Fuel Processing Technology 91 (2010) 116120

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Fuel Processing Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / f u p r o c

A novel technique for separating glycerine from palm oil-based biodiesel using ionic liquids
Maan Hayyan a, Farouq S. Mjalli a,, Mohd Ali Hashim a, Inas M. AlNashef b
a b

University of Malaya, Chemical Engineering Dept., Kuala Lumpur, Malaysia King Saud University, Chemical Engineering Dept., Riyadh, Saudi Arabia

a r t i c l e

i n f o

a b s t r a c t
Biodiesel production from abundant bio-sources has drawn the attention of the academic as well as the industrial communities in recent years. However, one of the most serious obstacles for using biodiesel as an alternative fuel is the complicated and costly purication processes involved in its production. The difculties involved in the separation of glycerine and other un-reacted reactants and by-products necessitate the development of new competent low cost separation processes for this purpose. In this work, a low cost quaternary ammonium saltglycerine-based ionic liquid is proposed as a solvent for extracting glycerine from the transesterication biodiesel product. The separation technique was tested on palm oil-based produced biodiesel with KOH as a reaction catalyst. The study investigated the effect of DES:biodiesel ratio and the DES composition on the efciency of the extraction process. The lab scale purication experiments proved the viability of the separation technique with a best DES:biodiesel molar ratio of 1:1 and a DES molar composition of 1:1 (salt:glycerine). The puried biodiesel fullled the EN 14214 and ASTM D 6751 standard specications for biodiesel fuel in terms of glycerine content. A continuous separation process is suggested for industrial scale application. 2009 Elsevier B.V. All rights reserved.

Article history: Received 10 June 2009 Received in revised form 3 September 2009 Accepted 4 September 2009 Keywords: Ionic liquids Biodiesel Glycerine Liquidliquid extraction

1. Introduction Biodiesel is a clean-burning diesel fuel produced from vegetable oils, animal fats, or grease. Its chemical structure is that of fatty acid alkyl esters (FAAE). Biodiesel as a fuel gives much lower toxic air emissions than fossil diesel. In addition, it gives cleaner burning and has less sulfur content, and thus reducing emissions. Because of its origin from renewable resources, it is more likely that it competes with petroleum products in the future. To use biodiesel as a fuel, it should be mixed with petroleum diesel fuel to create a biodiesel-blended fuel. Biodiesel refers to the pure fuel before blending. Commercially, biodiesel is produced by transesterication of triglycerides which are the main ingredients of biological origin oils in the presence of an alcohol (e.g. methanol, ethanol) and a catalyst (e.g. alkali, acid, enzyme) with glycerine as a major by-product [1,2]. After the reaction, the glycerine is separated by settling or centrifuging and the layer obtained is puried prior to using it for its traditional applications (pharmaceutical, cosmetics and food industries) or for the recently developed applications (animal feed, carbon feedstock in fermentations, polymers, surfactants, intermediates and lubricants) [3].

Corresponding author. E-mail address: farouqsm@yahoo.com (F.S. Mjalli). 0378-3820/$ see front matter 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.fuproc.2009.09.002

Due to being renewable, having better quality of exhaust gas emissions and its biodegradability, biodiesel is becoming very popular in the European Union (EU) which has set an objective to secure for motor biofuels a market share of 20% of total motor fuel consumption by 2020. By 2010, the United States is expected to become the world's largest single biodiesel market, accounting for roughly 18% of world biodiesel consumption, followed by Germany. New and large single markets for biodiesel are expected to emerge in China, India and Brazil [46]. However, one of the most serious obstacles to use biodiesel as an alternative fuel is the complicated and costly purication processes involved in its production. Therefore, biodiesel must be puried before being used as a fuel in order to full the EN 14214 and ASTM D6751 standard specications listed in Table 1; otherwise the methyl esters formed cannot be classied as biodiesel. Removing glycerine from biodiesel is important since the glycerine content is one of the most signicant precursors for the biodiesel quality. Biodiesel content of glycerine can be in the form of free glycerine or bound glycerine in the form of glycerides. In this work we refer to the total glycerine, which is the sum of free glycerine and bound glycerine. Severe consequences may result due to the high content of free and total glycerine, such as buildup in fuel tanks, clogged fuel systems, injector fouling and valve deposits. The traditional means of removing glycerine is mainly by gravity separation or centrifugation. The methanol may in some cases be

M. Hayyan et al. / Fuel Processing Technology 91 (2010) 116120 Table 1 Biodiesel specications according to EN 14214, and ASTM D6751 standards. Property EN 14214 Test method Ester content Linolenic acid content Content of FAMEa with 4 double bonds MAGb content DAGc content TAGd content Free glycerine Total glycerine Water and sediment or water content Methanol content (Na + K) content (Ca + Mg) content P content Oxidative stability (110 C) Density (15 C) Kinematic viscosity or viscosity (40 C) Flash point Cloud point Sulfur content Carbon residue Cetane number Sulphated ash Total contamination Copper strip corrosion (3 h, 50 C) Acid number or acid value Iodine value Distillation temperature (90% recovered)
a b c d

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ASTM D 6751 Limits 96.5% (mol mol ) min 12.0% (mol mol 1) max 1.0% (mol mol 1) max 0.80% (mol mol 1) max 0.20% (mol mol 1) max 0.20% (mol mol 1) max 0.02% (mol mol 1) max 0.25% (mol mol 1) max 500 mg kg 1 max 0.20% (mol mol 1) max 5.0 mg kg 1max 5.0 mg kg 1 max 10.0 mg kg 1 max 6 h min 860900 kgm 3 3.55.0 mm2 s 1 120 C min 10.0 mg kg 1 max 0.30% (mol mol 1) max 51 min 0.02% (mol mol 1) max 24 mg kg 1 max 1 (degree of corrosion 0.50 mg KOH g 1 max 120 g I2100 g 1 max
1

Test method ASTM D 6584 ASTM D 6584 ASTM D 2709 UOP 391 ASTM D 4951 ASTM D 445 ASTM D 93 ASTM D 2500 ASTM D 5453 ASTM D 4530 ASTM D 613 ASTM D 874 ASTM D 130 ASTM D 664 ASTM D 1160

Limits 0.020% (w/w) max 0.240% (w/w) max 0.050% (v/v) max 5.0 mg kg 1max 0.001% (w/w) max 1.96.0 mm2 s 1 130 C min Not specied 0.05% (w/w) max 0.050% (w/w) max 47 min 0.020% (w/w) max No. 3 max 0.50 mg KOH g 1max 360 C max

EN 14103 EN 14103 EN 14105 EN 14105 EN 14105 EN 14105 EN 14105 EN ISO 12937 EN 14110 EN 14108 prEN 14538 EN 14107 EN 14112 EN ISO 3675 EN ISO 3104 EN ISO 3679 EN ISO 20864 EN ISO 10370 EN ISO 5165 ISO 3987 EN 12662 EN ISO 2160 EN 14104 EN 14111

FAME = fatty acid methyl esters. MAG = monoacylglycerines. DAG = diacylglycerines. TAG = triacylglycerine.

removed using ash evaporation. Neither process is 100% efcient hence a nal purication stage is needed in order to meet the requirements of EN 14214 and ASTM D 6751 Standards. The untreated biodiesel contains several impurities namely; free and total glycerine, soap, metals, methanol, free fatty acids (FFA), catalyst, water, and glycerides. The engine life can be reduced by high levels of impurities [7]. Several methods have been used to separate fatty acid methyl esters (FAME) from other components. However, there are two generally accepted methods to purify biodiesel: wet and dry washing. The more traditional wet washing method is widely used to remove excess contaminants and leftover production chemicals from biodiesel. Since both glycerine and methanol are highly soluble in water, water washing is very effective in removing both contaminants and until recently was the most common method of purication. It also has the advantage of removing any residual sodium salts and soaps, the latter being a byproduct of high FFA feeds, due to their water solubility. However, the inclusion of additional water to the process offers many disadvantages, including increased cost and production time. A highly polluting liquid efuent is generated. Signicant product loss can be carried out for retention in the water phase. Furthermore, emulsion formation when processing used cooking oils or other feeds with high FFA content can happen due to the soap formation [7,8]. Dry washing replaces water with an ion exchange resin or a magnesium silicate powder to neutralize impurities. Both dry washing methods are being used in industrial plants. Other methods are used to purify biodiesel such as using membrane reactors, and the addition of lime and phosphoric acid [911]. Nonetheless, there are numerous problems associated with the costs and complications of operating biodiesel synthesis on an industrial scale [1]. Ionic liquids (ILs) have been accepted as a new green chemical revolution which excited both the academia and the chemical industries. This new chemical group can reduce the use of hazardous and polluting organic solvents due to their unique characteristics as well as taking part in various new syntheses. ILs are known as salts

that are liquid at or below 100 C in contrast to high-temperature molten salts [12,13]. As solvents, ILs possess several advantages over conventional organic solvents, which make them environmentally compatible [14 20]. Among these favourable characteristics, is their ability to dissolve many different organic, inorganic, and organometallic materials and their high polarity. They are immiscible with many organic solvents; moreover, the solvation properties of ILs can be tuned for a specic application by varying the anioncation combinations. In addition to all these properties, ILs have very low vapour pressure making them less ammable and safe for industrial application. However, the environmental fate and any potential toxicity issues for most ILs are still largely unknown and up to the present, only a few preliminary reports on the toxicological properties of them were available. The development of low cost ionic liquids (ILs) termed deep eutectic solvents (DES) has recently received intense interest due to their potential as environmentally benign solvents and their unusual solvation properties. A DES is a mixture of two or more compounds which has a melting point lower than that of either of its components. They are liquids at temperatures of 100 C or below and exhibit similar solvent properties to the conventional ILs. They comprise mixtures of organic halide salts, such as choline chloride with an organic compound which is a hydrogen bond donor (HBD) capable of forming a hydrogen bond with the halide ion, such as amides, amines, alcohols, carboxylic acids and many more [21]. The liquid state of DES is produced through freezing point depression, whereby hydrogen-bonding interactions between an anion and an HBD are more energetically favoured relative to the lattice energies of the pure constituents [22]. DESs have several advantages over traditional ionic liquids in that they are easy to prepare in a pure state. They are nonreactive with water. Furthermore, toxicological properties of the components used for DES have been determined and are available, with some DES being biodegradable [23].

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Few large-scale applications for the DESs are readily available. Electro winning of metals from complex oxide matrices and the electro polishing of stainless steel are two applications of DESs due to their unexpected solvent properties which enable them to dissolve metal oxides. Like other conventional ionic liquids, one issue that is associated with the use of DESs is their viscosity compared to molecular solvents. This has a concomitant effect upon the conductivity, which is important for electrochemical applications such as those mentioned above [24]. Recently, Abbott et al. [25] have shown that low cost ionic liquids called deep eutectic solvents DESs are successful as extraction media for glycerine from biodiesel product mixtures. The main objective of this work is to use quaternary ammonium saltglycerine based DES in the removal of total glycerine from palm oil based biodiesel. The process is then optimized for the best ratio of DES composition. Moreover, the biodiesel to DES ratio is also investigated in terms of its extraction capabilities. Our target is to produce glycerine puried biodiesel according to the EN 14214 and ASTM D6751 Standards. 2. Experimental methodology For the synthesis of biodiesel, the following materials were used: rened palm oil (FFM Sdn Bhd), methanol (Merck 99%), and potassium hydroxide (KOH) as a catalyst (HMGM Chemicals >98%). Methanol and potassium hydroxide were pre-mixed to prepare potassium methoxide, and then added to palm oil in the reactor with a mixing speed of 400 rpm for 2 h at 50 C. The molar ratio of palm oil to methanol was 1:10. Finally, the mixture was left overnight to settle forming two layers, namely: biodiesel phase (upper layer) and the glycerine-rich phase (lower layer). To prepare the DESs used in this work choline chloride (ChCl) (Merck 99%) was dried under vacuum, and mixed with glycerine (Merck 99.5%) in different ChCl to glycerine mole ratios (1:1, 1:1.25, 1:1.5, 1:2, and 1:3). The mixture was stirred at 300 rpm and 50 C for a period of 1 h until a homogenous transparent liquid was formed. The DES was then added to the biodiesel phase in different quantities according to the biodiesel:DES molar ratios of (1:1, 1:1.5, and 1:2). The samples were agitated using a shaker for 1 h at 170 rpm and nally left for settling for 2 h. Samples of 0.5 g were collected from the upper layer after settling. The samples were ltered with a vacuum lter and mixed with 5 ml of the solvent tetrahydrofuran (THF) under stirring. The analysis was done using HPLC (Waters 600E) with an auto sampler and differential refractive index detector. The HPLC specications and analysis conditions are given in Table 2. The refractive index detector was purged for at least one hour prior to

use and monitored for a steady baseline. System suitability test was run. The HPLC system was examined to ensure that the system suitability test was acceptable. When the system suitability test was accepted, the collected samples were run. 3. Results and analysis 3.1. Biodiesel production Palm oil was selected as the feedstock for biodiesel production. This selection was based on the fact that this biomaterial is readily available in huge quantities and has relatively low production costs in South East Asian countries in general and particularly in Malaysia. The transesterication reaction product is puried from the glycerine byproduct using liquidliquid extraction with DES as a solvent. KOH and methanol were chosen to synthesize the biodiesel due to their ability to convert triglyceride to fatty acid methyl esters (FAME). Palm oil to methanol ratio of 1:10 was selected to produce biodiesel since this ratio gives the best yield and quality, lower glycerine by-product as well as lower fatty acid free residual [26]. Following biodiesel synthesis, free glycerine was separated from crude biodiesel by gravity settling. Analysis using HPLC showed that 0.28 wt.% total glycerine was still there in the rened biodiesel. This value is higher than that acceptable by international standards (EN 14214 and ASTM D 6751) for the total biodiesel glycerine content. 3.2. Extraction of glycerine Choline chloride:glycerine mixture was selected to form a DES in different ChCl:glycerine mole ratios. Fig. 1 shows the freezing points and the viscosities of the mixture as a function of glycerine mole fraction [24]. As indicated in the gure, the minimum eutectic temperature and viscosity was achieved at 0.67 glycerine mole fraction. The DES molar ratios under investigation of 1:1 to 1:3 (corresponding to 0.50.75 glycerine molar fractions in Fig. 1) attained the lowest viscosity and freezing point ranges (293.8316.7 cP and 281.8240.5 K respectively). Lower solvent viscosity enhances the mixing efciency and consequently the mutual mass transfer rate of glycerine between the two phases. Moreover, using DES that has the lowest freezing point increases the amount of glycerine that can be extracted without causing the freezing point of the DES to increase above the process temperature. This in turn improves the solvent extractive capabilities. The synthesized DES was used to extract the glycerine from the synthesized biodiesel. Three molar ratios of biodiesel to DES were investigated, namely, 1:1, 1:1.5, and 1:2. Two distinct layers of the two phases were observed after settling. The analysis revealed that the DES is completely separable and no emulsion was formed. The amount of glycerine extracted as a function of DES composition is depicted in Fig. 2. In general, it was found that all ratios can reduce the

Table 2 HPLC specications and analysis conditions. Analytical instruments HPLC system

Column Guard column Analytical conditions Mobile phase Flow rate Column temperature Detector temperature Sparge gas Sparge rate Detector sensitivity Injection volume

Waters HPLC pump Waters 600E system controller Waters model 401 Differential Refractive Index Detector Waters 717 Plus Auto sampler Waters Millennium software Size: 300 7.8 mm Description: Phenogel 5 U 50 A 50 7.8 mm

THF, HPLC grade 1 mL/min, isocratic 25 C 35 C Helium 30 mL/min 32 10 L

Fig. 1. Diagram of DES freezing points and viscosities at different glycerine mole fractions, (Abbott et al. [25]).

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of 1:1.5 and 1:2 extractive feed ratios) biodiesel:DES mixtures for selectively dissolving more glycerine from the biodiesel phase. Additionally, the distribution coefcient prole for the higher DES composition molar ratios of 1:1.5 to 1:3 (0.60.75 glycerine molar fraction in DES) are at which indicates the minor effect of increasing glycerol content of the DES above the optimum composition values of 1:1 or 1:1.25. Table 3 gives the relative percentage of extracted glycerine for the three tested DES ratios. It is clear from the results shown in the table that the biodiesel:DES ratio is more effective than the DES composition ratio in improving the extraction efciency. Changing the biodiesel:DES ratio from 1:1.5 to 1:1 resulted in more than doubling the extracted glycerine. On the other hand, a similar DES composition ratio change resulted in a 10% increase in the extracted glycerine.
Fig. 2. Total glycerine left in the biodiesel after extraction.

3.3. Solvent recovery In order to justify the use of DES as a probable solvent for glycerine from biodiesel, it is crucial to come up with feasible recovery of choline chloride from the used DES after extraction. There are many methods to recover the salt from the used DES extract phase. Although distillation lends itself as a candidate separation method, however due to the high boiling point of glycerine (182 C at 20 mm Hg), distillation becomes an energy intensive process, but a possible one. In this case vacuum distillation may replace conventional distillation to reduce the energy requirements. Another possible separation method is to re-crystallize the choline chloride, either by cooling or by addition of an anti-solvent. In this work, 1-butanol was used as an anti-solvent and mixed with the extract phase. 1-butanol to extract phase were prepared in two compositions (8 wt.% and 15 wt.% 1-butanol) and the mixture was subcooled to 20 C. Choline chloride crystals were observed and separated by ltration under vacuum. The separated quantities of the solid choline chloride were in agreement with that reported in the literature [24]. This indicates that crystallization is a low-cost alternative that can be used for the salt recovery. In this case the recovered salt can be mixed with the puried glycerine to reproduce the DES, which can then be utilized back in the extraction process. The lab scale experiment can be scaled up to the industrial scale easily as suggested in the schematic of Fig. 4. The output of the transesterication reaction is fed to a decanter to separate the free glycerine which is sent to a glycerine treatment facility. Untreated biodiesel and the synthesized DES are fed to the extractor, where mass transfer occurs separating the glycerine from the biodiesel to the DES phase. The used DES is then mixed with an anti-solvent agent and the mixture is fed to a crystallization unit to separate the ammonium salt. The complete separation of the crystallized salt can be achieved by a rotary drum lter. This salt is then recycled for use as a DES ingredient. 4. Conclusion Laboratory scale batch-wise experiments were conducted to separate the glycerine from transesterication biodiesel product. The extraction process involved different compositions of a quaternary ammonium salt (choline chloride) to glycerine as a solvent. A ratio of 1:1 was found to give the best extraction yield. Moreover, biodiesel to

total glycerine content in biodiesel to a certain extent. It is clear that the percentage of extracted glycerine is inversely proportional with the Biodisel:DES molar ratio. The other factor that affects the extraction process is the DES composition molar ratio (ChCl:glycerine). This is dictated by the synthesis specication of the DES. As the DES composition ratio (ChCl:glycerine) changes from 1:1 to 1:3 (i.e. 0.5 to 0.75 glycerine molar fraction in Fig. 2), its ability to remove glycerine from the extraction mixture is reduced. This can be explained by the fact that lower glycerine content DES has a greater tendency to attract more glycerine molecules forming a higher ratio DES. However, this capability is reduced as the glycerine content in DES increases. This is indicated by the little change in the total glycerine prole at the higher DES ratios (1:1.5 to 1:3). Moreover, the gure indicates the existence of an optimum DES composition for each extraction feeds ratio. The optimum DES composition is 1:1 (0.5 glycerine molar fraction in DES) for the case of 1:1 biodiesel:DES ratio and 1:1.25 (0.55 glycerine molar fraction in DES) for the 1:1.5 and 1:2 biodiesel: DES ratios. To study the extraction efciency of the proposed DES solvent, the distribution coefcient of glycerine was calculated for different DES compositions and biodiesel:DES ratios. The distribution coefcient was calculated as the ratio of the molar concentration of glycerine in the DES phase to that in the biodiesel phase under equilibrium conditions. The results are shown graphically in Fig. 3 as a function of glycerine molar fraction in the used DES. There is an inverse relationship between the effect of varying the biodiesel:DES molar ratio and the extraction efciency. As the DES content in biodiesel:DES ratio increases, the glycerine distribution between the two extraction phases shifts more to the biodiesel phase resulting in a corresponding decrease in the extraction efciency. Fig. 3 also reveals the high capacity of the 1:1 (for the case of 1:1 extractive feed ratio) and the 1:1.25 (for the case

Table 3 Extracted glycerine (wt.%) for the tested DES. DES ratio (ChCl:glycerine) 1:1 1:1.25 1:1.5 1:2 1:3 Biodiesel:DES ratio 1:1 51.25% 45.45% 45.89% 45.46% 46.85% 1:1.5 17.14% 25.71% 10.71% 12.50% 6.78% 1:2 13.92% 22.86% 1.78% 3.21% 2.50%

Fig. 3. Distribution coefcient of total glycerine extracted from biodiesel.

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Fig. 4. Schematic of the proposed process for the purication of biodiesel. 1 Transesterication reactor, 2 decanter, 3 DES synthesis mixing tank, 4 extractor, 5 mixing tank, 6 crystalizer, 7 rotating lter.

DES ratio was found to be more important than the DES composition ratio in affecting the extraction efciency. Carefully selecting this ratio, results in the best distribution of solute in the extraction system. The puried biodiesel fulls the international standards of EN 14214 and ASTM D 6751 in terms of glycerine content. The used solvent can be recovered by crystallizing the ammonium salt. An industrial process for the recovery is described. More investigations need to be conducted in the area of process optimization and solvent recovery. The suggested separation technique overcomes conventional purication methods shortcomings and provides a low cost alternative. References
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