Solid acid catalysts produced by sulfonation of petroleum coke: Dominant role of aromatic hydrogen.

Carbon based solid waste materials have been intensively investigated for the preparation of solid acid catalysts through sulfonation, but the acidity varies significantly depending on the material. In this study, the role of aromatic hydrogen in sulfonation with concentrated HSO was investigated using petroleum coke (petcoke), graphite, and biochar as the carbon materials. Through ball milling and calcination, the amount of aromatic hydrogen on the petcoke could be increased or decreased, respectively. After sulfonation at 80 °C with concentrated HSO, the produced acidity (i.e., -SOH groups) increased as the amount of aromatic hydrogen increased from essentially no acidity on graphite to 0.55 mmol/g on biochar and 1.25 mmol/g on petcoke (particle sizes of 45-90 μm) indicating the importance of aromatic hydrogen during sulfonation. Calcination (350 °C for 1 h) of the petcoke before sulfonation decreased the acidity to 0.59 mmol/g, while ball milling (with isopropanol and silica for 24 h) increased the acidity to 3.73 mmol/g. The sulfonated petcoke samples were used as catalysts for the esterification reaction between octanoic acid and methanol at 60 °C and the turnover frequencies were 48-85 h. The results give insights on the preparation of solid acid catalysts from carbon materials and highlight the application of petcoke without activation as a feedstock for esterification catalysts.