Considering that the low recovery efficiency and the massive loss of valuable metals by the traditional pyrometallurgical process smelting low‒nickel matte. Therefore, this paper focuses on studying the optimal process parameters and the mechanism of sulphation roasting followed by water leaching achieving efficient synchronous extraction of nickel (Ni), copper (Cu), and cobalt (Co) from low‒nickel matte with sodium sulfate as the sulfating addictive. Under optimal conditions, the recovery efficiency of Ni, Cu, and Co metals can achieve 95%, 99%, and 94%, respectively, whereas the recovery efficiency of Fe metal is less than 1%. The results revealed that the mechanism of the sulfating roasting pretreatment could form a liquidus eutectic compound sulfates [Na2Me(SO4)2] (Me = Ni, Cu, Co) at the solid–solid interface, which plays a significant role in promoting the leaching efficiency of valuable metals. Not only enhance the reaction kinetics of sulfation, but improve the utilization efficiency of SO2/SO3. Thus, the sulfation roasting‒water leaching process developing an efficient and eco-friendly pathway to simultaneous extraction of Ni, Cu, and Co valuable metals from low grade sulfide ores.
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