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Transactions of
Nonferrous Metals
Society of China
Trans. Nonferrous Met. SOC.China 17(2007) 429- 433

Electrochemical process of titanium extraction

CH. RVS. NAGESH, C. S. RAMACHANDRAN
Defence Metallurgical Research Laboratory, Hyderabad, A.P. India-500058
Received 20 November 2005; accepted 9 January 2006
Abstract: A wide variety of processes are being pursued by researchers for cost effective extraction of titanium metal.
Electrochemical processes are promising due to simplicity and being less capital intensive. Some of the promising electrochemical
processes of titanium extraction were reviewed and the results of laboratory scale experiments on electrochemical reduction of TiOz
granules were brought out. Some of the kinetic parameters of the reduction process were discussed while presenting the quality
improvements achieved in the experimentation.
Key words: electrochemical reduction; titanium dioxide; titanium; kinetic parameters

1 Introduction
Titanium metal has enormous potential for a wide
variety of applications but its usage and consumption
have been limited to aerospace and few other areas
mainly because of the high cost of metal. Currently
titanium is extracted from titanium oxide ore by a series
of process steps involving: 1) chlorination of oxide
concentrate to prepare titanium tetrachloride (TiC14), 2)
reduction of TiCI, by magnesium metal (Kroll process),
3) vacuum distillatiodleaching of reduced mass.
Electrolysis of the by-product MgClz is a parallel process
carried out for recovering magnesium metal and chlorine.
Sodium reduction of TiC14 (Hunter process) had also
been operated till early 1990s but its commercial
application at present is limited. Fused salt electrolysis of
Tic14 in alkali chloride mixtures has been extensively
pursued in Dow-Howmet, USA and Ginatta, Italy. But
the process could not be commercialized due to several
problems such as multi-valency of the metal, selection of
materials of construction of the cell and other
techno-economic factors.
Extractian of titanium directly from titanium
dioxide has been proven to be futile due to high affinity
of the metal towards oxygen and high process
temperatures. Conventional carbothennic reduction and
metallothermic reduction methods did not yield titanium
of required purity owing to limiting thermodynamic
constraint and high chemical reactivity of the metal.

Fused salt electrolysis of TiOz in floride/phosphate baths

to prepare titanium metal was not successful due to
problems such as complexities in the cell design, poor
solubility of oxide in the melts, recombination of metal,
problems associated with purity of the metal.

2 Electrochemical reduction processes

The current practice of Kroll process for titanium
sponge production has undergone tremendous
improvements and advancements, resulting in significant
improvement in energy savings as well as quality of the
product[ 11. Apparently the Kroll technology has assumed
stagnation and there is hardly any scope existing for
bringing down the cost of titanium metal further by this
method. There have been a wide variety of efforts to
develop an alternate process of titanium extraction to
produce the metal at a cheaper price. Extensive study on
electrochemical de-oxidation of titanium in molten
calcium chloride electrolyte led to the development of
electrochemical reduction processes. The following is a
brief description of important electrochemical/
electrometallurgical reduction processes that are being
developed.

2.1 FCC process

The process patented by FRAY, FARTHING and
CHEN of Cambridge University, UK[Z-31, involves
removal of oxygen from solid titanium dioxide by
subjecting it to electrolysis in molten calcium chloride

Corresponding author: CH.RVS. NAGESH; E-mail: [email protected]

430

CH. RVS. NAGESH, et al/Trans. Nonferrous Met. SOC.China 17(2007)

Table 1 Other electrochemical processes of titanium extraction

bath using graphite as anode. The process involves

preparation of TiOz compacts/pellets from the oxide
powder that are sintered and taken as cathode. In this
process it is understood that, oxygen diffuses out of the
oxide through crystal defects under the conditions of
applied DC voltage that is also aided by the formation of
electrically conductive 'magnelli' phase at high
temperature. Oxygen ions pass through molten CaC12
electrolyte to form CO/C02 gas at the graphite anode.
The process is vigorously being pursued by TIMET,
USA at California University, Berkeley for scale up and
commercial adaptation[4].

under study
Name/organization
MER Corporation,
USA

BHP Billiton process

'

2.2 0s process
The calciothermic reduction of Ti02 and in-situ
electrolysis of CaO in molten calcium chloride was
extensively studied by O N 0 and SUZUKI[S] for
preparing titanium sponge granules. The 0s process,
thus combines the calciothermic reduction at about 900
"C and hsed salt electrolysis of CaO in CaC12 at DC
voltage in the range 2.7-3.2 V in a single set up
comprising a reduction zone and an electrolytic zone. In
a conceptual cell design proposed by this process,
titanium dioxide powder is continuously fed into a
titanium crucible and from the bottom of the crucible
molten CaC12 with dissolved CaO is taken out and fed
into the electrolytic compartment. Calcium metal is fed
into the cruc.ible from the electrolytic chamber. The
process is under investigation for improvements and
scale up.
2.3 OIT liquid titanium process
Quebec Iron and Titanium(QIT), Canada has
recently patented a new titanium extraction process[6], in
which titania slag as obtained by beneficiation of
ilmenite can be treated in an electric arc furnace to
remove impurity oxides and then subsequently subjected
to electrolysis using molten CaFz as electrolyte to
electrowin titanium that can be tapped out in liquid
condition. A few other processes for titanium extraction
based on electrometallurgy that are being tried on
laboratory scale are given in Table 1.

3 Experimental
At the Defence Metallurgical Research Laboratory,
Hyderabad(DMRL) experimental work on laboratory
scale has been carried out to study the electrochemical
reduction of TiOz in molten calcium chloride bath (Fig. 1).
Studies are also under way at DMRL to explore the
kinetics of the process. The following is a description of
experimental work and discussion of the results.

Electronically
Mediated Reaction
(EMR)/Molten Salt
Electrolysis (MSE)
Process

Process
Anode reduction of TiOz,
electrolysis in molten halide
mixture to deposit titanium
metal on cathode
Electrochemical reduction of
TiO, in calcium chloride bath
Electrolytic reduction of Ti02
without physical contact of
oxide and calcium using
Ca-Ni alloy and CaClz
electrolyte

powder/

Product
Powder/
flake
Sponge

Powder

Binder

Granules

Cathode

Titanium sponge
Fig.1 Steps in electrochemical reduction process for titanium

sponge production
Initially bench scale experimental work was
conducted in which different pre-forms of titanium
dioxide were subjected to electrochemical reduction in
calcium chloride bath at a temperature range of 800-900
"C to study the important parameters of the process, and
the details of which were presented elsewhere[7]. This
has led to the current activity of cell operation on a batch
size of 100-200 g of sponge.
The schematic of the cell is shown in Fig.2 that
consists of a stainless steel retort heated by an electrical
resistance hrnace. The retort is closed by a lid that
has provision of nozzles for electrode leads, argon gas
supply and vent gas outlet. TiOz granules prepared from
the oxide powder are sintered and taken into a stainless
steel perforated basket that is inserted into a graphite
crucible placed in the retort with the help of a steel rod.
The steel rod and graphite crucible are connected to the
two terminals of a DC power source. Typical
experimental procedure involves: 1) loading of weighed

CH. RVS. NAGESH, et aVTrans. Nonferrous Met. SOC. China 17(2007)

quantity of calcium chloride into the graphite crucible

and melting; 2) loading of weighed quantity of oxide
granules into the steel basket and assembly of the system
so that the basket with granules lies well above the melt
level; 3) melting of salt and lowering of the basket to a
pre-determined level; and 4) application of DC voltage
and continuation of electrolysis for selected time.
During the electrolysis argon gas is purged into the
system and vent gases are allowed to pass through a
bubbler filled with baryta solution. At the end of the
electrolysis, the basket is lifted up above the melt level
and the system is cooled to room temperature under
argon gas cover. At room temperature the basket with
metallized granules is thoroughly washed with water,
acetic acid and dilute HC1 to remove the adhered salt
completely. The metallized granules are then dried and
taken for characterization.

I----

16rnm steel rod

43 1

titanium dioxide to the oxide-salt interface; 2) transport

of oxygen ions through molten electrolyte towards
graphite anode; and 3 ) liberation of CO/C02 gas at the
anode. Among these steps oxygen diffusion in solid
titanium dioxide is the slowest and becomes the rate
controlling step. Diffusion of oxygen in the oxide
depends on parameters such as defects concentration,
temperature, and electrical conductivity. The ionic
mobility may be computed employing a simple model[8]
such as y= Vq62I kT , where U is vibration frequency,
q is charge of ion and 6 is mean free path. Electrical
conductivity of titanium dioxide was measured in the
temperature range of 25-1 000 C. The conductivity
measurement method followed the standards of setup as
well as procedure listed in the ASTM standard D257-99.
Typical measurement involves placing of the oxide
specimen in a tubular furnace and heating to high
temperature and application of DC voltage of the order
of milli volts and measuring current response (in milli
amps) employing Ketheley instrument continuously
every few seconds. It is found that there is a sharp
increase in conductivity (Fig.3) at a temperature of
about 930 C , which is explained by the formation of
highly conductive magnelli phase[3]. The rate of
oxygen ion removal from the oxide-salt interface might
also influence the bulk diffusion of oxygen within the
oxide.

Inconel
retort
Furnace

C
U

vfolten

CaClz

level
- Ti02
granules
Graphite

crucible

o l e

100

Fig.2 Schematic of experimental set-up

A number of experiments were conducted to study

various parameters such as bath temperature,
inter-electrode distance,
DC
voltage.
Some
improvements in the cell configuration could be
incorporated for achieving better results.
In an electrochemical reduction process, the overall
reaction can be described as: O(Metal)+e=02- (Molten
salt). At graphite anode, 02-(Molten salt)+C=CO/C02.
The reduction process involving complete removal of
oxygen from the oxide is viewed to take place by the
following steps: 1) diffusion of oxygen from bulk

300

500

700

- 900
1

Temperature/%
Fig3 Variation of electrical conductivity of Ti02 with

temperature

4 Discussion
During the reduction process the cell current is
found to be gradually increasing while the cell voltage is
kept constant, which may be explained by the fall in
resistance of the oxide granules due to metallization. The
cell current comprises current due to ionic conductivity
and current due to electronic conductivity of the oxide.

432

CH. RVS. NAGESH, et al/Trans. Nonferrous Met. SOC.China 17(2007)

The ionic currents are expected to reduce as the

metallization progresses. The electronic current is
expected to increase as the electrical resistance of the
system falls at high temperature. However, detailed study
of these aspects only can bring out the current patterns.
As the electrolysis is initiated, formation of white
precipitate is noticed in the baryta bubbler indicating the
occurrence of desired de-oxidation reactions. On the
basis of conversion of oxygen removed from the oxide to
CO/C02 that is absorbed in baryta and change in rate of
formation of carbonate further insight into the kinetics of
the process may be determined.
SEM and EDAX characterization of the washed and
dried granules show a network of metallic species, i.e.
titanium particulate with very low levels of oxygen as
seen from Figs.4 and 5. Photographs of initial oxide
granules and metallized species generated aRer the
experiment and a button (measuring approximately 50
mm in diameter and 5 mm in thickness) melted out of the
sponge by non-consumable arc melting are shown in
Fig.6. Characterization of the button by hardness testing,
chemical analysis and metallography reveals good
metallization in the samples. The hardness of the button
is found to be as high as BHN 270, which must be due to
higher oxygen and carbon contents that were analyzed to
be about 1% and 0.6% respectively. However, higher
oxygen content in the button could be due to the fact that
it is very difficult to separate partially metallized
granules from the fully metallized granules which are

FigA SEM photographsOf sponge

reduction of Ti02

by electrochemical

EnergyIkeV
Fig.5 Typical EDAX profile of sponge granule

Fig.6 Photographs of sintered oxide granules(a), titanium

sponge granules(b) and button melted out of sponge granules(c)

CH. RVS. NAGESH. et aVTrans. Nonferrous Met. SOC.China 17(2007)

melted into button. The degree of metallization is found

to be improved with increased electrolyte temperature.
However, at higher temperatures it is found that the
carbon content in the metal increases. It should be noted
that pick up of carbon is noticed even in the early
experimental work reported on de-oxidation of titanium
by electrochemical means[9]. Some improvements in cell
parameters could lead to reduced carbon impurity
content of the metal as seen from Fig.7, which shows
carbon X-ray images taken by EPMA of initial melts and
recent melts with improvements. There are some
improvements with respect to other impurity elements as
seen from Table 2 that shows the chemical analysis of the
button samples of the initial and recent melts.

433

Table 2 Chemical analysis of titanium button pieces (mass

fraction. %\
Initial melt
Recent melt
Element
0.6
0.028
Fe
0.7
0.010
Ni
0.2
0.021
Si
0.1
0.035
Cr
0.4
0.03 1
A1

scope to improve the process and quality of the product.

Various fundamental aspects of the process including
kinetics are being explored for further understanding of
the process.

Acknowledgements
The authors are thankful to Dr. A. M. Sriram
Murthy, Director, DMRL for permitting to publish this
work. They are grateful to Defence Research &
Development Organization(DRD0) for initiating this
activity and extending financial support. They also wish
to acknowledge the help received from Dr. V. V. Bhanu
Prasad and Sir V. V. Rama Rao of CCG & EPMA groups
of DMRL. Technical support to carry out the resistance
measurement of TiOz received from Dr. A. K. Suri,
BARC is gratefully acknowledged.

References

Fig.7 Carbon X-ray images of titanium samples: (a) Initial

melts; (b) Recent melts

5 Conclusions
The results obtained on electrochemical reduction
process have been very encouraging. There is a lot of

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