Thermodynamic Consideration of the Direct Removal of Oxygen from Titanium by Utilizing Metallothermic Reduction of Rare Earth Metal Halides

Toru H. Okabe, Gen Kamimura, Takanari Ouchi
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Abstract

As the demand for titanium (Ti) continues to grow, so too does the use of Ti scrap, underscoring the need for innovative techniques for the efficient removal of oxygen (O) impurities from Ti scrap. Despite the immense challenge of directly removing oxygen from Ti–O solid solutions and the current lack of industrially applicable deoxidation methods, the current work explores a groundbreaking approach to address this issue. The thermodynamic analysis of a new technique for eliminating oxygen dissolved in solid Ti was conducted, leveraging the deoxidation properties of rare earth metals (REMs) such as Sc, Y, and La. This cutting-edge method relies on the in-situ production of REMs through the metallothermic reduction of REM halides. It was shown that Sc or Y metal can be synthesized via the reduction of ScCl3 by Mg or YCl3 by Li or Na, respectively. Ti with oxygen concentrations below 100 mass ppm can be obtained by leveraging the deoxidation properties of the Sc and Y metals produced in situ during the metallothermic reduction process, which contribute to deoxidation through their subsequent oxychloride-forming reactions. Employing REM halides in tandem with Li, Na, and Mg enables the efficient removal of oxygen impurities from Ti, even though these reactive metals have only weak deoxidation properties for Ti on their own. Remarkably, the proposed technique achieves oxygen concentrations significantly lower than those obtained using Ca metal as a deoxidant. In the future, this pioneering deoxidation method could be used to reduce CO2 emissions and energy consumption during Ti production while promoting resource circulation as a key technology for Ti recycling.

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利用稀土金属卤化物的金属热还原从钛中直接脱氧的热力学考量
随着对钛(Ti)需求的不断增长,钛废料的使用量也在不断增加,这凸显了从钛废料中有效去除氧(O)杂质的创新技术的必要性。尽管从钛-氧化物固溶体中直接去除氧气是一项巨大的挑战,而且目前缺乏工业上适用的脱氧方法,但目前的研究工作探索了一种突破性的方法来解决这一问题。利用稀土金属(REMs)(如钪、钇和镧)的脱氧特性,对消除溶解在固体钛中的氧气的新技术进行了热力学分析。这种前沿方法依赖于通过稀土金属卤化物的金属热还原来就地生产稀土金属。研究表明,Sc 或 Y 金属可分别通过 Mg 还原 ScCl3 或 Li 或 Na 还原 YCl3 合成。利用金属热还原过程中在原位生成的 Sc 和 Y 金属的脱氧特性,可获得氧浓度低于 100 质量ppm 的钛。将 REM 卤化物与 Li、Na 和 Mg 结合使用,可有效去除 Ti 中的氧杂质,尽管这些活性金属本身对 Ti 的脱氧性能很弱。值得注意的是,该技术所获得的氧浓度大大低于使用 Ca 金属作为脱氧剂所获得的氧浓度。未来,这种开创性的脱氧方法可用于减少钛生产过程中的二氧化碳排放和能源消耗,同时作为钛循环利用的一项关键技术促进资源循环。
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