Nitric Acid Functionalization of Petroleum Coke to Access Inherent Sulfur

Sulfonated carbon-based catalysts have been identified as promising solid acid catalysts, and petroleum coke (petcoke), a byproduct of the oil industry, is a potential feedstock for these catalysts. In this study, sulfur-containing (6.5 wt%) petcoke was used as a precursor for these catalysts through direct functionalization (i.e., without an activation step) with nitric acid to access the inherent sulfur. Catalysts were also prepared using sulfuric acid and a mixture of nitric and sulfuric acid (1:3 vol ratio). Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and titration were used to identify and quantify the acid sites. The activities of the prepared catalysts were determined for the esterification of octanoic acid with methanol. Petcoke had few −SO3H groups, and correspondingly no catalytic activity for the reaction. All acid treatments increased the number of −SO3H groups and promoted esterification. Treatment with nitric acid alone resulted in the oxidation of the inherent sulfur in petcoke to produce ~0.7 mmol/g of strong acid sites and a total acidity of 5.3 mmol/g. The acidity (strong acid and total) was lower with sulfuric acid treatment but this sample was more active for the esterification reaction (TOF of 31 h−1 compared to 7 h−1 with nitric acid treatment).