Valorization of rice husk silica waste: Organo-amine functionalized castor oil templated mesoporous silicas for biofuels synthesis

Abstract

Rice husk is a rich source of waste silica which has potential for application in the preparation of porous materials for use as catalyst supports or sorbents. Here we report on the synthesis of rice husk silica (RHS) and mesoporous templated rice husk silica (MT-RHS) using sodium silicate, obtained from rice husk ash, and castor oil as a pore directing agent. The resulting silicas were functionalized with 3-aminopropyltriethoxysilane (APTS) or 3-diethylaminopropyltrimethoxysilane (DEPA), and their catalytic activity evaluated in the transesterification of model C4–C12 triglycerides (TAG) to their corresponding fatty acid methyl esters, of relevance to biodiesel synthesis. Castor oil templating enhances the surface area of rice husk silica, and introduces uniform 4 nm mesopores, albeit as a disordered pore network. Post-synthetic grafting of silica by APTS or DEPA resulted in base site loadings of 0.5 and 0.8 mmolg−1 respectively on RHS and MT-RHS. Turnover frequencies of amine-functionalized MT-RHS were 45–65% greater than those of their amine-functionalized RHS counterparts for tributyrin transesterification. Switching from a primary (APTS) to tertiary (DEPA) amine increased activity three-fold, delivering 80% tributyrin conversion to methyl butyrate in 6 h. DEPA-MT-RHS was effective for the transesterification of C8 and C12 triglycerides, with methyl caproate and methyl laurate selectivities of 93% and 71% respectively in 24 h.