1 molar ratio of methyl acetate/oil, 20% wt. of Novozym 435/wt. of oil, and 4855 C). The same group68 further conducted Novozym 435-catalyzed synthesis of biodiesel from triolein and waste canola oil using methyl acetate as the
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acyl acceptor and [BMIM][PF6 ] as the co-solvent. In a small-scale shake ask, 83% biodiesel yield was observed from triolein and 72% from waste canola oil; in a jacketed conical reactor, lower yields were obtained (54% from triolein and 30% from waste canola oil) due to poor mixing of two phases. Furthermore, this group69 suggested that the above enzymatic transesterication reaction followed the PingPong BiBi mechanism, and the use of [BMIM][PF6 ] actually lowered the initial reaction rates due to mass transfer limitations around the immobilized lipase. Ha et al.70 demonstrated a continuous operation (0.3750.75 mL h-1 ) of Novozym 435-catalyzed transesterication of vinyl laurate and 1-butanol in [OMIM][OTf] through a double-layer type continuous stirred tank reactor (Fig. 1). The advantage of this process is in situ removal of the product (butyl laurate), pushing the equilibrium to the product side. The highest product concentration of 2.71 mol L-1 was observed at a steady state of 0.375 mL h-1 ow rate. Lozano et al.71 indicate that triolein is soluble in [C18 MIM][Tf2 N] (m.p. 53 C); as a result, the Novozym 435catalyzed transesterication of triolein and methanol resulted

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+ N(CH2CH3)3
n

H Zhao, GA Baker

O
n

N + N

OAc

OAc-

Scheme 3. Imidazolium and ammonium based ILs consisting of alkyloxyalkyl-substituted cation and acetate anion (abbreviated as [CH3 (OCH2 CH2 )n -EtIm][OAc] and [CH3 (OCH2 CH2 )n -Et3 N][OAc], respectively) (n = 2, 3, . . . ).

Figure 1. Illustration of a double-layer type continuous stirred tank reactor for continuous production and in situ separation of butyl laurate: (1) feed reservoir, (2) pump, (3) reactor, (4) product phase, (5) inner reactor, (6) IL phase, (7) magnetic stirrer, and (8) product reservoir70 (Reproduced by permission of Elsevier).

in 96% biodiesel yield in 6 h. In another study, De Diego et al.72 found that triolein was soluble in hydrophobic ILs such as [C16 MIM][Tf2 N] and [C18 MIM][Tf2 N], and thus carried out a homogeneous transesterication of triolein with methanol in these two ILs catalyzed by Novozym 435, producing quantitative yields for at least six continuous operation cycles. Interestingly, at the completion of reaction, a three-layer mixture was formed: a top layer containing biodiesel, a middle layer containing glycerol and excess methanol, and a bottom layer containing IL and enzyme. This enables simple separation and purication of biodiesel. In addition, De Diego et al.73 systematically investigated the lipasecatalyzed transesterication of triolein in a series of imidazolium ILs with different alkyl chain lengths (C10 to C18 ) and different anions (Tf2 N , PF6 , and BF4 ), and found the lipase activity increased with the alkyl chain length to a maximum (the highest synthetic activity in [C16 MIM][Tf2 N]) and then decreased; the biodiesel yields of Novozym 435-catalyzed conversions of different oils in [C16 MIM][Tf2 N] after 24 h were in the range 9397%. Lozano et al.74 further developed a continuous enzymatic reactor, using Novozym 435 coated with hydrophobic ILs (i.e. [C18 MIM][Tf2 N]), for biodiesel synthesis from triolein in supercritical CO2 at 60 C and 180 bar, showing high operational stability of the lipase (up to 82% biodiesel yield after 12 cycles of 4 h). In addition, they observed that the lipase activity was improved by the increase in the IL anions hydrophobicity (Tf2 N > PF6 > BF4 ). Yu et al.75 suggest a synergistic effect of microwave irradiation and ionic solvent (such as [EMIM][PF6 ]) on Novozym 435-catalyzed transesterication of soybean oil with methanol; under microwave irradiation, a 92% yield of biodiesel was achieved in [EMIM][PF6 ] at optimized conditions, while only 70% yield was obtained under conventional heating. The Yang group76 achieved a higher biodiesel yield (86%) in [BMIM][PF6 ] than in t-butanol (52%) for

Penicillium expansum lipase-catalyzed transesterication of corn oil with methanol; they also observed negligible conversions when hydrophilic ILs (containing anions such as MeSO4 , OAc , NO3 , and H2 PO4 ) were used instead. Liu et al.77 examined the enzymatic transesterication of soybean oil with methanol in 19 ILs catalyzed by Burkholderia cepacia lipase, and suggested the lipase activity decreased with the order of anions PF6 > Tf2 N > OTf > BF4 > CH3 SO3 Cl . The highest biodiesel yield of 82% was observed in [OmPy][BF4 ], and it was argued that a low -helix content of the lipase in ILs (from FT-IR analysis) was responsible for the high enzyme activity. de los R os et al.78 investigated Novozym 435-catalyzed conversion of sunower and waste cooking oils to biodiesel in 10 different ILs. This group conrmed that the lipase activity was improved by decreasing the anions nucleophilicity (CALB activity in the order of PF6 , Tf2 N > OTf > BF4 ) and increasing the cations hydrophobicity. The triglyceride conversion was also affected by the methanol/substrate molar ratio, water content and IL viscosity. The highest sunower oil conversion of 60% was observed in [OMIM][PF6 ] at optimized conditions (methanol/sunower oil = 12:1 molar ratio, 1% water, 900 rpm, 40 C and 24 h). The Xu group79 evaluated the biodiesel synthesis by the enzymatic methanolysis of rapeseed oil in a number of ILs, and reported a 98% biodiesel yield in Ammoeng 102; the computer modeling study indicated that the amphiphilic property of Ammoeng 102 promotes efcient interactions between IL molecules and immiscible substrates, while different partition behaviors of biodiesel and glycerol in ionic solvent drive the reaction equilibrium to the product (biodiesel) side. The Yang group80 extracted about 41% (w/w) lipids from microalgae Chlorella vulgaris and also identied the main fatty acid composition; furthermore, they performed the enzymatic synthesis of biodiesel from microalgal oil in [BMIM][PF6 ] catalyzed
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Ionic liquids for biodiesel synthesis by Penicillium expansum lipase or Novozym 435, resulting in yields of 91% and 86%, respectively (only 49% and 44%, respectively, in t-butanol). Lozano et al.81 immobilized CALB onto new nanostructured supports (via a covalent attachment of 1-decyl-2methyimidazolium cations to a polystyrene divinylbenzene porous matrix), and demonstrated the high performance of immobilized lipase in catalyzing the methanolysis of triolein in both t-butanol and supercritical scCO2 (18 MPa and 45 C) with high yields (up to 95%). They also indicate that the presence of t-butanol in scCO2 is essential to prevent the blockage of enzyme active sites by polar glycerol.

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+ N CH2

SO3H

N + N CH 2 HSO4-

SO3H
n

HSO4a: n = 3; b: n = 4 HSO4+ N CH2 n SO3H

c: n = 3; d: n = 4

e: n = 3

Scheme 4. Structures of Brnsted acidic ILs.

ILS AS CATALYSTS IN BIODIESEL SYNTHESIS

There are many acidic ILs being prepared and used as catalysts for biodiesel synthesis. Wu et al.39 studied the transesterication of cottonseed oil with methanol catalyzed by Brnsted acidic ILs carrying sulfonic acid group in cations (Scheme 4). The catalytic efciency was correlated with the Brnsted acidity of IL catalysts, and thus 1-(4-sulfonic acid) butylpyridinium hydrogen sulfate (Scheme 4(b)) was identied as the best catalyst. A 92% biodiesel yield was obtained under an optimized condition (methanol:oil:IL = 12:1:0.057 (molar ratio) at 170 C for 5 h). Zhang et al.82 also prepared a number of Brnsted acidic ILs and applied them as catalysts for the esterication of long-chain fatty acids (such as oleic acid, stearic acid, myristic acid, palmitic acid and mixed acids); they further chose N-methyl-2-pyrrolidonium methyl sulfonate ([NMP][CH3 SO3 ]) as the best and recyclable catalyst giving 9495% yields at 70 C for 8 h under optimum conditions. Han et al.40 obtained up to 94% biodiesel yield when the transesterication of waste oils with methanol was catalyzed by a sulfonic acid group-containing IL at 170 C for 4 h. Liang et al.41 performed the conversion of soybean oil to biodiesel catalyzed by a chloroaluminate type of IL, [Et3 NH]Cl-AlCl3 (x (AlCl3 ) = 0.7), and achieved a 98.5% yield with no saponication under the optimum reaction conditions. Liang and Yang83 prepared a multi SO3 H functionalized Brnsted acidic IL (Scheme 5) as the catalyst for biodiesel synthesis from rapeseed oil and methanol, achieving a 98% biodiesel yield under optimized conditions. Li et al.84 found that acidic N-((4-sulfo)butyl)pyridinium triuoromethylsulfonate was capable of catalyzing the transesterication of Jatropha oil with methanol at 100 C to obtain up to 92% biodiesel yields. Guo et al.85 found that the mixture of [BMIM][CH3 SO3 ] and FeCl3 could be an effective catalyst for the conversion of Jatropha oil with a high-acid value (13.8 mg KOH/g) to biodiesel, where metal ions in ILs acted as Lewis acidic sites. A high biodiesel yield of 99.7% was achieved at an optimal condition of 45 g Jatropha oil, 9 mmol [BMIM][CH3 SO3 ]-FeCl3 (mole fraction of FeCl3 : 0.7), methanol/oil molar ratio 6/1, 120 C, and 5 h. Due to a high free fatty acids (FFA) value in the crude palm oil, Elsheikh et al.86 suggest a two-step process: esterication of FFA catalyzed by Brnsted acidic ILs (i.e. [BMIM][HSO4 ]), and KOH-catalyzed transesterication of triglycerides. For the rst step, a 91% FFA conversion was obtained under optimal conditions (4.4 wt% [BMIM][HSO4 ], methanol/crude palm oil = 12:1 molar ratio, 160 C, 600 rpm and 2 h); the second step was carried out at 1.0 wt% KOH, methanol/oil = 6:1 molar ratio, 60 C, 600 rpm and 1 h, achieving an overall biodiesel yield of 98%. Ghiaci et al.87 prepared a number of Brnsted acidic ILs derived from 1-benzyl-1H-benzimidazole,
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SO3H HSO3 N+ N+ N + N+ SO3H 4 HSO4-

SO3H
Scheme 5. A multi -SO3 H functionalized Brnsted acidic IL.

and found that one of them [3,3-(hexane-1,6-diyl)bis(6-sulfo-1(4-sulfobenzyl)-1H-benzimidazolium) hydrogensulfate] produced the highest catalytic activity (95% yield in 5 h) and best recyclability in the transesterication of canola oil with methanol. This acidic IL could also catalyze the transesterication of other vegetable oils and alcohols, achieving satisfactory yields (8595%). The production separation was straightforward as three layers were formed after the reaction: upper biodiesel layer, middle glycerol layer and bottom IL catalyst layer. The same group88 further demonstrated that the bentonite organoclay modied by 3,3-(butane-1,6-diyl)bis(6-sulfo-1-(4-sulfobenzyl)-1Hbenzimidazolium) hydrogensulfate was effective in catalyzing the esterication of long-chain fatty acids (such as oleic acid, lauric acid, palmitic acid and stearic acid) to their methyl esters in 6 h with yields of 8698%. Zhou et al.89 reported that ve Brnsted acidic ILs (carrying propyl sulfonic acid groups on their cations) showed high catalytic activities and reusability toward the biodiesel preparation from tung oil. Fang et al.90 studied the esterication of free fatty acids with low alcohols (from methanol to butanol) catalyzed by dicationic acidic ILs (Scheme 6), and found that the reaction mixture became homogeneous one-phase upon heating to 70 C and the product settled as a separate layer after cooling. High conversions (9396%) were obtained with this new reaction system, and the catalyst could be reused at least six times with little loss in activity. The same system was also applied to soybean for biodiesel production, achieving up to 94% conversions. Although basic ILs are not commonly used as catalysts in biodiesel synthesis, Zhou et al.91 investigated several imidazolium hydroxides (such as [BMIM][OH]) as recyclable catalysts for the transesterication of glycerol trioleate with methanol, and obtained a biodiesel yield of 87% at 120 C for 8 h (methanol/triglyceride = 9:1 molar ratio).

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HO3S HSO4-

+ N

+ N
n

SO3H
HO

+N

X-

HSO4X = Cl or OAc

n = 2, 3 or 6
Scheme 6. Structures of dicationic acidic ILs.

Scheme 7. Structures of cholinium salts (choline chloride and choline acetate).

BIODIESEL SYNTHESIS IN DEEP EUTECTIC SOLVENTS

Recently, the Abbott group92-94 demonstrated that a mixture of solid organic salt and a complexing agent can form a liquid at temperatures below 100 C, so-called deep eutectic solvents (DES), or deep eutectic ILs (DEILs). The mechanism is that the complexing agent (typically a H-bond donor) interacts with the anion and increases its effective size, which in turn reduces the anion interaction with the cation and thus decreases the freezing point (Tf ) of the mixture. A classic example is the mixture of choline chloride (m.p. = 302 C, 2-hydroxyethyl-trimethylammonium chloride, Scheme 7) and urea (m.p. = 133 C) in a 1:2 molar ratio resulting in a room-temperature liquid (Tf = 12 C).92 Although the research community is ambivalent on whether these deep eutectic solvents should be formally classied as ILs because they contain a signicant molecular component, they denitely share a number of attractive solvent features with regular ILs. The major advantage of this approach is that inexpensive and non-toxic compounds can be used and the properties of the liquid can be nely tuned with different combinations of organic salts and complexing agents. Considering that many inexpensive quaternary ammonium salts are available and there is a wide choice of amides, amines, carboxylic acids, alcohols and metal salts that can be used as complexing agents,93 97 the possibility of forming new and inexpensive eutectic ILs is enormous. In particular, choline chloride, so called vitamin B4 , is produced on the scale of Mtonne (million metric tons) per year as an additive for chicken feed and many other applications. This ammonium salt is not only cheap and easy to make, but also non-toxic and biodegradable. Therefore, eutectic ILs based on cholinium can be biodegradable and inexpensive. The Dom nguez de Mar a group98 formed new eutectic ILs by pairing choline chloride with renewable levulinic acid or sugar-based polyols, and suggest that the addition of glycerol leads to lower viscosities. In addition, eutectic ILs can dissolve many metal salts, aromatic acids, amino acids, glucose, citric acid, benzoic acid and glycerol.92,93,99 101 Also, choline chloride is an essential micronutrient and human nutrient,102 and cholinium alkanoates (including acetate) are environmentally benign and biodegradable.103 One major application of cholinebased eutectic solvents is electrodeposition and electropolishing of metals,99,104,105 which has been reviewed for several types of eutectics.106 108 In addition, these new solvents are being actively exploited as benign solvents for a number of chemical and enzymatic reactions.59 The following section focuses on their utilizations as catalysts or (co-)solvents in biodiesel preparation. The eutectic mixture of choline chloride and zinc chloride (1:2 molar ratio) was used as a Lewis acidic catalyst (Zn2 Cl5 as predominant species) for the transesterication of soybean oil with methanol, resulting in a 55% conversion under optimum conditions (methanol/oil molar ratio 16:1, 10% catalyst, 70 C and 72 h).109 A similar transesterication of palm oil catalyzed by choline chloride/ZnCl2 (1:2) or choline chloride/FeCl3 (1:2)

along with 95 vol% H2 SO4 produced up to 92% methyl ester.110 However, these eutectic mixtures involving metal halides usually have relatively high freezing points (usually > 25 C) and very high viscosities (such as 281 Pa s at 25 C for choline chloride/ZnCl2 at 1:2).96,109 More recently, Zhao et al.111 developed biocompatible eutectic ILs (such as choline chloride/glycerol at 1:2 and choline acetate/glycerol at 1:1.5) that were capable of maintaining high CALB activity and stability, advocating their promising application in the enzymatic preparation of biodiesel. In addition, those eutectic solvents derived from cholinium salts and glycerol have lower viscosities (80 mPa s at 50 C) than that of choline chloride/urea 1:2 (120 mPa s at 50 C).111 Furthermore, choline chloride/glycerol (1:2 molar ratio) was evaluated as a co-solvent in Novozym 435-catalyzed transesterication of soybean oil with methanol to achieve up to 88% triglyceride conversions in 24 h.112

ILS AS EXTRACTION SOLVENTS IN BIODIESEL PRODUCTION

ILs have also been used as extraction solvents in biodiesel production for different purposes: (a) lipid extraction from biomass; (b) extraction of free fatty acids (FFA) before reaction; (c) extraction of glycerol from biodiesel after reaction; and (d) extraction of unsaturated fatty acid esters from biodiesel. Lipid extraction from biomass Young et al.113 discovered that a mixture of methanol and [EMIM][MeSO4 ] (mass ratio 1.2:1) was effective for extracting lipids out of microalgae and different oil seeds; instead of dissolving the lipids, the solvent mixture allowed the auto-partition of lipids to a separate immiscible phase for easy harvesting. A similar study by Kim et al.114 indicates that 1:1 (v/v) mixtures of methanol and ILs (such as [BMIM][CF3 SO3 ] and [EMIM][MeSO4 ]) are capable of dissolving algal biomass, leaving lipids insoluble as a separate layer. The total lipids recovered by some IL mixtures were higher than the with Bligh and Dyers method, and such an improvement could be attributed to the dipolarity/polarizability and hydrogenbond acidity of ILs (rather than their hydrogen-bond basicity) as conrmed by a multi-parameter regression based on the linear solvation energy relationship. Extraction of free fatty acids Manic et al.115 examined the use of ILs (i.e. Ammoeng 100 and [BMIM][dca]) and PEGs (Mw = 200, 400, 2000 and 4000) as alternative solvents for removing FFA (linoleic acid as a model acid) from soybean oil. The liquidliquid phase equilibrium data suggest that ILs and PEGs are fully miscible with linoleic acid, but not miscible with soybean oil. In particular, the highest values of linoleic acid distribution coefcient were observed in Ammoeng 100. That study implied the high potential of using these solvents for biodiesel deacidication.
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Ionic liquids for biodiesel synthesis

www.soci.org Although great strides have been made on the laboratory bench, several obstacles remain to employing ILs in industrial-scale biodiesel production, including: (1) the high cost of ILs, particularly those based on the imidazoliums and pyridiniums. One alternative is to develop low-cost ILs such as those derived from less expensive alkylammonium and piperidinium salts, or the use of DESs based on inexpensive choline salts; (2) the high viscosities common to most ILs, which may limit mass-transfer kinetics, causing poor operability. The judicious incorporation of ether chains in the cations or the selection of viscosity-reducing anions (e.g. dicyanamide, tricyanomethanide, tetracyanoborate, thiocyanate) may aid in lowering IL viscosities;59,121 and (3) concerns over IL toxicity122 124 and biodegradability.123 125 In particular, as promising and inexpensive alternatives to conventional ILs, DESs deserve more attention as benign reaction media for the chemical and enzymatic preparation of biodiesel. Another important aspect of future work in this area will include extending these approaches to non-edible oils (e.g. castor, jatropha, rubber seed, polanga, karanja) which do not compete with potential food sources. The economic viability of biodiesel production can also be enhanced by implementing used cooking oils, which are otherwise wasted and are available throughout the world, especially in developed countries (e.g. fast food restaurant chains). An additional advisable path forward is the greater consideration of alternative inexpensive lipases such as Penicillium expansum lipase, as well as the stimulating but grander challenge of designing articial lipase mimics for use in ILs. Studies directed at devising nanoscale or porous enzyme supports to enhance the thermal, solvent, and operational stability of lipases are also warranted. Finally, accomplishing the enhanced and expedient recovery of ILs with minimal energy expenditure so that they may be recycled and reused is an imposing problem seeking solution, both within the area of biodiesel synthesis and ubiquitously within the wider eld of IL research itself.

Salt/glycerol (1:1)

Biodiesel + Glycerol

Biodiesel DES

Scheme 8. Extraction of glycerol from biodiesel via forming DES.

Extraction of glycerol from biodiesel Interestingly, some deep eutectic solvents were found capable of removing glycerol from biodiesel product (Scheme 8). A 1:1 mixture of quaternary ammonium saltglycerol was used to extract glycerol from biodiesel product mixtures, and salts including choline chloride, [ClEtMe3 N]Cl, and [EtNH3 ]Cl were most effective in glycerol removal.101 The mixture of choline chloride/glycerol (1:1) was found effective in extracting glycerol from biodiesel, resulting in 51 wt% of glycerol removal when the biodiesel/eutectic mixture ratio was kept at 1:1 (molar ratio).116 In addition, choline chloride/ethylene glycol (1:2.5 molar ratio) and choline chloride/2,2,2-triuoroacetamide (1:1.75, molar ratio) were shown effective in glycerol removal from palm oil based biodiesel.117 Shahbaz et al.118 indicate that eutectic solvents formed between methyltriphenylphosphunium bromide and ethylene glycol (or triethylene glycol) are effective in removing glycerol, as well as monoglycerides and diglycerides, from palm oil-based biodiesel. Extraction of unsaturated fatty acid esters from biodiesel To reduce NOx emissions and to improve the oxidation stability of biodiesel, Li et al.119 extracted unsaturated fatty acid esters (i.e. methyl linolenate (18:3) and methyl linoleate (18:2)) from soy-derived biodiesel using -complexing sorbents. The new sorbents were constructed by covalently attaching ILs (the imidazolium type of PF6 and BF4 ) onto silica followed by coating these silica-supported ILs with silver salts (AgBF4 or AgNO3 ). One of the sorbents (AgBF4 /SiO2 Im+ PF6 ) exhibited a higher sample capacity and selectivity in extracting 18:3 ester than conventional sorbents. A similar study by this group120 reported the high selectivity of a new adsorbent based on mesoporous silica (SBA-15) (i.e. AgBF4 /SBA-15HPSiOEtIM+ PF6 ) for separating polyunsaturated triacylglycerols such as linolenin.

ACKNOWLEDGEMENTS
The support by Henry Dreyfus Teacher Scholar Award is acknowledged. We also thank Dr. Wei He at University of Tennessee, Knoxville for providing reprints of papers.

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In biodiesel production, ILs can perform several different vital roles, acting variously as acid/base catalyst, (co)solvent for chemical or enzymatic reaction, and as extraction solvent. Many ILs have already demonstrated high potential in biodiesel production, with substantial benets, such as high product yield, compatibility with enzyme catalysts, and facile post-synthetic separation (i.e. biodiesel generally forms as an upper layer whilst glycerol and ILs form other layers), bringing some added values to classic biodiesel synthesis. When selecting or designing an IL intended for biodiesel applications, several factors must be considered, keeping these goals in mind: (1) as catalysts or solvents, the ideal system must achieve a high biodiesel yield under mild conditions within a relatively short reaction time; (2) during enzymatic preparation, the solvent should allow the maintenance of high lipase activity and confer stability in the presence of methanol and glycerol; (3) the components should demonstrate low toxicity and high biodegradability, as well as being (4) relatively inexpensive.
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