Abstract

It is found that when a tungsten anode is electrochemically dissolved in a acidic fluorides of alkali metals (K,Na)H₂F₃ and hydrogen fluoride at a temperature of t ~ 37°C, the resulting atomic fluorine reacts completely with tungsten to form WF₆. The latter dissolves in the melt, forming complex compounds (K,Na)₂WF₈ and (K,Na)WF₇, which is accompanied by an increase in the melting point of the electrolyte. The addition of up to 23 mol % LiF and saturation of the electrolyte by WF₆ lowered its melting temperature below 18°C, which, in an electrochemical process at a temperature of 35–40°C and an anode current density of 0.3–0.5 A/cm², made it possible to obtain simultaneously gaseous WF₆ at the anode and H₂ at the cathode. During the gas-phase deposition of tungsten, dense layers are formed from the resulting gaseous mixture with a stoichiometric ratio of components at a temperature of 550–600°C, and the resulting HF is captured by an electrolyte and used to produce a mixture of WF₆ + H₂, ensuring the circulation of reagents and the absence of stored waste. Based on the results, a short fluoride cycle in tungsten technology is presented. It uses two operations: the electrochemical synthesis of a gaseous mixture of WF₆ + H₂ in an electrolyzer with a filling anode made of fragments of metal tungsten and the reduction of WF₆ by hydrogen with capture the resulting HF, allowing one to reduce the chain of technological devices in the cycle by almost 2 times with a significant reduction in production costs. The hardware and technological scheme of the production chain for the environmentally friendly production of tungsten products with a capacity of ~48.5 t/year, which can be replicated and modified to produce the necessary products, is presented.

中文翻译：

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钨技术中的氟化物循环短

摘要

据发现，当钨阳极被电化学溶解于（钾，钠）H的碱金属的酸性氟化物₂ ˚F ₃和氟化氢在温度吨〜37℃，所得到的原子氟反应完全钨以形成白领₆。后者溶解在熔体中，形成复合化合物（K，Na）₂ WF ₈和（K，Na）WF ₇，其伴随着电解质熔点的升高。添加高达23 mol％的LiF和WF ₆使电解质饱和，可将其熔融温度降低至18°C以下，在电化学过程中，温度为35–40°C，阳极电流密度为0.3–0.5 A /厘米^{如图2所示}，可以同时获得阳极处的气态WF ₆和阴极处的H ₂。在钨的气相沉积过程中，所形成的气体混合物在550-600°C的温度下会形成致密层，其成分的化学计量比很大，所产生的HF被电解质捕获并用于产生WF ₆ + H ₂，确保试剂的循环和没有存储的废物。根据结果​​，提出了钨技术中的短氟化物循环。它使用两个操作：WF ₆ + H ₂气体混合物的电化学合成在一个电解槽中，该电解槽具有由金属钨碎片制成的填充阳极，并通过氢气还原WF ₆并捕获生成的HF，从而使循环中的工艺设备链减少了近2倍，从而显着降低了生产成本。提出了环保生产钨产品的生产链的硬件和技术方案，年产能约为48.5吨，可以复制和修改以生产必要的产品。