Free Radical and Cationic Addition due to Clay Minerals Found in Bitumen Froth at 250 °C Probed with Use of α-Methylstyrene and 1-Octene

Abstract

Following previous evidence that hydrothermal treatment of bitumen froth does not lead to bitumen upgrading at 250 °C and promotes viscosity increase, the current study explores the free radical and cationic reactivity of clay minerals found in bitumen froth in promoting heavier material formation through addition reactions. The current investigation employed α-methylstyrene (AMS) and 1-octene as probe molecules instead of bitumen froth, and their conversion at 250 °C in the presence of clay minerals kaolinite and illite was studied in batch reactors. Thermal conversion of AMS and 1-octene at 250 °C in the absence of minerals was observed to be low. In the presence of clay minerals, not only the conversion of AMS and 1-octene was increased but also reactions such as dimerization of AMS and alkylation of 1-octene and toluene (used as solvents) were mainly promoted, leading to heavier product formation. Double-bond isomerization of 1-octene and cumene formation from AMS was side reactions that were also promoted by the clay minerals. Suppression of mineral-related conversion by pyridine and selectivity to different reaction products that enabled differentiation between free radical and cationic reaction pathways indicated that the mineral-related conversion was predominantly cationic in nature. Using the reactions in the presence of minerals and pyridine as surrogates for alkaline bitumen froth, it was concluded that even under alkaline conditions, minerals could promote heavier material formation through cationic addition.