热化学还原法制备金属钛的技术研究进展

doi:10.12034/j.issn.1009-606X.218279

摘要/Abstract

摘要： 金属钛及其合金性能优异，是重要的功能与结构材料。元素钛虽储量丰富，但极易与其它金属及氧氮氢碳等间隙元素反应，特别是与氧化学结合力强，使金属钛的提取非常困难。目前金属钛的主流生产方法是Kroll法，虽经多年优化且已高度成熟，但生产成本及能耗较高。为降低金属钛的生产成本，提出了诸多热化学与电化学新方法。本工作综述了近十余种不同热化学还原法，包括以TiCl4为前驱体的Kroll法、Hunter法、ADMA法、TiRO法、气相还原法、CSIR-Ti法、ITP-Armstrong法及ARC法和以TiO2为前驱体的预成型还原法(PRP)、熔盐辅助的液钙还原法、导电体介入还原法(EMR)、镁热还原?金属钙脱氧两步法及氢气协同镁热还原(HAMR)法，还有以钛酸盐为原料的氟钛酸盐热还原法。常用的还原剂主要是活泼金属单质及其合金，包括钙、镁、铝、钠。论述了这些方法的技术特点及研究现状。这些工艺大都处于实验室或中试研究阶段，其工业化潜力也不尽相同，最终在产品质量和经济成本上能否比Kroll法更具优越性尚需验证。

关键词: 金属钛, 四氯化钛, 二氧化钛, 氟钛酸盐, 热化学还原

Abstract: Titanium metal and its alloys are popular structural and functional materials due to their excellent properties. Even though titanium element is abundant in the earth, its extraction is very difficult because of its strong chemical affinity to other metals and interstitial elements including O, N, H, C, especially oxygen. The plasticity of titanium metal is sensitive to even trace oxygen content. It has been well acknowledged that it is extremely challenging to produce titanium metal with low enough oxygen. The currently commercialized method to produce Ti metal is the Kroll process, which has been optimized for years and highly matured, but it is costly and energy-intensive. In order to reduce the product cost of titanium metal and thus widen its applications, many new methods have been proposed in recent decades, which can be categorized into two main groups, thermochemical methods and electrochemical methods. This article made a mini-review of the developed thermochemical methods from the aspects of technical features and research status, including the Kroll process, the Hunter process, the ADMA process, the TiRO process, the gas reduction process, the CSIR-Ti process, the ITP-Armstrong process, and the ARC process which using TiCl4 as the precursor, the preform reduction process (PRP), molten salt facilitated Ca reduction process, electronically mediated reaction (EMR) process, Mg reduction?Ca deoxygenation two-step process, and the hydrogen assisted magnesiothermic reduction (HAMR) process which using TiO2 as the precursor, and thermochemical reduction of fluorotitanate. The common reductants are reactive metals and their alloys, including Ca, Mg, Al, and Na. These processes are still at the laboratory or pilot-plant stage, and it is recognized that the potential of industrialization of these methods is different, thus an uncertain time is needed to verify if these methods have advantages over the Kroll process on quality and production cost.

Key words: titanium metal, TiCl4, TiO2, fluorotitanate, thermochemical reduction

朱小芳李庆张盈房志刚郑诗礼孙沛夏阳. 热化学还原法制备金属钛的技术研究进展[J]. 过程工程学报, 2019, 19(3): 456-464.

Xiaofang ZHU Qing LI Ying ZHANG Zhigang Zak FANG Shili ZHENG Pei SUN Yang XIA. Mini-review on the preparation of titanium metal by the thermochemical processes[J]. Chin. J. Process Eng., 2019, 19(3): 456-464.

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