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

蒙德、兰格和昆克于1890年发现，从已加工矿石中提取镍的主要工业工艺之一是通过形成和随后分解镍(CO)4。氧化矿石暴露在80-100oC的纯CO中会产生挥发性和有毒的羰基；在180oC下分解会产生高纯度的镍固体，广泛用于不锈钢的制备、粉末冶金以及电化学处理和沉积。由淡水河谷(前国际镍公司)运营的Clydach(英国威尔士)和铜崖(加拿大安大略省)炼油厂采用这种机制，使用主要在萨德伯里地区开采的镍矿石。尽管该工艺表面上很简单，而且开发时间很长，但该工艺的效率变化很大，最终镍产品的物理化学性质不如许多工业应用所希望的那样均匀；这些质量控制变化对相关的镍行业产生了重大的财务后果。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调整，但这些变化的原因尚不清楚。来自工厂运营的坊间证据表明，反应堆中控制不善的S可能在这些变化中发挥了关键作用；S是故意添加的，也存在于用于羰化的矿石冰铜中。

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.