【摘要】 由于“镧系收缩”效应，钨(W)和钼(Mo)表现出相近的化学性质，这使得钨钼在自然成矿过程中往往共生，同时也使得钨冶炼过程钼的分离成为难题。早期钨冶炼的原料主要是易选易冶的黑钨矿，由于结晶化学的原因，单斜晶系的黑钨矿晶格中很难混入钼原子，所以其伴生钼含量低，分离任务很小，钨冶炼流程中甚至没有专门的除钼工序。但随着黑钨矿资源的逐渐消耗，难处理的白钨矿逐渐进入钨冶炼流程，四方晶系的白钨矿晶格中钼很容易发生类质同象取代，导致进入钨冶炼系统中的伴生钼越来越多，相应的对钨钼分离技术的需求也随之增加。再加上高端钨产品对纯度的要求逐步严厉，除钼问题更加突出，除钼方法也不断推陈出新。本文从钨矿原料转变、钨冶炼流程发展、下游钨产品需求变化等多个角度分析多种钨钼分离技术的适用性与优缺点。更多还原

【Abstract】 Tungsten（W） and molybdenum（Mo） share remarkably similar chemical properties due to their comparable atomic radii and oxidation states, rendering their separation a persistent and complex challenge in tungsten extractive metallurgy. As a critical strategic resource, tungsten is indispensable in high-performance materials like cemented carbides, where even trace amounts of molybdenum can significantly degrade product quality by forming detrimental intermetallic compounds such as Co₃（Mo, W）₃C, leading to reduced bending strength and fracture toughness. Historically, wolframite, with its inherently low co-existing molybdenum content, minimizes the separation pressure in tungsten processing. However, with the progressive depletion of wolframite resources, the industry has increasingly shifted towards scheelite— a raw material known for its higher molybdenum content due to isomorphic substitution within its cubic crystal lattice. This transition has dramatically intensified the demand for efficient W-Mo separation technologies. Concurrently, the burgeoning requirements from advanced downstream industries for ultra-high purity tungsten products necessitate the development of even more stringent and profound molybdenum removal strategies.This study systematically charts the evolution of W-Mo separation technologies, directly correlating their development with shifts in primary tungsten raw materials and increasing purity demands. The MoS₃ precipitation method historically utilized molybdenum’s stronger affinity for sulfur in acidic solutions, precipitating MoS₃ while tungsten remained in solution. While offered short cycles and low costs, it generates toxic H₂S gas, and provides insufficient removal for high-purity demands, leads to its gradual replacement due to environmental and efficiency concerns. The ion exchange method exploits morphological differences of polyoxomolybdates and polymolybdates at varying pH values for separation. More effectively, after sulfidization of the mixed solution, it relies on the resin’s preferential adsorption of thiomolybdate ions(MoS₄^2-) in alkaline environments. While highly selective, challenges include difficult molybdenum recovery from loaded resins, often require harsh oxidative elution that can degrade the resin’s lifespan and increase operational costs. Solvent extraction utilizes various extractant, often in synergistic combinations（e.g., tertiary amines like N235, organophosphorus compounds such as tributyl phosphate（TBP） and trialkylphosphine oxide（TRPO））, to selectively target and extract molybdenum species from acidic or alkaline solutions. This method can achieve high separation efficiencies but often involves complex multi-stage countercurrent operations and faces issues like extractant degradation during destructive stripping, as well as concerns regarding organic phase residues and the management of high-salinity wastewater and hazardous phosphorus/arsenic sludge. A significant advancement is the selective precipitation method, performed in alkaline solutions. This innovative process first converts molybdenum to thiomolybdate(MoS₄^2-) via sulfidation. Subsequently, transition metal ions(Cu²⁺) are introduced to form highly insoluble thiomolybdate precipitates, effectively separating molybdenum from the tungstate solution. This approach boasts high separation efficiency, minimal tungsten loss, and the notable capability to simultaneously co-remove other impurities like arsenic, tin, and antimony as thio-salts. Its inherent compatibility with alkaline tungsten leaching processes, coupled with its environmental advantages, has established it as a leading and widely adopted "standard" technology in China’s tungsten extractive metallurgy, having received national recognition.In the future, W-Mo separation technologies face increasingly complex challenges. These include the continuing decline in tungsten ore grades, a growing reliance on diversified raw materials including complex low-grade ores and secondary resources, and critically, the escalating demand for ultra-high-purity tungsten products. The trajectory for future W-Mo separation research and development must prioritize achieving broader applicability across diverse raw material compositions, delivering even greater removal depths to meet these demanding purity specifications, and ensuring production process is both environmentally sustainable and highly efficient.更多还原