An Attempt for Extraction of Titanium form Indian Beach Sand 121

An Attempt for Extraction of Titanium from Indian

Beach Sand
S.K. Maity*, P. Bhattacharyya*, B. Nayak*, M. Chandrashekhar*,
P.N. Mohandas** and V. Ananth***
*National Metallurgical Laboratory, Jamshedpur **Regional Research Laboratory, Trivundrum
***Central Electrochemical Research Institute, Karaikudi

ABSTRACT: In the present paper, the characterization and beneficiation studies carried out with beach sand
of Kerala coast and further value addition to prepare synthetic rutile and extraction of titanium from synthetic
rutile are presented. Beneficiation route involving pre-concentration followed by high tension and magnetic
separations was found to produce Ilmenite. Further value addition studies involving reduction followed by
oxidation and leaching could produce synthetic rutile containing more than 90% TiO2. An attempt has been
initiated to elctro-win titanium metal on a molten metal pool preferably on Al, by electrochemical reduction
of rutile. Rutile-carbon composite were used as anodes in a molten mixture of alkali chlorides at around
800°C. Molten Al pool was used as cathode. During electrolysis Ti particles formed and sinked into the
molten Al. Ti was estimated by AAS. Optical and SEM showed the presence of dendritic needles of titanium
rich phase in the Al matrix. The EDAX analysis on the needle shaped particles suggest the formation of
TiAl2. The current efficiency of this process was up to 30%.

1. INTRODUCTION attention of the researchers and investors. In this

Titanium and its alloys are very attractive
materials due to the higher weight to strength
ratio and high resistance towards corrosion.
Titanium aluminide based intermetallics and
composites are emerging as high temperature
materials that can be used in jet turbines and
aircrafts (Froes et al., 1992).
However, due to the high cost of
processing of titanium and titanium based
alloys, the researchers show their interest to
reduce the production cost using metallo-
thermic reduction, electro winning and net
shape powder metallurgy techniques.
Substantial improvements have been made
during the last decade in the technology for
production of titanium and titanium alloys.
Improvements in the metallothermic reduction
processes namely Kroll’s and Hunter’s
processes report an energy consumption of
30 KWH/ kg of purified titanium sponge. The
electrolytic processes proposed by Ginatta of
Italy, claimed a saving of about 12 KWH/ kg
(Ginattu et al., 1988). The lower production
cost of electrolytic titanium alloys with respect
to metallothermic processes is drawing
electrowining, the titanium-based raw material is
titanium chloride. Recently in much discussed FFC
processes, the raw material is TiO2 (Fray et al.,
2000). In the proposed study the starting raw
material was beach sand. India has large reserve of
it. India, endowed with a coastline of over 6000 km,
hosts some of the largest and richest shoreline
placers. The state of Kerala is by far the best in
India, in terms of titanium mineral placer resources
—especially of ilmenite (Ali et al., 2001). Rutile
(tetragonal TiO2) and Ilmenite (FeO.TiO2) are the
main minerals which are exploited for commercial
production of titanium metal. Indian recoverable
reserve of titanium minerals, estimated at 374.62
million tons of ilmenite and 21.02 million tons of
rutile, account for more than 21% of the global
titanium resources but still it has not resulted in
proliferation of its value added industries. As a result
the country is highly dependent on export of low
value ilmenite (Patra
et al., 2004 and Nair et al., 2000). In the present study,
titanium was extracted from the electrochemical
reduction synthetic rutile which was prepared from
ilmenite recovered from Indian beach sand. The
following processes were involved in this study:
(a) Preparation of highly purified ilmenite from
122  Mineral Processing Technology (MPT 2007)
beach sand, (b) Preparation of a concentrated
titanium based compound, say, “synthetic
rutile” and (c) Electrolysis of “rutile”. The
primary motive was development of low cost,
low energy processes of value addition towards
better utilization of national resources.
2. EXPERIMENTAL
Total 21 sub-samples, each weighing about
10 kg., were collected from 18 km. stretch of
CP (Chavakkad Ponnani) area by CESS-
Thiruvanantapuram and sent to NML. A
Process flow sheet has been developed at
bench scale level, to produce high quality
ilmenite concentrate (containing >95%
ilmenite), following physical beneficiation
route which involves preconcentration, high
tension and magnetic separartion. Further value
addition studies were carried out at RRL,
Trivundrum to prepare synthetic rutile. The
process involves essentially the following
steps: (1) Carbothermic reduction of ilmenite to
convert the iron oxide to metallic iron,
(2) Catalytic conversion of the metallic iron to
solid iron oxide which can be easily separated
from the aqueous medium, (3) Rutilation of the
Fig. 1: Sketch of the experimental cell
product at higher temperature which is essentially an
oxidation step and (4) Dilute HCl leaching of the
rutileted product. The product “synthetic rutile”
obtained contained more than 94% TiO2 in it.
The different proportions of prepared synthetic
rutile powder (–300 mesh) were mixed thoroughly
with carbon paste (soderberg paste). The mixture
was kept at 400C for 8 hours and cooled inside the
furnace. This mixture was compressed in a hydraulic
press in a die fabricated by die steel to form a
cylindrical block of 33 mm diameter with about
70 mm high. The blocks were backed at 700–900°C
for 8 hours in inert atmosphere. After baking one set
were used for measuring the porosity, apparent
density, conductivity and crushing strength. The
composite blocks used for electrolytic studies were
provided with 3 mm steel lead.
The I–V characteristics were studied on the
system: composite anode, molten Al cathode and
alkali metal chloride melt at 700 to 900°C. The pre
electrolysis was carried out to remove moisture and
other impurities in the fused electrolytes (NaCl +
KCl). The electrolysis of composite anode in the
chloride melt was conducted around 800°C using
molten Al pool as cathode in an inert atmosphere.
The sketch of the electrolytic cell for conducting the
electrochemical studies is shown in Fig. 1.
An Attempt for Extraction of Titanium form Indian Beach Sand 123
All the experiments were conducted under
constant current conditions. The cell was operated
a capacity of maximum of 10 A. After the
electrolysis the whole materials was allowed to
cool in the controlled atmosphere and the frozen
cathode metals was undergone for AAS, optical,
SEM and EDAX investigations.

3. RESULTS AD DISCUSSIONS

Samples collected from 18 km. stretch of CP area

at almost 1 km. apart. Total Heavy Mineral
(THM) content at each different sampling
location is shown in Fig. 2. The Ilmenite prepared
at bench scale level from the beach sand of CP
area are shown in Fig. 3. The XRD studies (Fig.
4) confirms that the concentration of ilmenite was
more than 96%. Ilmenite concentrate produced
could be easily converted to synthetic rutile
containing around 95% TiO2 (Fig. 5)
(Bhattacharyya et al., 2006 & 2006). Fig. 3: Concentrates having more than 96%
Ilmenite prepared from beach sand

120
% Heavy Minerals

100

80

60

40

20

0
CP 3
CP 5

CP 11
CP 13
CP 1

CP 7
CP 9

CP 19
CP 21
CP 15
CP 17

Location of sampling

Fig. 2: Heavy mineral distribution at different

sample collection locations of CP area Fig. 4: X-ray Diffraction of Ilmenite

The physical characteristics of the carbon

campsite anode (Fig. 6) is most important for the
electrochemical studies. Therefore physical
characteristics of these blocks containing 60%,
70%, and 80% rutile underwent for density,
porosity, electrical resistivity and crushing
strength measurement. The density and porosity
of the backed composite anodes blocks increased
with increase in titanium dioxide (rutile) content.

Fig. 5: Synthetic rutile from ilmenite concentrate

124  Mineral Processing Technology (MPT 2007)
Fig. 6: Synthetic rutile-carbon composite anode
The electrical resistivity also is increased with
increase in oxide content, but it is decreased with
increase in baking temperature. The study of
crushing strength offered a different look. The
blocks with 60% and 70% rutile offered lower
strength compared to the blocks containing 80%
rutile.
The I–V of the composite anode and molten
Al cathode with respect to Ag/AgCl electrode in
Fig. 7: I-V characteristics of molten Al cathode with respect to Ag/AgCl electrode
in NaCl and KCl melt
the NaCl – KCl melt (800°C) were shown in
Fig. 7. The I-V curves include two clear reduction
waves and third one is not very significant. The
final wave corresponds to the discharge of the
alkali metal ions of the bath. The wave which
appears just prior to alkali metals ions discharge
corresponds to the reduction of Ti (II) and Ti (III)
ions to Ti (0). Extrapolation of waves to Zero
current value give the discharge potential of Ti
(II) to Ti (0) (–0.95V) and Na/K ions to metal (–
1.90V). It may be worth mentioned that the wave
corresponding to the reduction of Ti+4 ions to
lower valent ions is not clearly visible.
The anode with 70% rutile showed good dis-
solution behavior. Moreover, it has superior
physical properties like density, crushing strength
and electrical conductivity. The results (AAS
analysis of Ti metal in aluminum matrix) revealed
that Faradic efficiency of this process is low and it
was 10 to 30%. This is normally expected from a
small laboratory experimental cell. It is expected
that oxygen from the lattice of TiO2 comes out to
react with carbon to form CO/CO2. The Ti ions
combine with Cl– ions to form TiCl4 (in-situ) or Ti
complexes with alkali chlorides. These were
supported by the gas evolution at anode and the
pinkish colour of the melt.
An Attempt for Extraction of Titanium form Indian Beach Sand
The possible chemical and electro-
chemical reactions at the composite anode may
be as follows (Ananth et al., 1998 and Ratvik,
1987, Ananth and Maity, 2001)
At lower potential:
TiO2 → TiO+2 + O2–
TiO+2 + 4Cl– → TiCl4 + O2–
Ti Cl4 + NaCl → Na2 Ti Cl6 (complex)
O2– + C → CO + 2e
2O2– + C → CO2 + 4e
At higher potential:
Cl– → Cl2 + 2e
The in-situ formation of TiCl4 was taking
place on the composite anode surface and it
was reduced to titanium particles on the surface
of molten Al cathode. The particles thus
formed, after growing to a certain thickness,
sinked into the molten Al. The optical
metallographs (Fig. 8) of the cathode metal
sample showed the finer precipitates of second
particles in the Al matrix which is confirm as
similar toTiAl2 by EDAX.
Fig. 8: Optical micrograph of cathode metal
at 400X shows the needle shaped Ti particle
in Al matrix
Al used as cathode has two advantages.
The Ti particle once deposited on molten Al
and sinks into it. Due to the surface tension of
Al metal no non-metallic materials stay in the
melt. Secondly, once Ti is entrapped in Al,
further oxidation is prevented due to the better
thermodynamic stability of Ti compared to Al.
125
The results obtained from the study paves a path for
a feasibility of extraction of Ti in the form of Ti – Al
intermetallics. The lower efficiency of the processes
might be result of the disproportionate reactions
occurring in the fused salt bath containing Ti ions
(Oki et al., 1987). It can be minimized if more care
will be taken to avoid air entry into the cell.
4. CONCLUSIONS
This study concludes that good quality ilmenite,
which in turn be converted to synthetic rutile, can be
recovered from beach placers of unexploited CP
area. Further, the electrochemical study was an
attempt to extract Ti metal. It showed the feasibility
of fabrication of titanium dioxide- carbon composite
anode and deposition of Ti particles in the molten Al
cathode in small laboratory scale. However, at the
higher temperature the Ti remained as Ti-Al
intermetallics. Keeping in view the future global
need for Ti, present study has immense importance
towards conservation of national resources.
5. ACKNOWLEDGEMENT
The authors wish to express their sincere thanks to
Prof. S.P. Mehrotra, Director, NML, Jamshedpur and
Dr. Baba, Director, CESS, Trivundrum. Thanks are
also due to other colleagues of NML, CECRI, RRL-
Trivundrum.
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