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New Ether-Functionalized Ionic Liquids for Lipase-Catalyzed Synthesis of Biodiesel

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Abstract

Ionic liquids (ILs) are being explored as solvents for the enzymatic methanolysis of triglycerides. However, most available ILs (especially hydrophobic ones) have poor capability in dissolving lipids, while hydrophilic ILs tend to cause enzyme inactivation. Recently, we synthesized a new type of ether-functionalized ionic liquids (ILs) carrying anions of acetate or formate; they are capable of dissolving a variety of substrates and are also lipase-compatible (Green Chem., 2008, 10, 696–705). In the present study, we carried out the lipase-catalyzed transesterifications of Miglyol® oil 812 and soybean oil in these novel ILs. These ILs are capable of dissolving oils at the reaction temperature (50 °C); meanwhile, lipases maintained high catalytic activities in these media even in high concentrations of methanol (up to 50% v/v). High conversions of Miglyol oil were observed in mixtures of IL and methanol (70/30, v/v) when the reaction was catalyzed by a variety of lipases and different enzyme preparations (free and immobilized), especially with the use of two alkylammonium ILs 2 and 3. The preliminary study on the transesterification of soybean oil in IL/methanol mixtures further confirms the potential of using oil-dissolving and lipase-stabilizing ILs in the efficient production of biodiesels.

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Notes

  1. Most imidazolium ILs are based on anions of BF −4 , OTf−, MeSO −4 , Tf2N−, PF −6 , and SbF −6 . Poor yields were seen in most hydrophobic ILs except in [OMIM][Tf2N].

  2. One unit hydrolyzes 1.0 microequivalent of fatty acid from triacetin in 1 h at pH 7.4 at 37 °C.

  3. One unit is the amount of immobilized enzyme which forms 1% octyl laurate (GC, area percent) from 0.5 mmol lauric acid and 1.0 mmol 1-octanol in 10 mL water-saturated isooctane in 1 h at 20 °C.

  4. One unit corresponds to the amount of enzyme which liberates 1 μmol oleic acid from triolein per minute at pH 7.5 and 37 °C.

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Acknowledgements

Acknowledgment is made to the Donors of the American Chemical Society Petroleum Research Fund (46776-GB1) for partial support of this research. The valuable and stimulating discussion with Dr. Jonathan H. Melman is greatly acknowledged.

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Authors and Affiliations

  1. Chemistry Program, Savannah State University, Savannah, GA, 31404, USA

    Hua Zhao, Zhiyan Song, Olarongbe Olubajo & Janet V. Cowins

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  1. Hua Zhao
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  2. Zhiyan Song
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  3. Olarongbe Olubajo
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Correspondence to Hua Zhao.

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Zhao, H., Song, Z., Olubajo, O. et al. New Ether-Functionalized Ionic Liquids for Lipase-Catalyzed Synthesis of Biodiesel. Appl Biochem Biotechnol 162, 13–23 (2010). https://doi.org/10.1007/s12010-009-8717-6

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