Effect of Thermal Treatment on Coke Reactivity and Catalytic Iron Mineralogy

Iron minerals in coke can catalyze its gasification and may affect coke behavior in the blast furnace. The catalytic behavior of iron depends largely upon the nature of the iron-bearing minerals. To determine the mineralogical changes that iron could undergo in the blast furnace, cokes made from three coals containing iron present in different mineral forms (clays, carbonates, and pyrite) were examined. All coke samples were heat-treated in a horizontal furnace at 1373, 1573, and 1773 K and then gasified with CO2 at 1173 K in a fixed bed reactor (FBR). Coke mineralogy was characterized using quantitative X-ray diffraction (XRD) analysis of coke mineral matter prepared by low-temperature ashing (LTA) and field emission scanning electron microscopy combined with energy dispersive X-ray analysis (FESEM/EDS). The mineralogy of the three cokes was most notably distinguished by differing proportions of iron-bearing phases. During heat treatment and subsequent gasification, iron-containing minerals transformed to a range of minerals but predominantly iron-silicides and iron oxides, the relative amounts of which varied with heat treatment temperature and gasification conditions. The relationship between initial apparent reaction rate and the amount of catalytic iron mineralspyrrhotite, metallic iron, and iron oxideswas linear and independent of heat treatment temperature at total catalyst levels below 1 wt %. The study showed that the coke reactivity decreased with increasing temperature of heat treatment due to decreased levels of catalytic iron minerals (largely due to formation of iron silicides) as well as increased ordering of the carbon structure. The study also showed that the importance of catalytic mineral matter in determining reactivity declines as gasification proceeds.