The 6th International Workshop on Industrial Technology of Rare Metals
Developments of novel recycling process for scraps of titanium metal
Y. Hamanaka, Y. Taninouchi, T. H. Okabe
Institute of Industrial Science, the University of Tokyo
Keywords: titanium, chloride waste, recycling, reaction mediator, samarium chloride
Increasing demand for titanium (Ti) and its alloys in the aerospace, chemical, and power
generation industries has led to the recycling of metallic Ti becoming ever more important.
Global production of Ti consequently increased three-fold between 2000 and 2012, with the
generation of Ti metal scrap also rising because of the large amount of off-grade product and
scrap that is generated during the smelting and metal working processes shown in Fig. 1. This
trend is likely to continue for at least the foreseeable future, as there is every indication that
the main consumer of Ti alloys (the aerospace industry) will continue to steadily develop.
There is also the potential for Ti to become a far more commonly used metal in the future
given that its mineral resources are relatively abundant. There is, therefore, a clear need for
the development of an effective Ti recycling technique.
Upgraded TiO2 Coke Cl2
Chloride waste Carbo-chlorination / Purification
(FeClx etc.)
TiCl4 COx Mg
Off-grade
sponge Reduction / Separation
Ti sponge Additive MgCl2
High-grade
scrap Remelting Electrolysis
Ingot of Ti or Ti-alloy Cl2 Mg
Swarf, etc. Metal working
End-of-life
product Metal product
Fig.1 Typical process flow chart for the production
of Ti products using the Kroll process and the
scraps generated from the process.
Current Ti remelting techniques essentially have little or no refining capability for major
impurities such as oxygen (O) and iron (Fe). As a result, only metal scraps that have low
levels of contamination and are well-sorted by alloy composition (i.e., high-grade scraps) are
returned to the ingots by remelting. Low-grade scraps unsuitable for remelting are often
reused as additives in the production of steel, etc., or are simply discarded as waste. For
example, off-grade Ti sponge can be used to deoxidize steel and/or improve its mechanical
properties; though in some cases, it is first converted into ferro titanium. However, when
considering the high production cost of Ti metal, it is clearly preferable that such low-grade
scraps are instead upgraded to a much higher value product. This presentation therefore
provides a review of the current status of recycling technology for Ti metal scraps.
A novel chlorination technique based on the iron chloride (FeClx) waste genetrated by the
Kroll process etc. has been previously proposed as the basis for establishing an upgrade
The 6th International Workshop on Industrial Technology of Rare Metals
process for Ti metal scraps.1) The recovery of Ti in the form of titanium tetrachloride (TiCl4)
achieved by this method is advantageous with regards to impurity control, and so is favorable
for the recycling of low-grade scraps. Moreover, this process can also minimize the problems
associated with chloride waste disposal. However, the direct reaction between Ti and FeClx
illustrated in Fig. 2(a) is hindered by the slow kinetics of Ti chlorination and high
volatilization of FeClx.2) To overcome these disadvantages, the authors have proposed a new
chlorination technique that is based on using a reaction mediator in molten salt, as shown in
Fig. 2(b).3) On the basis of various thermodynamic analyses of lanthanoid chlorides,
samarium trichloride (SmCl3) has been found to be a suitable reaction mediator; Ti metal is
chlorinated into gaseous TiCl4 by SmCl3 in the molten salt, and the reaction by-product
SmCl2 can be regenerated into SmCl3 by FeClx. Each reaction was experimentally
demonstrated at 1100 K in molten magnesium chloride (MgCl2). Although the authors only
demonstrated the fundamental feasibility of the technique, it can be concluded that newly
proposed process will be useful for the development of an efficient and environmentally
friendly recycling process for scraps of Ti metal.
(a)
Ti FeClx
(Scrap) (Chloride waste)
physical contact
TiCl4 Fe
(b)
Ti RCln FeClx
(Scrap) (Chloride waste)
in molten salt
TiCl4 RCln- Fe
Chlorination of Regeneration of
Ti metal reaction mediator
Fig.2 Reaction pathways for the chlorination of Ti in
metal scraps using FeClx chloride waste.
(a) Previously reported chlorination technique.1,2)
(b) Newly proposed chlorination technique.3)
References
[1] R. Matsuoka and T. H. Okabe: Proc. Symp. on Metallurgical Technology for Waste
Minimization, (134th TMS Annual Meeting, San Francisco, United States, 2005)
http://www.okabe.iis.u-
tokyo.ac.jp/japanese/for_students/parts/pdf/050218_TMS_proceedings_matsuoka.pdf.
[2] H. Zheng and T. H. Okabe: J. Alloy. Compd. 461 (2008) 459466.
[3] Y. Taninouchi, Y. Hamanaka and T. H. Okabe: Mater. Trans. (in press)
