Glycerol carbonate synthesis via transesterification of enriched glycerol and dimethyl carbonate using a Li-incorporated MCM-41 framework

Abstract

Waste crude glycerol was successfully enriched and utilized as an inexpensive source for producing value-added chemicals, such as glycerol carbonate (GC) – a valuable compound with extensive industrial applications. The Li/MCM-41 heterogeneous catalyst was synthesized and used for the transesterification of enriched glycerol and dimethyl carbonate (DMC) to produce GC. The catalyst's physicochemical properties were characterized using thermogravimetric, Hammett indicator, inductively coupled plasma-optical emission spectroscopy, nitrogen adsorption–desorption, X-ray diffractometry, scanning electron microscopy, and Fourier-transform infrared spectroscopy analyses. Reaction conditions were optimized using response surface methodology and analysis of variance, yielding an accurate quadratic model to predict the GC yield under different transesterification variables. The results revealed that 5%Li/MCM-41 served as the optimal catalyst, achieving the highest TOF of 4.72 h⁻¹. The DMC: enriched glycerol molar ratio had the greatest impact on the GC yield, with an R² = 0.9743 and adjusted R² = 0.9502. The optimal GC yield (58.77%) with a final purity of 78% was attained at a 5.15 wt% catalyst loading relative to the initial amount of enriched glycerol, DMC: enriched glycerol molar ratio of 4.24 : 1, and a reaction temperature of 86 °C for 165 min. The 5%Li/MCM-41 heterogeneous catalyst could be reused for four cycles with a decreased GC yield from 58.77% to 45.72%. Thus, the Li/MCM-41 catalyst demonstrated a remarkable efficiency and potential as a heterogeneous catalyst for synthesizing GC. This method not only contributes to environmental sustainability by making use of a byproduct from biodiesel production but also aligns with the principles of a circular economy.