Understanding the reaction dynamics of glycerol conversion into glycerol carbonate by transesterification of carbonic acid esters over CaO

Abstract

The conversion of glycerol into value-added products is crucial for reducing waste generation in the biodiesel industry. In this context, glycerol carbonate has emerged as a promising molecule, capable of being produced through various processes, with glycerol transesterification being considered the most environmentally friendly method. In order to investigate the transesterification process comprehensively, this work focused on reactions between glycerol and different carbonic acid esters (dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate), utilizing calcium oxide (CaO) as a basic catalyst. The catalyst was obtained commercially and characterized by X-ray diffraction (XRD), infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). The catalyst characterizations showed that it consisted of nano and micrometric particles with high purity, making it suitable for use without prior pretreatment. The reactions were conducted in a batch reactor using dimethylformamide as a solvent, and the products were analyzed by gas chromatography (GC-FID and GC-MS). Experiments were performed to investigate the effects of different reaction parameters on the formation process of glycerol carbonate and potential co-products. CaO showed moderate catalytic activity in glycerol conversion, which occurred in three steps, forming glycerol carbonate with high selectivity, along with small amounts of co-products, glycidol and glycerol tricarbonate. Thus, considering the results obtained in this and other studies, it was possible to identify that moderately strong basic catalysts favor simple reaction mechanisms, predominantly yielding glycerol carbonate. Conversely, highly basic catalysts induce more complex reaction mechanisms, resulting in significant formation of co-products.