Materials Transactions, Vol. 58, No. 3 (2017) pp.

319 to 321
Special Issue on New Proposals on Titanium Production and Molten Salts
©2017 The Japan Institute of Metals and Materials

Titanium Sponge Production Method by Kroll Process at OTC

Kotaro Nakamura*, Takahiro Iida, Nobuo Nakamura and Tadao Araike
Osaka Titanium Technologies Co., Ltd., Amagasaki 660–8533, Japan

Titanium sponge is industrially produced by the Kroll process. OTC has been manufacturing titanium sponge using the Kroll process since
1952 and now has the capacity to produce 40,000 ton of titanium sponge a year. Titanium sponge made by the Kroll process is widely used, but
that used for aircraft parts is ranked Premium Quality (PQ) grade and only a few producers, including OTC, can make it because of the high
reliability required. Demand for PQ grade titanium sponge is increasing, so cost reductions within the Kroll process are needed. OTC has re-
duced costs by using middle-to-low-grade raw materials, producing the world s largest sponge cake, and improving productivity.
[doi:10.2320/matertrans.MK201634]

(Received November 1, 2016; Accepted December 27, 2016; Published February 25, 2017)
Keywords: titanium sponge, Kroll process

1. Introduction electronic components and so on.

On a special note, both the number of commercial airplanes
It has been almost 70 years since the first industrial produc- to be delivered and the ratio of titanium content per aircraft
tion of titanium began in 1947 in the USA. OSAKA Titanium are increasing. Figure 1 shows the changes in delivery vol-
technologies Co., Ltd. (OTC) began manufacturing titanium umes of commercial aircraft and the demand for titanium
sponge by the Kroll process in 1952. used in aircraft over the years. There is increasing demand for
Table 1 shows the history of OTC. OTC has the capacity to titanium. Taking this demand into account, OTC is improving
produce 40,000 ton of titanium sponge annually and achieved its sponge titanium productivity and cost efficiency. Many
a cumulative total output of 600,000 ton in 2016. technological improvements are introduced in this paper.
Titanium sponge made by the Kroll process is widely used
in applications such as aircraft (engines and fuselages), plants 2. Kroll Process
(electric power plants, desalination plants, and heat exchang-
ers), consumer products (eye-glass frames and golf clubs), Figure 2 shows the Kroll process flow. The Kroll process
consists of four processes.1–6)
i. Chlorination and purification of titanium ore
Table 1 Chronological table of OTC milestones in titanium sponge produc- The raw materials are chlorinated and distillated to pro-
tion.
duce pure titanium tetrachloride (TiCl4).
Year Key events ii. Reduction and vacuum separation
1952 Built the first titanium pilot plant in Japan. Pure titanium tetrachloride is reduced using molten mag-
1977 Completed reduction/separation furnaces (2-ton batch). nesium to produce titanium sponge and fed to vacuum distil-
1978 Commenced operation of integrated titanium U-furnace lation to remove residual magnesium and magnesium chlo-
(5-ton batch). ride (MgCl2) in the titanium cake.
2006 Increased annual production capacity of titanium sponge iii. Electrolysis of magnesium chloride
to 24,000 ton. The magnesium chloride, which is a by-product of the re-
2011 Increased annual production capacity of titanium sponge duction reaction, is decomposed into magnesium and chlo-
to 40,000 ton. rine gas. This magnesium and chlorine gas are reused in the
2016 Achieved cumulative total output of 600,000 ton. reduction and chlorination processes.

Fig. 1 Results and forecast of delivery volumes of commercial aircraft and demand for titanium mill products.

*
Corresponding author, E-mail: knakamura@osaka-ti.co.jp
320 K. Nakamura, T. Iida, N. Nakamura and T. Araike

Fig. 3 Process flow for making TiCl4.

Fig. 2 Kroll process flow.

iv. Crushing and sizing the titanium sponge cake

The sponge cake is crushed by a guillotine press machine,
shearing machine, and jaw crusher. Then, the crushed titani- Fig. 4 Process flow of reduction and vacuum separation. (a) reduction pro-
um is blended and packaged into a drum. cess, (b) vacuum separation process.

2.1 Chlorination and purification of titanium ore

Figure 3 shows the TiCl4 process flow. Titanium ore and precipitates to the bottom of the vessel due to its heavier den-
coke are fed into the chlorinator. Chlorine gas is blown into sity, and is periodically removed by pressurizing the vessel
the chlorinator. The chlorination reaction is caused according with argon gas.
to eq. (1). After the reduction reaction is completed, vacuum separa-
tion is begun. The vessel is heated from the outside with an
TiO2 + C + 2Cl2 → TiCl4 + CO/CO2 (1)
electric heater. A vacuum is generated inside the vessel. As a
Titanium ore is stripped of its oxygen and binds with the result, the magnesium chloride and the magnesium remaining
chlorine, forming crude titanium tetrachloride. in the titanium sponge evaporate, and high purity titanium
Next, the crude TiCl4 is distilled to remove impurities. In sponge is obtained. The condenser vessel is reused for the
this process, highly purified TiCl4 is produced from ore that next reduction reaction.
contained impurities. The purity standard of pure TiCl4 is 5N The reduction-vacuum separation are batch processes, so
(99.999%) grade, therefore a large amount of impurities are we improved per-batch yield and automated the process.
removed in this process. However, as production yield increases, it becomes diffi-
The raw materials account for a large portion of the titani- cult to control the heat balance. For example, sufficient heat
um sponge production costs. output is required during reduction while efficient heat input
Therefore, we radically advanced our technologies to uti- is required in vacuum separation. We solved these issues by
lize relatively low cost, middle-to-low-grade raw materials. using computer simulation and improving the furnace. As a
Establishing technologies for sorting and mixing raw mate- result, OTC raised what was the world s highest productivity
rials, and stabilizing chlorinator operation enabled OTC to even more, as now we are capable of producing more than 13
blend about 70% middle-to-low-grade raw materials in the tons per batch.
process. OTC successfully developed technologies that en-
abled the use of middle-to-low-grade materials without sacri- 2.3 Electrolysis of magnesium chloride
ficing quality. In this process, the magnesium chloride produced in the
reduction process is decomposed into chlorine and magne-
2.2 Reduction and vacuum separation sium by electrolysis. The chlorine is returned to the chlorina-
Figure 4 shows the process flow of reduction and vacuum tion and distillation process, and the magnesium is returned
separation. to the reduction and vacuum separation process for reuse.
After molten magnesium is fed into the vessel, liquid tita- In order to increase the productivity of electrolysis, OTC
nium tetrachloride is fed into the vessel and a reduction reac- switched from monopolar cells to multipolar cells (Fig. 5).
tion is caused to obtain titanium sponge. The reaction formu- Now, OTC is using 5-pole cells and has dramatically im-
la is shown in eq. (2). proved productivity and, by way of that, current efficiency as
well.
TiCl4 + 2Mg → Ti + 2MgCl2 (2)
Magnesium chloride, which is produced as a by-product,
 Titanium Sponge Production Method by Kroll Process at OTC 321

Table 2 Quality of ASTM grade1, 4N5 and 5N grade (unit: ppm).

Fe Ni Cr Al Si As Sn Sb O N
ASTM Grade 1 2000 - - - - - - - 1800 300
4N5 Grade 15 3 3 3 3 3 3 3 400 30
5N Grade 5 1 1 1 1 1 1 1 300 30

and foremost, it is ranked PQ grade, which is required espe-

Fig. 5 OTC s electrolysis cells. cially for aircraft parts. It is also high quality, as OTC can
stably produce 5N-purity titanium using our highly advanced
Kroll method. (Table 2 shows some purity examples.) Re-
garding oxygen content, OTC can produce titanium sponge
with oxygen levels of less than 200 ppm.7)

4. Conclusion

Demand for titanium has been increasing. OTC will con-

tinue to serve these demands of the titanium industry. We
think that the productivity of the Kroll process can be im-
proved even more, so we will continue technical development
of the Kroll process in the future.
Fig. 6 Crushing, sizing and packaging process flow.
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3. OTC Titanium Sponge Quality (2015).

OTC s titanium sponge has the following features. First