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To produce Na2SnO3, which is widely used in the ceramics and electroplating industries, a novel process for the preparation of sodium stannate from cassiterite concentrates was developed successfully by the authors’ group. It was found that sodium stannosilicate (Na8SnSi6O18) was easily formed due to the main gangue of quartz in cassiterite concentrates, which was almost insoluble and decreased the quality of Na2SnO3. The formation and transitions of Na8SnSi6O18 in the SnO2–SiO2–Na2CO3 system roasted under a CO–CO2 atmosphere were determined. The results indicated that the formation of Na8SnSi6O18 could be divided into two steps: SnO2 reacted with Na2CO3 to form Na2SnO3, and then Na2SnO3 was rapidly combined with SiO2 and Na2CO3 to form low melting point Na8SnSi6O18. In addition, Na8SnSi6O18 can be decomposed into Na2SiO3 and Na2SnO3 by using excess Na2CO3.

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.