An insight on acyl migration in solvent-free ethanolysis of model triglycerides using Novozym 435

• Ethanolysis of S, M and LCFA triglycerides (TG) catalyzed by Novozym 435.
• Focusing on the secondary reaction of acyl migration.
• 2-Monoglyceride was favored by long reaction times and large biocatalyst loading with saturated S and MCFA TG.
• Acyl migration increased the yield of ethyl esters and minimized the content of 2-monoglyceride.
• Conversion of acylglycerides with unsaturated LCFA was low due to limitations in their access to the active site of the lipase.

In this work, the ethanolysis of triglycerides catalyzed by immobilized lipase was studied, focusing on the secondary reaction of acyl migration. The catalytic tests were performed in a solvent-free reaction medium using Novozym 435 as biocatalyst.The selected experimental variables were biocatalyst loading (5–20 mg), reaction time (30–90 min), and chain length of the fatty acids in triglycerides with and without unsaturation (short (triacetin), medium (tricaprylin) and long (tripalmitin/triolein)).The formation of 2-monoglyceride by ethanolysis of triglycerides was favored by long reaction times and large biocatalyst loading with saturated short- to medium-chain triglycerides. In the case of long-chain triglycerides, the formation of this monoglyceride was widely limited by acyl migration.In turn, acyl migration increased the yield of ethyl esters and minimized the content of monoglycerides and diglycerides. Thus, the enzymatic synthesis of biodiesel was favored by long-chain triglycerides (which favor the acyl migration), long reaction times and large biocatalyst loading.The conversion of acylglycerides made from long-chain fatty acids with unsaturation was relatively low due to limitations in their access to the active site of the lipase.