Experimental and theoretical studies of the carbonylation and decarbonylation reactions involving nickel

用于从加工矿石中提取镍的主要工业工艺之一是通过Ni（CO）4的形成和随后的分解，如Mond，Langer和Quincke在1890年发现的。 氧化矿石在80-100 oC下暴露于纯CO会产生挥发性和有毒的羰基;在180 oC下分解会产生高度纯化的Ni固体，广泛用于制备不锈钢、粉末冶金和电化学加工和沉积。 Vale（原INCO）在Clampaach（英国威尔士）和Copper Cliff（加拿大安大略）经营的精炼厂采用了这种机制，使用的镍矿石主要在萨德伯里地区开采。 尽管该方法明显简单且开发时间长，但该方法的效率变化很大，并且最终镍产品的物理化学性质不如许多工业应用所需的均匀;这些质量控制变化对相关镍工业具有显著的财务后果。 尽管对矿石原料、添加剂和操作条件进行了广泛的工业测试和经验性调整，但这些变化的起源尚不清楚。 来自工厂操作的轶事证据表明，反应器中控制不良的S可能在这些变化中起着至关重要的作用; S是故意添加的，并且也存在于用于羰基化的矿石锍中。

One of the leading industrial processes used for the extraction of nickel from processed ores is via the formation and subsequent decomposition of Ni(CO)4, as discovered by Mond, Langer and Quincke in 1890. Exposure of the oxidized ore to pure CO at 80-100 oC produces the volatile and toxic carbonyl; decomposition at 180 oC produces a highly purified Ni solid, which is widely used in the preparation of stainless steels, powder metallurgy, and electrochemical processing and depositions. This mechanism is employed at refineries in Clydach (Wales, UK) and Copper Cliff (Ontario, Canada) operated by Vale (formerly INCO), using Ni ores that are mostly mined in the Sudbury area. Despite the apparent simplicity of the process and its long development, the efficiency of the process is highly variable, and the physico-chemical properties of the final Ni products are less homogeneous than desired for many industrial applications; these quality control variations have significant financial consequences for the associated Ni industry. The origins of these variations are not known, despite extensive industrial testing and empirical adjustments to the ore feedstocks, additives, and operating conditions. Anecdotal evidence from plant operations suggest that poorly controlled S in the reactors may play a crucial role in these variations; S is added deliberately and is also present in the ore matte used for carbonylation.