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Tin-, iron-bearing tailing is a typically hazardous solid waste in China, which contains plenty of valuable tin, iron elements and is not utilized effectively. In this study, a multistage utilization process was put forward to get the utmost out of the valuable elements (tin and iron) from the tailings, and a gradient-recovery method with three procedures was demonstrated: (1) An activated roasting followed by magnetic separation process was conducted under CO-CO2 atmosphere, tin and iron were efficiently separated during magnetic separation process, and 90.8 wt% iron was enriched in magnetic materials while tin entered into non-magnetic materials; (2) The tin-enriched non-magnetic materials were briquetted with CaCl2 and anthracite and roasted, then tin-rich dusts were collected during the chloridizing roasting process; (3) The roasted briquettes were infiltrated in melting NaNO3 to prepare NaNO3/C-PCMs by a infiltration method. Three kinds of products were obtained from the tailings by the novel process: magnetic concentrates containing 64.53 wt.% TFe, tin-rich dusts containg 52.4 wt.% TSn and NaNO3/C-PCMs for high temperature heat storage. Such a comprehensive and clean utilization method for tin-, iron-bearing tailings produced no secondary hazardous solid wastes, and had great potential for practical application.

Sodium stannate (Na2SnO3) has been successfully prepared by a novel process of roasting cassiterite concentrates and sodium carbonate (Na2CO3) under CO–CO2 atmosphere, namely soda roasting-leaching process. However, more than 22 wt. % tin of the cassiterite was not converted into Na2SnO3 and entered the leach residues. Quartz (SiO2) is the predominant gangue in the cassiterite, and phase evolution of SnO2–SiO2–Na2CO3 system roasted under CO–CO2 atmosphere was still uncertain. In this study, the effect of SiO2 in cassiterite concentrates on preparation of Na2SnO3 was clarified. The results indicated that Na8SnSi6O18 was inevitably formed when cassiterite and Na2CO3 were roasted above 775 °C under CO–CO2 atmosphere via the reaction of SnO2 + 6SiO2 + 4Na2CO3 = Na8SnSi6O18 + 4CO2, and formation of Na8SnSi6O18 would be increased with increasing roasting temperature and Si/Sn mole fraction. In addition, it was found that Na8SnSi6O18 was insoluble in the leachate at pH value range of 1–14, which, therefore, was enriched in the leach residues. The silicon content of the cassiterite concentrates should be controlled as lower as possible to obtain a higher conversion ratio of Na2SnO3.