Quaternary Ni-Zn-Mg-Al Bifunctional Nanoclays as Catalytic Precursors for the Production of Glycerol Carbonate

Quaternary Ni-Zn-Mg-Al metallic mixed oxide (MMO) catalysts were synthesized by co-precipitation from layered double hydroxide precursors. The effect of varying Zn content on physicochemical properties and catalytic performance was evaluated. Mg-Al and ternary Ni-Mg-Al and Zn-Mg-Al catalysts were synthetized for comparative purposes. XRD, N2 sorption, MP-AES, CO2-TPD, NH3-TPD, SEM, and EDS characterized the materials’ physicochemical properties. The tested reaction was the transesterification between glycerol and dimethyl carbonate to obtain glycerol carbonate to improve the biodiesel industry. The catalyst containing both Ni and Zn showed the highest glycerol conversion among the evaluated materials. This was related to the increased number and strength of surface basic and acid active sites. Specifically, a high density of strong basic sites and acid ones in the quaternary catalysts was required for the reaction mechanism. The catalyst with 20 at% of Zn (MMO-Ni15Zn20) achieved the highest glycerol carbonate yield (89.6%) under mild reaction conditions and was solvent-free. MMO-Ni15Zn20 catalytic performance was associated with its high total basicity and predominance of strong basic sites and a moderate amount of acid sites. The differences observed between catalytic performances suggest that these results depend on the influence of structural, textural, acid, and basic properties. Reuse tests of the MMO-Ni15Zn20 catalyst showed moderate stability, with a progressive decrease in activity due to the loss of strong basic sites and the formation of agglomerated regions. Nevertheless, MMO-Ni15Zn20 maintained a GC selectivity of 100% in the successive cycles.