Effectiveness of both ZnCl2- and SnCl2-containing molten salt catalysts for hydrogenation of Big Ben coal in the absence of a solvent

Hydrogenation of Big Ben coal (Australian bituminous coal) with 9.8 MPa H₂ for 3h at 400 °C has been carried out using a batch autoclave system in the presence of a molten salt catalyst such as ZnCl₂, SnCl₂, ZnCl₂-KCl-NaCl (3:1:1 mol ratio) and SnCl₂-KCl (3:2). The hexane-soluble (HS) yield decreases in the order: SnCl₂-KCl, SnCl₂, ZnCl₂-KCl-NaCl, ZnCl₂. The use of SnCl₂-containing melt is characterized by higher yields of both HS and benzene-soluble (BS) fractions and the suppression of gas yield compared with the use of ZnCl₂. The average aromatic unit and the molecular weight of HS increase in the order: ZnCl₂, ZnCl₂-KCl-NaCl, SnCl₂, SnCl₂-KCl. Chromatographic separation of HS fractions indicates that the saturate content is lowest and polar-material content is highest with the SnCl₂-KCl melt: this fact coupled with the structural parameters suggests that HS material with SnCl₂-KCl melt has, on average, a reasonably-high-molecular-weight skeleton which has more alkyl chains and heteroatoms. Micrographs of resulting benzene-insoluble (Bl) materials clearly indicated that the Bl particles were larger when ZnCl₂ was used than when the other melts were used, the Bl particles in these cases being of similar size. Lewis acidity and the viscosity of the molten salt appear to be related, in part, to the size of the Bl particles.