Kinetic Modeling of Sunflower Oil Methanolysis Catalyzed by Calcium‐Based Catalysts

Abstract

The kinetic model originally developed for quicklime-catalyzed methanolysis of sunflower oil was tested for another three calcium-based catalysts, namely, neat CaO, Ca(OH) 2 , and CaOÁZnO. This model includes the changing reaction mechanism and the triacylglycerol (TAG) mass transfer. The applicability and generalization capability of this model for heterogeneous methanolysis reaction catalyzed by calcium-based catalysts was evaluated. As indicated by the high coefficient of determination and the relatively small mean relative percentage deviation, the model was a reliable predictor of the time variation of TAG conversion degree in the sunflower oil methanolysis over all four calcium-based catalysts within the ranges of the reaction conditions applied. This model is recommended in general for describing the kinetics of sunflower oil methanolysis over calcium-based catalysts.

NIR Monitoring and Modelling of Soybean Oil Methanolysis with Multivariate Curve Resolution-Alternating Least Squares with Correlation Constraint

“…This assumption implies that the instantaneous concentrations of monoacylglycerols and diacylglycerols are small as a result of their consumption rates being fast; 1,5 (ii) since the methanol is added in excess in relation to the initial amount of vegetable oil, the reverse reaction is considered negligible; 3 (iii) the composition of the reaction mixture was considered uniform, perfectly mixed; 1,5,37 (iv) the free fatty acid (FFA) content in the vegetable oil was considered negligible; therefore, the neutralization of the free fatty acids was neglected. The saponification side reaction was also neglected.…”

“…Till present, there is no consensus about the kinetic behavior of the methanolysis reaction. [2][3][4][5][6] Thus, there are diverse studies on the kinetics of methanolysis for biodiesel production using different types of vegetable oils and catalysts (homogeneous and heterogeneous), based on different methods for analytical monitoring of the reaction, that report different results.…”

“…Other works considered the global reaction and developed a kinetic model based on triacylglycerols concentration. 3,5,9 Jain and Sharma 10 carried out analysis of the methanolysis process of pre-esterified Jatropha curcas oil catalyzed by NaOH and developed a first order kinetic model based on the percentage of methyl ester yield, based on the global reaction and ignoring the intermediates.…”

Biodiesel production by methanolysis of waste lard from piglet roasting over quicklime

“…In fact, the reaction order varies with the progress of the reaction from the zeroth order to the first order [25,28]. More complex models [28][29][30] that involve the liquid-liquid mass transfer limitation have been recently verified for the calcium-based catalysts including pure CaO, quicklime, CaOÁZnO and Ca(OH) 2 [31,32].…”

“…The main aim was to analyze the methanolysis reactions of the lard-based raw materials over quicklime and CaO and to describe the reaction kinetics using the kinetic model combining the changingand first-order reaction rate laws with respect to TAGs and FAMEs. Since recently, this kinetic model has been used in modeling the kinetics of oily feedstocks methanolysis reaction over calcium-based catalysts [28,31,33,34]. Several catalytically active calcium-based species like CaO itself, methoxide, glyceroxide and glycerolate may act in the methanolysis reaction as a catalyst.…”