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Short Fluoride Cycle in Tungsten Technology
Russian Journal of Non-Ferrous Metals ( IF 0.6 ) Pub Date : 2020-12-28 , DOI: 10.3103/s1067821220060127
Yu. M. Korolev , A. N. Timofeev

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:

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〜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。

更新日期:2020-12-28
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