Process Optimization of Glycerol-to-Triacetin Conversion in Clean Technology Applications: In Situ Water Removal for Enhanced Reaction Performance in Sustainable Biodiesel Byproduct Valorization 10.32526/ennrj/24/20250278
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Abstract
Increasing biodiesel production generates excess glycerol, which has a declining economic value. Converting glycerol into triacetin, a value-added fuel additive, offers a promising solution. However, the reversible nature of the esterification reaction and the formation of water reduce selectivity. Therefore, this study was conducted to evaluate the effect of in situ water removal on reaction performance in terms of acetic acid conversion and the resulting triacetin product. Experiments were conducted in a batch reactor through three clearly defined stages. In Stage 1, the optimal glycerol-acetic acid molar ratio (1:3-1:5) was determined at 100°C and 700 rpm, using a 5% natural zeolite catalyst (based on acetic acid mass), and a reaction time of 4 h with in situ water removal. In Stage 2, residual water was removed by fractional distillation at 105°C until bubbling ceased. Stage 3 comprised the main reaction, where the distillate containing monoacetin, diacetin, triacetin, and glycerol was reacted with fresh acetic acid at the optimal ratio, while in situ water removal continued to enhance triacetin formation. Acetic acid conversion was analyzed by acid-base titration using 0.5 N NaOH, and triacetin was identified by GC-MS. This innovation showed excellent results, achieving 94.00% conversion of acetic acid with 85.58% selectivity for triacetin at 110°C and a 1:5 glycerol-to-acetic acid molar ratio. These results showed that in situ water removal intensified esterification by shifting the equilibrium, enhancing triacetin conversion and selectivity. This strategy advances glycerol valorization and supports the production of sustainable fuel additives within integrated biorefinery systems.
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