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Solvent-free biodiesel epoxidation

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Abstract

Biodiesel emerged again recently as an alternative for fossil fuels. Besides energy, biodiesel can be used as raw material to synthesize high value products such as epoxides. Indeed, epoxides are versatile intermediates in organic synthesis for numerous reactions due to the high reactivity of the oxirane ring. Actually common epoxidation by peracids in organic solvent can last several hours according to the double bonds number. The solvent confers selectivity to the reaction, preventing di-hydroxylation. Alternatively solvent-free reactions can be done in shorter times, but hydroxylation is less controlled. Here, we set up the synthesis of epoxides from methyl and ethyl esters of waste cooking oil, without solvent or metal catalyst. We tested molar ratio of hydrogen peroxide and formic acid, double bond number, reaction time, and temperature. Results show that the highest epoxide yields and selectivity, with high conversion of the double bonds, were obtained for temperature reactions between 50 and 65 °C, reaction times from 2 to 3 h, and molar ratio of 20/2/1. For those conditions, the double bonds conversion is equal or near 100 %, with epoxide yield and selectivity between 85 and 93 %. Organic solvent suppression, besides being environmentally friendly, also saves reaction time and subsequent purification steps.

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Acknowledgments

The authors would like to thank FINEP, CNPq, and CAPES for their financial support.

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Correspondence to Dimitrios Samios.

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Lehnen, D.R., Guzatto, R., Defferrari, D. et al. Solvent-free biodiesel epoxidation. Environ Chem Lett 12, 335–340 (2014). https://doi.org/10.1007/s10311-013-0448-9

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  • DOI: https://doi.org/10.1007/s10311-013-0448-9

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