Optimization of the Solvent-Free Lipase-Catalyzed Synthesis of Fructose-Oleic Acid Ester Through Programming of Water Removal

Fructose oleate, an environmentally-friendly biobased surfactant, was prepared using solvent-free suspensions of saccharide in a mixture of acyl donor and monoester (the latter present at ≥5 wt% initially) continuously recirculated through a closed-loop packed bed bioreactor (PBBR)-based system at 53 °C, with the PBBR containing immobilized Rhizomucor miehei lipase (Lipozyme^®IM, Novozymes, Franklinton, NC, USA). To replenish the acyl acceptor consumed during the time course of reaction, the medium was isolated, fructose added, and a suspension formed by rigorous stirring at 80 °C for 6 h followed by centrifugation to remove larger particles, with the placement of the acyl acceptor replenishment treatments during the time course of reaction were optimized. Water removal via free evaporation was augmented during the latter portion of the time course (using a molecular sieve packed column, N₂ bubbling, vacuum pressure, or a combination of the latter two), with an optimal performance achieved when initiating N₂ + vacuum (\( 2. 1 6\,{\text{mg}}_{{{\text{H}}_{ 2} {\text{O}}}} \,{\text{h}}^{{^{ - 1} }} \) removal rate) upon reaching 60% ester, to maintain the liquid-phase water content near 0.40 wt%. When employing the above-mentioned conditions, 92.6 wt% fructose oleate was produced within 132 h, yielding a productivity of \( 0. 2 9 7\,{\text{mmol}}_{\text{Ester}} \,{\text{h}}^{ - 1} \, {\text{g}}_{\text{lipase}}^{ - 1} \).