Results are presented for a comprehensive study of the chemical and material composition, as well as the macrostructure, of refractory samples after over 14 years service in a blast furnace hearth with a useful volume of 2200 m3. Sample carbon content is determined using a comprehensive method. Zinc-containing phase formation is established in both the ceramic nozzle area oxide refractories and within the carbon lining of the furnace tuyere zone and hearth. Furnace refractory wear is complex, predominantly by a thermochemical mechanism, and a slow rate due to garnish formation containing refractory compounds.