Review “Titanium: An Overview of Resources and Production Methods”

Mohammed El Khalloufi
Olivier Drevelle and Gervais Soucy

Titanium, a transition metal commonly used in high-strength, corrosion-resistant, and

thermally stable metal alloys, is proven to have great potential in the aerospace and protective
industries. However, its high production costs have until now been the main obstacle in
increasing its use compared to other base metals on the market. Although titanium is the
fourth most abundant structural metal in the earth's crust, with a content of about 0.6%, its
use is limited due to its high price. This metal appeared after iron, magnesium and aluminum,
but is still considered exotic. These economic barriers prevent titanium from reaching its full
potential in marine and automotive industrial applications. Today's primary production
process, the Kroll process, was introduced by Germany's DuPont in 1948. Although effective,
the process is intermittent, energy intensive, and labor intensive, making it expensive.
Therefore, global research continues to be carried out to find new extraction methods that are
more efficient and economical. Titanium has unique properties that have not yet been fully
explored, such as superior mechanical strength and certain chemical properties compared to
other base metals. Nonetheless, problems such as high energy loss and material loss are
associated with the production of this metal. The main sources of titanium are minerals such
as ilmenite and rutile, with major deposits spread across countries such as Australia, China,
Norway and others. Ilmenite, with a content of between 40% and 65% titanium dioxide,
dominates global titanium mineral production. The use of titanium in industry is mainly
driven by its low density, high tensile strength, resistance to corrosion both sea water and
acids, and its ability as an alloy metal with special properties. One commonly used alloy is
Ti6A-4V, often used in medical applications such as knee replacement implants.
Titanium alloys have many physical (light weight, good mechanical properties,
resistance to cryogenic temperatures) and chemical (resistance to electrochemical corrosion,
biocompatibility) advantages, which make them indispensable materials for civil and military
applications in such broad fields as energy, transportation, medical (MRI magnets for
observing the human body), water treatment, and transport of corrosive liquids and gases
(Figure 1).

Figure 1. Titanium applications of the Western world by market sector.

Titanium deposits are enormous, with current estimates assuming global reserves of
650 billion metric tons of titanium oxide. Minable deposits are found in South Africa at
Namaqualand and Richards Bay, Australia, Canada, Norway and Ukraine (Figure 2). The two
main minerals considered for use are ilmenite and rutile and although both are minerals
available for economical mining, TiO2 is a part of almost every mineral, sand and rock.

Figure 2. Distribution of the titanium ore reserves in the world.

Common titanium minerals are anatase, brookite, leucoxene, perovskite, titanite,

rutile, and ilmenite. However, only ilmenite, leukoxene, and rutile have important
commercial value. Ilmenite and rutile are the two main titanium minerals used in industrial
applications, especially for the production of pigment-grade titanium metal and titanium
dioxide.
Many methods are used for the production of Ti metal powder. Therefore, Ti powder
is a product of an extraction process that produces primary metal using titanium tetrachloride
(TiCl4) or titanium dioxide (TiO2) as feed material. The process of making titanium powder
directly as an extractive metallurgy product includes making Ti from TiCl4, purified TiO2,
and/or rectified titanium slag (UGS) with a TiO2 content greater than 90%. Enhanced
titanium slag (UGS) is one of the fundamental products of carbothermal reduction of titanium
ores such as ilmenite. Natural rutile and synthetic rutile are also included in this raw material
category. These processes can be categorized: (1) thermochemical methods and (2)
electrochemical methods.
The following are thermochemical methods: Kroll Process. Commercial production of
primary Ti metal is generally made through the Kroll or Hunter process. The standard process
against which new technologies are compared is the Kroll process (Figure 3).
 Figure 3. Scheme and reactions of the Kroll process of titanium sponge production.

In the process, magnesium metal (reducing agent) is injected into a retort filled with argon
and heated to 800–900 C. However, the oxide impurities contained in Ti slag are also
chlorinated, so purified TiCl4 is produced by purifying the metal. Crude TiCl4 before Mg
reduction. Although most of the MgCl2 byproduct, and excess magnesium, is depleted during
reduction, the product sponge contains residual magnesium and MgCl2 in its porosity.
Magnesium and MgCl2 are separated by vacuum distillation or helium sweeping followed by
leaching. Some sponges had to be decommissioned due to contamination of the autoclave
walls. According to one estimate, 70% of the total energy consumption is used for distillation
to produce sponge metal. This shows that the cost of metal refining is one of the main cost
drivers, apart from the costs of precursors and reductants.
Hunter Process, a popular process carried out in the reduction of TiCl4 using Na is the
Hunter process. The Hunter and Kroll processes are very similar in that they are considered
thermochemical processes based on the reduction of TiCl4 to produce Ti. Economically, the
Hunter process is considered uncompetitive with the Kroll process. The main difficulty is that
to produce one mole of Ti by reducing TiCl4 requires four moles of Na, whereas for 1 mole
of Ti only two moles of Mg are needed. Moreover, producing Na via electrolysis is at least as
expensive as producing Mg. This problem makes processing Na more expensive than using
Mg. However, the Hunter process can also produce Ti powder as a replacement for Ti sponge.
In the Hunter process, TiCl4 and Na are introduced gradually into the reactor. This process is
generally carried out at a temperature of 800 C. Ti is formed on the surface of the liquid bath,
where TiCl4 gas is exposed to Na. Ti crystals are then formed and placed at the bottom of the
liquid bath. According to the operating parameters, some Ti particles can form Ti sponge,
while others are deposited as Ti powder. The purity of the powder produced via the Hunter
process is often higher (99%). Table 3 provides a comparison between the Kroll and Hunter
processes.
 Table 1. Comparison between Kroll and Hunter processes

Armstrong Process, Armstrong Process is considered the most advanced process. It

uses the same reaction as Hunter's process. Therefore, an important advantage of the
Armstrong process is continuity of operation, pumping liquid sodium into the reactor to react
continuously with TiCl4 gas (Table 4). The resulting Ti and NaCl powders were collected
from the reactor via a sodium stream. After the unreacted liquid Na is removed by filtration,
the Ti powder is purified by washing the salt. Armstrong products can be described as mini
sponges, namely microporous particles. Figure 6 shows aspects of Armstrong's process.

Figure 4. The Armstrong flow diagram.

TiRO Process, This process was developed by CSIRO (Commonwealth Scientific and
Industrial Research Organization) in Australia and uses the same reactions as the Kroll
process but in a fluidized bed reactor where gas-solid fluidization takes place, which greatly
increases the reaction rate and reduces both operations. and capital costs. The TiRO process
consists of two main steps: reduction of TiCl4 in a fluidized bed with Mg powder and
vacuum distillation to remove the by-products MgCl2 and Mg.
 Figure 5. Diagram of the process TiRO.

Based on the information above, TiCl4 can be reduced with sodium or magnesium. The main
characteristics of the powder are well detailed in Table 4 below. All the processes below use
TiO2 as raw material to produce high purity titanium powder.

Table 2. Comparison between characteristics of TiCl4 reduction-based processes.

Then for the electrochemical method, there is the Cambridge FFC Method. For decades,
titanium synthesis was considered difficult if the amount of oxygen was low. However, in
2000, a new method was introduced, which showed that TiO2 could be completely reduced in
solid form to the metal in molten calcium chloride, which is a cheap and non-toxic product.
This technique is known as the Cambridge FFC process (Figure 8). It operates in a molten
salt environment, usually in the range of 800C to 1100 C. CaCl2 is used as a salt because
CaCl2 can dissolve and transport oxygen ions. TiO2 reduction during the FFC process is
achieved through ionization of oxygen from the titanium-containing cathode, which diffuses
to the anode and is removed.
 Figure 6. A schematic illustration of the CTF’s Cambridge process.

The conclusion, Titanium has remained an essential metal because of its wide use in different
fields. Its demand in the industry has prompted unprecedented technical progress. Natural
ilmenite is the most abundant titanium-bearing mineral in the earth’s crust. The mineral
ilmenite has been significantly grown since his discovery. Nowadays, it is the most crucial
ore of titanium. The presented review shows the presence of enormous techniques for
manufacturing titanium powder and titanium metal. Many of these processes are at various
stages of development. The incentive for the development of new processes is often firmly
rooted in the ambition to achieve a low-cost alternative to the Kroll process for the
production of primary Ti metal. Marketed chloride-based thermochemical processes, such as
the Kroll and Hunter processes, are batch operations and require high-quality natural rutile or
improved synthetic slag, such as feeding and using cost-sensitive chlorination and
thermochlorination steps. Many improvements have been made to thermochemical processes,
but they offer few opportunities for cost reduction beyond current technology. Several
development methods have generated considerable interest and scale-up efforts, including the
Armstrong process and the FFC Cambridge process. The former is an example of using a
continuous process for the reduction of TiCl4 with Na or Mg while the latter is an example of
the various electrochemical methods that convert TiO2 into Ti metal in molten salt. A
recently developed method, named the HAMR process, is based on destabilizing the Ti-O
system by using hydrogen as a temporary alloying element during the magnesium thermal
reduction of TiO2. However, compared with the Kroll, these producers are expanding their
production to meet the unprecedented demand for titanium. Overall, it is expected that it will
take several years before any new process will be in commercial production and compete
with the Kroll process.