ReaxFF simulations of petroleum coke sulfur removal mechanisms during pyrolysis and combustion

Green petroleum coke (petcoke) is used as a feedstock for raw carbon material or as a fuel. Petcoke with high sulfur (S) content (>4 wt%) is typically restricted to fuel use unless extensive S removal is successful. Here, the S removal mechanisms during both pyrolysis and combustion were explored using the Reactive Force Field (ReaxFF) MD approach. A structural representation (C₁₆₄₈H₇₇₂O₅₉N₂₄S₄₇) of a green Qingdao petcoke was generated coupling high-resolution transmission electron microscopy lattice fringe image analysis and analytical data. This structure was consistent with elemental, aromaticity (FT-IR), the pair correlation function (XRD), and functional group (S, O, and N from XPS) data. The ReaxFF pyrolysis simulation produced gas and tar yields of 44.7 and 11.0 wt% at 3000 K after 250 ps of simulation. The combustion simulation on the same initial structure was performed in an O₂ environment. During the pyrolysis simulation, the first-step for S-removal was thiophenic sulfur conversion to C_1–4S (mostly C₂S), COS, or CNS. The heteroatom pyrolysis overlapped, for this structure, at these conditions. However, for the combustion simulation earlier conversion of thiophenic sulfur to COS was observed. No N–S containing structures occurred in this O-rich environment, as pyrrolic and pyridinic N quickly oxidized into CON or NO compounds. The S transformation during combustion can be summarized by COS → CO₂S → CO₃S → CO₄S. The H atoms reacted with S-containing gases like COS/C₂S/CNS producing HS and H₂S rather than with the coke-S.