Ancient to modern ironmaking – examining the effect on the behaviour of phosphorus and other impurities in iron ore by doping with calcium oxalate (CaC2O4.H2O)

Charcoal produced from Syzygium Zeylanicum (local name: Yakada Maran = iron killer) trees were widely used in ancient Sri Lankan iron smelting practices. In this study, relict charcoal from Syzygium Zeylanicum tree trunks, branches and leaves were analysed for the first time. Unusually high concentrations of calcium oxalate (CaC2O4.H2O – CaOX) crystals were identified preserved in plant cell structures by optical mineralogy and SEM analysis. Thermogravimetric Analysis (TGA) of CaOX showed that it displayed three decomposition stages, releasing H2O at 177°C, CO at 493°C and CO2 at 750°C. Following the identification of CaOX in Sri Lankan charcoal, a series of reduction tests on a low-grade, high-P iron ore fine sample (high SiO2: 5 wt. per cent; Al2O3 4 wt. per cent; P: 0.135 wt. per cent) doped with CaOX were carried out at various temperatures. Samples were analysed by XRF, SEM and EPMA to determine the degree of reduction and the effect of reduction on the deportment of impurities, in particular P. Reduction tests at 800°C and 900°C with 5 wt. per cent CaOX showed that the reducibility increased to over 65 per cent. At temperatures above 900°C, P was located mainly within a fine, interstitial glass matrix suggesting that the CaOX flux enhanced removal of P from iron-rich pre-cursor phases to form glass. Preliminary magnetic separation tests to remove the P-rich interstitial glass were unsuccessful due to the fine grain size. Further complete reduction tests at temperatures above 1200°C with addition of coke to convert the iron oxides into Fem were conducted with samples doped with 10 wt. per cent CaOX, 10 wt. per cent CaCO3 and equivalent undoped samples. Results confirmed the preferential P-incorporation into a glassy matrix in the CaOX samples although some rare P incorporation into the metallic phase was noted. Experimental results, including comparisons with the CaCO3 fluxed and undoped samples, are discussed in view of the potential for CaOX flux for removing P (and potentially other impurities) from P-rich iron ores.