International Journal of Mineral Processing, 1 (1974) 2 8 7 - - 3 0 5

© Elsevier Scientific Publishing C o m p a n y , A m s t e r d a m - - Printed in The Netherlands

RECENT DEVELOPMENTS IN PROCESSING ILMENITE F O R TITANIUM

N.C. K O T H A R I
Department of Engineering, James Cook University of North Queensland, Townsville, Qld.
(Australia)
(Received D e c e m b e r 5, 1973; revised and accepted J u n e 27, 1974)

ABSTRACT
Kothari, N.C., 1974. R e c e n t d e v e l o p m e n t s in processing ilmenite for titanium. Int. J.
Miner. Process., 1: 287--305.
This review examines the literature on the processing of ilmenite during the last fifty
years. It is aimed at giving a simplified outline of the major processes currently used for
beneficiation and r e c o v e r y of t i t a n i u m dioxide and t i t a n i u m metal from ilmenite ores.
A t t e n t i o n has been drawn to the main parameters affecting the recovery of t i t a n i u m
dioxide. All m e t h o d s developed to date are o f the batch t y p e and on a laboratory scale
and require further evaluation on a larger scale if ilmenite is to be a m a j o r source o f metal
titanium.
A brief discussion on the e x t r a c t i o n of t i t a n i u m metal f r o m rutile has been given.

INTRODUCTION

Ever since the metal titanium burst from obscurity a few years ago, it has
been burdened with elegant superlatives. N o t since Hall discovered the process
for the electrolysis of bauxite, which inaugurated the aluminium industry, has
the world seen a new construction metal possessing such outstanding
characteristics, appear on the market. In contrast to aluminium, however,
where the method of production was developed first and applications for the
metal later, many applications for titanium are already known, b u t difficulties
in production methods must still be overcome.
Titanium is a light element which though discovered in 1790 was not
produced in useful quantity until 1945. In 1948, the Bureau of Mines and
other laboratories in the States were producing a few pounds of commercially-
pure titanium for experimental purposes. The year 1950, however, marked
the commercial d e b u t of the metal. By early fall 1950, total titanium produc-
tion for experimental purposes had risen to an annual rate of 60 tons. This
was increased to 5,500 tons in 1957. In 1957 the U.S.S.R. put up the Sputnik
and the U.S. Government decided to transfer its energies to aerospace activities,
therefore, causing a great reduction in the production of titanium. However,
development has gone ahead to a stage where 14,000 tons were produced in
the States in 1967. A very large increase in production is expected in the
288

seventies. Elsewhere in the world there is no significant production of the

metal. However, there is a small titanium industry in Great Britain, Europe
and Japan. The U.S.S.R. exports small quantities of titanium sponge.

THE ORES OF TITANIUM

The ores containing titanium minerals are widely distributed in m a n y parts

of the world. The two principal ores of titanium are futile (TiO2), a reddish-
brown coloured substance with metallic lustre and ilmenite (FeTiO3). Rutile,
the chief source of titanium, has a hardness of 6--6.5 and a specific granity of
4.18--4.25. It usually contains up to 10% iron in the form of iron oxides. It
is usually dark red or black in nature but can be brown, yellow, green or
violet. The ore gives a yellow or pale brown streak. There are varieties of
rutile containing larger amounts of iron, but these are not as desirable for the
production of titanium as is the high-purity rutile. Some of the minor ores
are nigrine, ilmenorutile, seyenite, brookite, and anatase.
Ilmenite is the second important ore of titanium which contains theoreti-
cally 52.7% TiO2. However the minerals found vary from 40 to 60% TiO2. It
does not have cleavage and fractures conchoidally. It has a hardness of 5--6
and a specific gravity of 4.3--5.5. The color is usually black and gives a
brownish-red to black streak. Ilmenite is slightly magnetic. The mineral varies
in composition through the limits of four minerals: crichtonite, geikielite,
pyrophonite and senaite. The chemical analyses of ilmenite ores from the
principal sources in the world are given in Table I. It is usually associated with
magnetite.

THE EXTRACTIVE METALLURGY OF TITANIUM

There are a number of economical and technical factors which must be

taken into account when discussing the extraction of titanium. In general
terms, rutile is treated differently from ilmenite ores, thus, the two types of
ore will be treated separately.
Prior to any processing the basic approach in treatment of titanium ores is
concentration by conventional mineral beneficiation techniques. The ore is
crushed and ground. The iron content (magnetite) is removed by magnetic
separation. The gravity separation methods (Hymphrey spiral, tabling,
filtering, drying, etc.) and flotation are used to separate silica, silicate and
aluminate. Electrostatic separation is used extensively to remove zircon, etc.
to obtain high-grade TiO2 from the beach sand. There are various ways of
treating concentrates depending on whether the goal is to produce a pure
titanium oxide for pigment or to produce metallic titanium (Fig.l).
 289

TT~
0

= ~ 1 1 1 1 1 1 ~ I

~mo~''o
~ . . . . . . . .

~ ~ I ~wo

~TI~I I//~
z

~ . . ~ ° ~ .

0
290

• CRUSHED~ '~ SCREEN

I ILMENITE ~ MAGNETIC ~_
iAND iRON r I SEPARATION r

[ 'OTAT'O ] IO
T
SH
E
PE
R
A
RG
AR
O
TA
IN
SV
T
IY
ji J

C
ONC
EN
TR
AT
E

~ ELECTROSTATCI~
SEPARAT
O
IN j '

I TAI NG t

~PlGMENT~ ITITANIUMI
Fig.1. Flowsheet of processing rutile.

A BRIEF OUTLINE OF PROCESSES F O R THE PRODUCTION OF TITANIUM FROM

RUTILE

Since this review covers mainly the recovery of titanium from ilmenite,
only a very brief summary of various processes of extracting titanium from
natural rutile is given here. Figure 2 depicts the production of titanium from
rutile.
Four important processes that axe developed on a pilot-plant scale for the
manufacture of titanium from natural rutile are: (1) the iodide process (Van
Arkel and De Boer, 1925, 1928; De Boer and Fast, 1926, 1930; Fast, 1938,
1939; Gosner, 1948); (2) the Kroll process (Kroll, 1930, 1940, 1940a; Dean
et al., 1946; Dean and Silkes, 1946; Stoddard and Pietz, 1947; Campbell et al.,
1948); (3) a continuous process developed at Batelle Memorial Institute
(Jaffee, 1949; Jaffee and Pitler, 1950); and (4) electrowinning of titanium.
 291

[ REDUCTION 7 T I ~ ~ Hz
CWITH
all_ ~ - 1 SPONGE j ~R~MOVED I

i WITH ~ WITH N
[CARBON l I HIGH CARBO' 5

' EOUOT'ON 17
WITH II
(i Na ALLOY] I ]TITANIUM 7
or ~ 88"L~ P__URITY
~

cW:TIH ~_~/_~ _I RME%CTNIONWITH IF~s.

j TI-[ArNIUM
'l'r~ E' iI

I I IODINE AT I l
co j 30oo0 j ...... i:_.
+ * . .... ~ [ REMELTED /
CO'z i ~ I N
IELECTROLYSISI IT'I,I IARC FURNACEJ

PURITY TITANIUM

ITrf~NlU~
Fig.2. Production of titanium from TiO2 (schematic).

The iodide process

Essentially the process depends on the formation of a volatile iodide by

reacting crude titanium with iodine in the absence of any other reactive gas:
TiI4 ~- Ti + 212 (1)

The Kroll process

A detailed account is given extensively in the literature (Gosner, 1948;

Kroll, 1930, 1940, 1940a; Dean et al., 1946). It produces oxygen-free
titanium using natural rutile which is transformed initially to TiCL and then
is decomposed to titanium metal (Fig.2).
TiO2 + C12 -~ TIC12 + O2 (2)
292

The free-energy change is usually negative. However, the addition of carbon

to the titanium oxide causes the reaction to take place in the forward
direction:
TiO2 + 2C + 2C12 -* TIC14 + 2CO (3)
The reaction is positive. The negative free-energy of formation of carbon
monoxide becomes the determining factor in the overall free-energy change
and efficiency of the process. The actual conversion of TiO2 to TIC14 in
reaction with C12/C is in t w o steps; 50% is converted b y the external reaction
as shown:
TiO2 + 2Cl: + 2C ~ TIC1, + 2CO (4)
and 50% b y the internal reaction:
TiO2 + 2C12 + 2CO -~ TIC14 + 2CO2 (5)
The sign and magnitude of the free-energy changes are largely dependent
upon the free-energy formation of the C12/C. TiCl~ is a colourless liquid that
boils at 136°C and is therefore vapour at the operating temperature. The
liquid TIC14 is reduced as follows:
TIC14 + 2Mg -~ 2Ti + 2MgCI2 (6)
The disadvantage of the Kroll process is that it is only a batch-type process,
but it still leads the field for the production of cheap titanium.

Continuous method

An improved m e t h o d of producing titanium developed at Batelle (Jaffee,

1949; Jaffee and Pitier, 1950) involves the continuous production of titanium
or titanium-alloy ingots, employing Mg and TIC14 as the raw materials. It
involves a two-step operation carried o u t in a single integrated unit.

Electrowinning of titanium

Attempts have been made to obtain high-purity titanium from TIC14 b y

electrolysis. Alpert et al. (1956, 1957, 1959) produced titanium b y electroly-
sis using a diaphragm cell with a silicon liner. Rand and Reimert (1954)
developed a laboratory cell for producing titanium by electrolysis of TIC14
onto a molten salt. The cathode in their cell was similar to that used by
Alpert b u t the cell lid had to be removed to obtain the deposit. The dripping
of TIC14 o n t o the molten salt caused TiCh vapours to rise and condense in
the cold parts of the cell creating operational and corrosion problems. Opie
and Svanstrom (1959) and Reimert (1963) modified the m e t h o d of introduc-
tion of TIC14. They suggested a basket-type cathode. The cell was operated
successfully without a diaphragm b u t the TIC14 reacted with the electro-
deposited Ti metal causing metal to disintegrate into powder. Head (1960,
 293

1961) carried o u t electrolysis of TIC14 in the presence of a hydrogen atmosphere.

The deposit produced on the cathode was impure.
Leone et al. (1967) proved that the electrolysis of titanium tetrachloride
using a molten-salt bath (LiC1--KC1--TiC12) as an electrolyte offers an
excellent industrial potential for the production of high-purity titanium
metal. The titanium tetrachloride is fed continuously below the surface of
m o l t e n electrolyte which is an eutectic mixture of salts (LiC1--KC1--TiC12)
with aluminium oxide diaphragms. Temperature varies between 500 and
550°C. The chlorine produced during the electrolysis is exhausted without
coming into contact with the metal cell structure due to use of an aluminium
oxide diaphragm. A schematic drawing of the production of titanium from
titanium tetrachloride by electrolysis is given in Fig.3.
The New Jersey Zinc Co. (1968) has built an integrated electrolytic
titanium pilot-plant for processing TIC14 obtained from Sorel slag. Here TIC14
is gravity-fed to the electrolytic cells containing an electrolyte made of a salt
mixture (KC1--LiC1--NaC1) at 400°C. The anode was in the centre surrounded
b y a perforated cathode. The porous nickel-metal diaphragms were used to
separate anode and cathode sections of the cell. The cell was operated at
a b o u t 13,000 A and TIC14 was added in a feed to current ratio of 2:1, i.e.
one ml of TIC14 needs about one Ah for complete reduction to elemental Ti
(Barnett, 1959). The deposit of Ti from the cathode was removed b y chiselling
and the C12 was returned for further use in the cell. The chiselled deposit of
Ti was subjected to leaching and classification.

THE EXTRACTION OF TITANIUM FROM ILMENITE ORES

Extensive deposits of ilmenite are found in various parts of the world

(Table I) and considerable attention has been given to upgrading these deposits
b y removing iron and other minor impurities (chromium, vanadium, etc.) to
form synthetic futile (TiO2) for pigment use and a source of titanium tetra-
chloride for production of titanium metal either b y the Kroll process or by
electrolysis (Henn and Barclay, 1970). Usually the ilmenite deposits contain
b e t w e e n 40--60% titanium dioxide and the other major constituent is iron
oxide. The t w o oxides combine together as a chemical c o m p o u n d in a
spinel form. This requires the mineral to be upgraded to rutile prior to its
utilization as TiO2. No k n o w n physical m e t h o d is available to separate Fe
from TiO2 in ilmenite. A chemical attack is the necessary prelude for upgrading.
The major processes currently used for beneficiation are given below:
(a) Smelting with coal or coke (Armant and Cole, 1949; Stoddard et al.,
1950; Stoddard and Wyatt, 1953, 1955; Banning et al., 1955; Roberson and
Banning, 1955; C)sterberg, 1960; Noda, 1965; Elger and Stickney, 1972) in an
electric furnace.
(b) Selective chlorination of ilmenite using hydrochloric acid or a combina-
tion of chlorine and carbon monoxide at elevated temperatures and pressures
294

A hCl, f~ed

^nnde C~th~e

ic ,

A~eous
N~OH

Stain~esss~e
tubeSte~l,l'~~--'~!~ee~e~ct~ele~ iI Ii

B C

J
.... Ji :

~l i: i!

I I
i! ~!

U
m0o{Jssf~v

Fig.3. Electrowinning of titanium. (Leone et al., 1967.) A. Electrowinning cell.

B. A n o d e and cathode assembly. C. T i t a n i u m deposits on cathode.
 295

(Manocha, 1953; Anderson and Row, 1956; Wilska, 1956; Frey, 1957; T'am
and Chang, 1957; Murach and Povedskaya, 1958; Kharkar and Patel, 1958;
Doraiswamy et al., 1959; Dunn, 1960; Patel and Jere, 1960; Bergholm, 1961;
Belyakova, 1962, 1963; Hughes and Arkless, 1965; Barksdale, 1966;
Sankaran et al., 1966; Sehra et al., 1966; Rabie et al., 1968; Cairns, 1969;
Shelton, 1971).
(c) Sulphidization of ilmenite using either H2SO4, H2S, sodium sulphide
with carbon or sulphur vapour at high temperatures under pressure (Tokimoto
and Hattori, 1955; Prasad and Tripathi, 1958; Sharova and Fotiev, 1959;
Gaskin and Ringwood, 1960; Tikkanen et al., 1963; Jain et al., 1970).
(d) Solid-state reduction of iron oxide in the presence of a catalyst and
subsequent removal of the oxide as a slurry (Tokimoto and Hattori, 1956;
Tokimoto et al., 1959; Becher, 1963; Becher et al., 1965).

Reduction of ilmenite by solid-state reaction

In recent years titania (TiO2) as a slag has been produced by smelting

ilmenite with coke in an electric furnace. Numerous publications are available
on the commercial technique for slag preparation (Armant and Cole, 1949;
Stoddard et al., 1950; Stoddard and Wyatt, 1953, 1955; Banning et al., 1955;
Roberson and Banning, 1955; C)sterberg, 1966; Noda, 1965). However, the
U.S. Bureau of Mines recently developed a new process for producing syn-
thetic rutile from ilmenite (Elger and Stickney, 1971, 1972). Figure 4 shows
a schematic flow diagram of preparation of titania-rich slag for obtaining
synthetic rutile. The ilmenite was first reduced by carbon (coke or coal) in
an electric furnace to produce pig iron and titania-enriched slag. Phosphorous
pentoxide had been used as a flux to form a glassy slag in which the major
impurities (oxides of Fe, A1, Mg, Mn, Ca, and Si) were dissolved. The futile
(TiO2) crystals 5--150 microns in size were formed in slag heated to tempera-
tures of 800--1,550°C. However, TiO2 crystals formed at temperatures above
1,300°C were of the highest purity. The TiO2 crystals formed at 800°C were
only 5 microns in size while increase in temperatures to 1,500°C increased
the rutile crystals to 150 microns in size. Crystals of this size were large
enough for recovery from the slag. The slag was crushed and ground to
-100--325 mesh to liberate the TiO2 crystals. The ground mass was treated
with 8.5% phosphoric acid solution at 50°C to dissolve the glassy slag matrix.
The TiO2 crystals from the leached slag were removed by tabling. The TiO2
content amounted to 94.4--96.8% while the titanium recovered represented
77--88%. The particle size of the ground slag played an important role in
leaching. Fine grinding (325-mesh particle size) decreased the recovery of
TiO2. Purity of synthetic rutile concentrates was dependent on temperatures
used in the P205 fluxing. As fluxing temperatures increased TiO~ content of
the slag increased. A temperature of 1,400°C was suitable for fluxing, how-
ever, the use of 1,500°C increased the size of rutile crystals. More than 90%
of titanium in the ilmenite was recovered as synthetic rutile (Elger and
Stickney, 1971, 1972).
296

FURNACE
moo-16oo'c|
-'~ PiG IRON ]
TITANIUM
RICH
SLAG

CRUSHED 8r I
GROUND TO
- 6 5 MESH

J SYNTHESIS OF RUTILEL
-[ ,ooo-,soo.c r
L
PRODUCT GROUND
TO -IO MESH j I
,~ LEAC!ING~
1
i
WASTE j
IBYPRODUCT SYNTHETIC
90-97 % RUTILE
TiO=
Fig.4. Production of synthetic rutile from ilmenite. (Elger and Stickney, 1972.)

A large number of investigations for reducing iron from ilmenite using

either solid or gaseous reducing agents such as carbon, hydrogen, carbon
monoxide or mixtures of hydrogen and carbon monoxide have been carried
out successfully on a laboratory scale (Tokimoto, 1955, 1956; Nakazowa,
1957, 1958; Osterberg, 1960; Walsh et al., 1960).

Chlorination of ilmenite

Preferential removal of iron from ilmenite by chlorination has been carried

out by a large number of workers (Manocha, 1953; Anderson and Rowe,
1956; Wilska, 1956a, b; Frey, 1957; T'am and Chang, 1957; Kharkar and
Patel, 1958; Murach and Povedskaya, 1958; Doraiswamy et al., 1959; Dunn,
1960; Patel and Jere, 1960; Bergholm, 1961; Belyakova, 1962; Belyakova and
Dvernyakova, 1963; Hughes and Arkless, 1965; Sankaran et al., 1965; Sehra
et al., 1966; Rabie et al., 1968; Cairns, 1969; Shelton, 1971).
The iron has been removed either by direct leaching of ilmenite using
hydrochloric acid (Anderson and Rowe, 1956; Patel and Jere, 1960; Sehra et
al., 1966) or by preferential chlorination in the presence of C and CO at
500--800°C resulting in a product containing 55--90% TiO~ (Monocha, 1953;
Kharkar and Patel, 1958; Patel and Jere, 1960). The fluidized-bed chlorination
 297

of ilmenite using a mixture of chlorine, carbon monoxide and carbon dioxide

at temperatures 800--1,100°C has been carried out by a number of researchers
(Doraiswamy et al., 1959; Dunn, 1960; Bergholm, 1961; Hughes and Arkless,
1965; Rabie et al., 1968). Doraiswamy et al. (1959) using a mixture of
CO--C12 ratio of 1.6 at a temperature of 900°C removed 97% of iron with a
loss of 1% TiO2. Dunn (1960) on the other hand obtained an artificial rutile
assaying 97--98% TiO2 with only 0.7% iron at 900--1,000°C in the presence
of a CO--C12 mixture and further chlorination at higher temperatures yielded
TIC14. Frey (1957) developed a continuous process of chlorinating iron o~:ides
at lower temperatures 800--950°C and titanium at 1,100°C using a mixture of
CO--C12. Bergholm (1961) chlorinated ilmenite using a CO--C12--CO2 mix cure
at 900°C. The iron chloride produced was oxidized to regenerate chlorine for
recirculation. Hughes and Arkless (1965) used two-stage fluidized-bed reactors.
In the first reactor the ilmenite was treated with a CO--CI~ mixture at 800°C
and this converted the iron oxide into the iron-chloride vapour which was
passed to the second bed where it oxidized to ferric oxide regenerating
chlorine.
The direct chlorination of ilmenite with hydrogen chloride gas results in
the following reaction:
FeO.TiO2 + 2HC1 ~ FeCl2 + TiO~ + H20 (7)
The formation of FeC12, a liquid with low volatility, causes some difficulty
in the upgrading process. However, in the presence of oxygen or air FeC12
changes to FeC13 which has a high vapour-pressure, and removes most of the
iron from the futile (Kubaschewski, 1956; Kelly and Mah, 1959). The reaction
is represented as:
1 2 2
2FeO.TiO2 + 2HC1 + ~ O ~ FeC13 + TiO2 + H20 (8)
3 -~-3 -3
(s) (g) (g) (g) (s) (g)
This reaction produces ferric chloride vapour from which chlorine can be
regenerated.
The work performed on Kerala beach sand (Sankaran et al., 1968) in
upgrading ilmenite has shown that the chlorination of ilmenite at 800°C using
hydrogen-chloride gas alone removes most of the impurities such as iron,
chromium, vanadium, etc. yielding a product having a rutile structure. The
use of a mixture of air--HC1 or air--Cl2 gas resulted in removing 99% of the
vanadium and 40--50% of the chromium from ilmenite and the product con-
taining 95--97% TiO2 was obtained. Figure 5 shows the flow diagram of
chlorination of ilmenite in the presence of air or O2.

1
FeO.TiO2 + ~ O2 ,~ Fe203 TiO2 + TiO2 (9)
298

1 1
-~ Fe203.TiO2 + 6HC1 ~ Fe2C16 + ~- TiO2 + 3H20 (up to 760°C)

2 FeCl3 (above 760°C) (10)

The upgrading of ilmenite in the presence of a CO--C12 gas mixture in a
fluidized bed reactor at temperatures 700--1,000°C has been carried o u t
successfully b y Rabie et al. (1968). Various factors such as the Co--C12 ratio,
particle size of concentrate, and temperature affecting chlorination were investi-
gated. The chlorination process increases with the increase in temperature,
decrease in particle size and increase in CO--C12 ratio at a b o u t 1.3--1.4. The
iron was removed as ferric-chloride vapour leaving a residue enriched in
titania. The reaction is given below:
2FeO.TiO2 + 2CO + 3C12 -+ 2TIO2 + 2FeC13 + 2CO (il)
(s) (g) (g) (s) (g) (g)

MAGNETIC
SEPARATION

ILMENITE
CONCENTRATE

R'OOiTT'NOJ
FURNACE I I FeCl 3 l
CONOENSORj

FOR PRODUCTION[
OF Ti CI4-" Ti j

Fig.5. Schematic flow diagram showing chlorination of ilmenite in the presence of an

air--HC1 mixture. (Sankaran et al., 1968.)

The rutile produced was practically free from iron and manganese, but
chromium and vanadium were only partly removed. Figure 6 shows the
schematic flow-diagram of chlorination in a fluidized bed.
From the foregoing it shows clearly that selective chlorination is capable
of upgrading ilmenite to an acceptable further use in converting TiO2 into
TIC14.
 299

A recent Dupont patent (Cairns, 1969) deals with the preparation of

titanium tetrachloride from ilmenite by the total chlorination at 850--1,050°C:
2FeO.TiO2 + 6C + 7C12 ~ 2TIC14 + 2FeC13 + 6CO (12)
The titanium tetrachloride from the reaction chamber is then separated by
partial condensation.
Attempts have been made to remove iron from ilmenite concentrate using
ammonia chloride (Ivashentsev, 1964; Safiullin and Belyaev, 1966, 1967).

ILMENITE
CONCENTRATE 1

FLUIDIZED T f ~ ~,

FOR PRODUCTION
OF Ti Chl -~Ti

Fig.6. Schematic flow diagram showing chlorination of ilmenite in fluidized bed. (Rabie
et al., 1968.)

Sulphidiza tion o f ilmen ite

The upgrading of ilmenite has been attempted by using sulphide gas,

Tikkanen (1963) leached ilmenite with dilute sulphuric acid (7--25%) in two
steps:
FeO.TiO2 + 2H2SO4 -~ FeSO4 + TiO2SO~ + 2H20 (13)

TiO2.SO2 + 2H20 -~ TiO(OH)2 + H2SO4 (14)

The reaction produces hydrolysis which tends to coat the dissolving

ilmenite particles inhibiting the dissolution. However, this effect was elimina-
ted by abrading the ilmenite particle with copper or quartz balls in a copper-
lined rotating autoclave during leaching.
Selective sulphidization of iron bY a sulphidizing roast and its subsequent
separation by leaching with acid was carried out with some success. The
product containing 97.7--98.9% TiO2 has been reported (Prasad and Tripathi,
1958; Sharova and Fotiev, 1959; Gaskin and Ringwood, 1960; Tikkanen et al.,
1963). Attempts have been made to beneficiate ilmenite with sodium
sulphate plus carbon (Tokimoto and Hattori, 1955; Prasad and Tripathi, 1958;
300

Sharova and Fotiev, 1959). Gaskin and Ringwood (196i) tried sulphidization
of iimvnite using sulphur vapour. Jain et al, (1970) experimented with a
preferential sulphidization of ilmenite in a static bed using hydrogen-sulphide
gas with a flow rate of about 20 cm3/min at 800--1,100°C for various lengths
of time. About 95% of the iron was converted to iron sulphide at 1,000°C
operating for 5 h or at 1,100°C for 4 h. The sulphidized product was leached
with boiling dilute hydrochloric acid (2N). However, leaching was found to
be most effective by employing 20% excess 2N boiling hydrochloric acid for
1/2 h. They (Jain et al., 1970) consider that the process is suitable for up-
grading ilmenite commercially. Figure 7 shows the schematic flow diagram
of sulphidization of ilmenite using hydrogen-sulphide gas.
Walker (1967) also treated finely ground ilmenite with concentrated
sulphuric acid in batch reactors. The reaction product consisting of ferrous,
ferric and titanium sulphates was further leached with dilute sulphuric acid to
remove iron salts. On hydrolysis, titanium sulphate was converted to insoluble
titanium hydrate which was washed and calcined to obtain titanium dioxide.
Working on the same principles, Judd and Palmer (1973) developed a cyclic
acid leaching process using dilute sulphuric acid. The final product was
titanium dioxide with 98% purity. The process is on a laboratory scale and
further evaluation is needed for its suitability as a commercial process.

ILMENITE [
CONCENTRATE I
+
SULPHIDI ZATION I rUNREACTED1 1
J CHAMBER ~ I--~ CONDENSOR]
-1 TEMP 8OO-IIOO,C I l H2S GAS I L

I SULPHIDIZEDI
PRODUCT J

=1 LEACHING
"I IRON COMPOUND

F~ TE--~ ~ -~CONDENSOR
J

-~TiOz 91%]
1
FOR TITANIUM
METAL

Fig.7. Flow diagram of sulphidization of ilmenite using hydrogen gas and dilute hydrochloric
acid. (Jain et al., 1970.)
 301

Reduction of iron oxide using catalyst

Becher et al. (1963, 1965) developed a process of removing iron oxide

from ilmenite by a solid-state reaction in two steps. In the first step the iron
oxides were reduced using coal to metallic iron. The reduced ilmenite was
agitated in aerated water in the presence of catalysts removing iron in the
form of rust. The TiO2 content was then separated by precipitation of iron
oxide which was then removed by decantation. Figure 8 shows a tentative
two stage reduction flow diagram of ilmenite in the presence of a catalyst.
The process is considered to be an attractive one when considering the recov-
ery of TiO2 for manufacturing pigment. The iron oxide removed as a by-
product can be sold as an iron-oxide powder. The process has a bright future
where ilmenite concentrate has a very low content of chromium and vanadium.

CONCLUSIONS

It is clear that much work needs to be done on the extraction of titanium

metal from ilmenite concentrate. The present high cost of titanium is in the
price of rutile which sells at about U.S.50/ton while ilmenite sells for
U.S.$20/ton. The development of titanium into commercially important
materials rests not so much on its uses as its availability. Unless new and
improved methods are available for its production in large quantities, it can

ILMENITE ]
CONCENTRATE
1
] REOOCT,ON L
CHAMBER
AT 9'00-1150°C [

+
REACTION FOR
CONVERTING Fe
INTO ~ Fe (OH)2~-Ti02~I--[~ ]
Fe ~OH)2+ TiO2 [
TEMP50-150°C

i PRECIPITATION 1
OF

Fig.8. Schematic flow diagram of two stage reduction of ilmenite in the presence of a
catalyst. (Becher et al., 1965.)
302

never compete with commercial metals such as aluminium and stainless steel.
Considerable research is needed to produce TiO2 from ilmenite. All methods
developed to date are of the batch type. Until we have a process for obtaining
pure titanium comparable with those for retrieving steel or aluminium,
titanium will have to remain under the classification "unusual m e t a l " if not
"rare metal".
The economics of upgrading ilmenite would be influenced to a considerable
extent by the availability of the raw material. The upgrading of ilmenite for
the production of a synthetic futile has been receiving considerable attention
in the beach sand industry throughout the world. Various processes of up-
grading ilmenite have been under study for quite a number of years. Only a
sorel slag or Becher process has been tried on a semi-industrial operation and
has shown some economic justification. There are m a n y difficulties associated
with chloride and sulphide processes. The chloride process has a great future.
With the re-use of chlorine atmospheric and water pollution can be minimized.
Bulk chlorine is now becoming available in various parts of the world and
hydrogen-chlorine gas is available as a by-product from the petro-chemical
and other industries. Consequently the cost of chloride processes would
become more competitive as time goes on. Furthermore chlorine or hydrogen
chloride can be regenerated and so the overall cost is reduced.
In the sulphide process, sulphur will be seriously considered from a pollution
point of view. It would help in reducing the effluent problem. Furthermore
this process has further limitations in countries where sulphur has to be
imported. The upgrading of ilmenite is always done by removing the iron.
Low temperature reduction of iron oxide to metallic iron has been started
semi-commercially in Western Australia.
If titanium is obtained from ilmenite and a continuous-extraction process
is needed instead of the batch type Kroll process, a dramatic saving would
result.

ACKNOWLEDGEMENTS

The author wishes to t h a n k Professor D.H. Trollope, Head of Engineering

for providing laboratory facilities and Mr. S. Peterson for his technical
assistance in the work.
The author is grateful to Dr. Brian Chappell for reading the manuscript.

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