Synergistic Effects Between Acidity and the Crystalline Phases of Thermally Activated Layered Zn Hydroxide Nitrate on the Methanolysis of Acidic Soybean Oils

Layered hydroxyl salts (LHS) is a promising catalyst in the field of methanolysis (transesterification and esterification reactions) of oil feedstocks. The catalytic activity of the catalyst can be enhanced with heat treatment. The present study investigated the relationship between thermal stability of the layered Zn hydroxide nitrate (ZHN), their acid-base properties, and the catalytic conversion of oil feedstocks to methyl ester. The solid, predominantly acidic catalyst was prepared at various temperatures (70-170 °C and tested for the acidic/basic properties using the Hammett indicators and titration method followed by functional group analysis using FTIR, crystallization using X-ray diffraction, and surface morphology using SEM. The combination of various characterization techniques gave an insight into the changes in the phases of the layered Zn hydroxide nitrate catalysts upon thermal treatment. Major phase changes occurred at temperatures somewhat above 80, and 140 °C. The catalysts were extensively studied to understand the underlying effects on the FAME yields obtained from catalytic conversion of oleic acid spiked soy bean oil (a model of an acidic oil feedstock) into methyl esters. The results of the optimization reactions reaffirmed the effect of the phase changes when the highest FAME yield was observed from two activated samples namely, Zn5_80 and Zn5_140. The optimized reactions condition of catalytic conversion of SO containing 10% OA at 5 °Cmin heating rate, 3 wt % catalyst concentration, 30:1 methanol to oil molar ratio, reaction time of 100 °C for 2 h gave 92% FAME yield when Zn5_140 was used as the catalyst. The detected of the single phase of Zn(OH)(NO) in Zn5_80, Zn(OH)(NO) and ZnO in Zn5_140 (2-phase system), including Zn(OH)(NO), Zn(OH)(NO), and ZnO in Zn5_170 (3-phase system), suggested all three phases contributes to the high catalytic activity in methanolysis of the acidic oils. Both Zn5_140 and Zn5_170 gave a comparably high FAME yields based on statistical analyses. This study ascertained the synergistic effects of the high acidity (>0.4 mmol/g) and the dominant active phases of the thermally treated layered Zn hydroxide nitrate on the high catalytic activity that favours esterification of acidic oil feedstocks.