Nitrogen functionality in “oil window” rank range vitrinite rich coals and chars

X-ray photoelectron spectroscopy (XPS) was used to characterize organic nitrogen species in coals and chars. The coals comprise a set of vitrinite-rich samples from the Penn State Coal Bank set, ranging from vitrinite reflectance (Rr) 0.42-1.60%. Chars were obtained after coal pyrolysis under an inert atmosphere at 800 °C and fast heating rate. In the coals, pyrrolic nitrogen was the predominant form, steadily decreasing with coal rank, while pyridinic and quaternary nitrogen showed pronounced variation with rank. In contrast to the coals, the chars show much less pyrrolic and pyridinic nitrogen, and more quaternary nitrogen. The chars were also characterized by having oxidized nitrogen and nitro sub-peaks, which were not observed for the coals. Apparently the occurrence of these forms is related to the decrease in the pyridinic nitrogen.