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SYNOPSIS Furnace wall tubes from 600 MW subcritical boilers at three coal-fired power stations were sampled and the fireside deposits examined to determine the mechanism of fireside corrosion. This involved an in-depth investigation into the morphology and composition of the fireside deposits and the conditions of the furnace that enable this type of attack. SEM-EDS analysis revealed high concentrations of oxygen, iron, and sulphur, QEMSCAN and XRD analyses identified the presence of Fe3O4, Fe2O3, FeS, and FeS2. Differential thermal analysis showed thermal activities at temperatures of 500-600°C, 900-1100°C, and 1100-1250°C, which are associated, respectively, with FeS2 oxidation to FeS and Fe2O3, at 475-525°C, formation of aluminosilicates at 925-1100°C, and melting of FeS around 1190°C. The absence of sodium and potassium eliminates the contribution of molten alkali sulphates to the corrosion. The consistent coexistence of iron sulphide and iron oxide is indicative of the substoichiometric conditions in the furnace, while the detection of pyrite suggests that the coal is not completely combusted, which points to a poor combustion process. These observations were affirmed by gas analysis at one of the stations, where very high levels of carbon monoxide were measured at the furnace wall (> 14 000 ppm) and furnace exit (> 3500 ppm). The high CO concentrations are indicative of limited combustion caused by limited O2. These reducing conditions promote the formation of FeS-rich deposit, which is the corrosive species responsible for degradation. Keywords: fireside corrosion, sulphidation, coal-fired boiler, furnace wall tubes. |