Hydrometallurgy 65 (2002) 31 – 36

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Kinetics of ilmenite dissolution in hydrochloric acid

Jacobus P. van Dyk a,*, Nanne M. Vegter a,1, P. Chris Pistorius b,2
a
Kumba Resources Limited, P.O. Box 9229, Pretoria 0001, South Africa
b
Department of Materials Science and Metallurgical Engineering, University of Pretoria, Pretoria 0001, South Africa
Received 12 January 2001; received in revised form 22 May 2002; accepted 22 May 2002

Abstract

The kinetics of ilmenite dissolution in hydrochloric acid is investigated with data previously published in literature. Based
on this, a leaching mechanism is proposed. The factors that influence changes in the rate-controlling step as leaching progresses
are also explained. Finally, the proposed leaching mechanism is used to explain the results of some experiments.
D 2002 Elsevier Science B.V. All rights reserved.

Keywords: Ilmenite; Hydrochloric acid; Leaching

1. Introduction ature, stirring, acid-to-ilmenite mole ratio and addi-

The aim of this paper is to investigate the kinetics
of ilmenite dissolution in hydrochloric acid. This is
done through a literature study that allows the pro-
posal of a mechanism for ilmenite leaching. The
proposed mechanism is used to explain the results
of certain experiments.
The ilmenite leaching reaction can be described by
the following chemical reaction:
FeTiO3 þ 2HCl ! Fe2þ þ TiO2þ þ 2Cl þ 2OH
The main parameters that can influence the rate of this
reaction are particle size, acid concentration, temper-
*
Corresponding author. Fax: +27-12-307-7407.
E-mail addresses: jaco.vandyk@kumbaresources.com
(J.P. van Dyk), nanne.vegter@kumbaresources.com (N.M. Vegter),
pistori@postino.up.ac.za (P.C. Pistorius).
1
Fax: + 27-12-674-1161.
2
Fax: + 27-12-362-5168.
tives. The influence of each of these parameters is
illustrated, where possible, through a comparison of
selected examples available in literature with the study
conducted by Jackson and Wadsworth (1976).
1.1. Particle size
Jackson and Wadsworth (1976) found that particle
size does not influence the rate of ilmenite dissolution.
Three size fractions were used namely  150 + 106,
 230 + 150 and  328 + 230 Am. The samples were
leached in 6 M HCl at 75 jC at an initial acid-to-
ilmenite mole ratio of 692:1. Both iron and titanium
went into solution under these conditions and almost
100% extraction of both elements was reached within
250 min for all size fractions.
Olanipekun (1999) found the opposite and showed
that particle size does influence the rate of ilmenite
dissolution. Three size fractions were used namely
+ 20 – 37, + 37 – 53 and + 53 –74 Am. The samples

0304-386X/02/$ - see front matter D 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 4 - 3 8 6 X ( 0 2 ) 0 0 0 6 3 - 4
32 J.P. van Dyk et al. / Hydrometallurgy 65 (2002) 31–36
were leached in 7.2 M HCl at 70 jC at an initial acid-
to-ilmenite mole ratio of 8:1. Both iron and titanium
went into solution under these conditions. The rate of
iron and titanium extraction increased as the particle
size decreased. The maximum amount of iron dis-
solution achieved was about 62% after 300 min. This
was for the + 20 – 37 Am fraction. At the same time,
about 58% of the titanium in this fraction dissolved.
1.2. Acid concentration
Both Hussein et al. (1976) and Jackson and Wads-
worth (1976) found that the rate of ilmenite dissolu-
tion is strongly dependent on acid concentration.
However, in the experiments conducted by Hussein
et al. (1976), mainly iron was dissolved, while in the
experiments by Jackson and Wadsworth (1976), both
titanium and iron went into solution. Hussein et al.
(1976) used four different acid concentrations ranging
from 2.16 to 6.48 M HCl. The leaching tests were
performed at 90 jC at initial acid-to-ilmenite mole
ratios that varied between 6:1 and 17:1, depending on
the acid strength. The maximum iron extraction was
about 35% after 160 min in the 6.48 M solution, while
only 7% of the iron was removed in the 2.16 M
solution after the same period. Jackson and Wads-
worth (1976) used 4, 5 and 6 M HCl solutions. The
leaching tests were conducted at 90 jC at initial acid-
to-ilmenite mole ratios, which depending on the acid
concentration, ranged from 188:1 to 353:1. After 400
min, 100% of the iron and titanium was extracted in
the 6 M HCl solution, while about 10% of the iron and
titanium were dissolved in the 4 M HCl solution in the
same time period.
1.3. Temperature
The rate of ilmenite dissolution increases rapidly as
the leach temperature rises. This was found by both
Jackson and Wadsworth (1976) and Sinha (1984), but
both iron and titanium went into solution in the
experiments conducted by Jackson and Wadsworth
(1976), while mainly iron dissolved in the experi-
ments conducted by Sinha (1984). Sinha (1984) con-
ducted his experiments at temperatures ranging from
80 to 108 jC. A 6 M HCl solution was used at an
initial acid-to-ilmenite mole ratio of 1:1. After 4 h,
almost 95% of the iron was extracted at 108 jC, while
less than 50% was extracted at 80 jC. Jackson and
Wadsworth (1976) used temperatures ranging from 60
to 90 jC. The acid concentration was 6 M HCl and the
initial acid-to-ilmenite mole ratio was 692:1. After
100 min, 100% of the iron and titanium was extracted
at 90 jC, while only 90% was extracted at 70 jC.
1.4. Stirring
Jackson and Wadsworth (1976) did not investigate
the effect of stirring speed, but Tsuchida et al. (1982)
and Sinha (1984) did include this parameter in their
investigations. Both Tsuchida et al. (1982) and Sinha
(1984) found no significant increase in the rate of iron
or titanium extraction with in an increase in stirring
speed in the range of 100– 500 min  1. Sinha (1984)
did, however, report that higher stirring speeds
resulted in the production of excessive quantities of
< 10 Am TiO2 fines. Tsuchida et al. (1982) conducted
his experiments with 11.4 M HCl at 70 jC and used
an initial acid-to-ilmenite mole ratio of 69:1. Sinha
(1984) conducted experiments with 6 M HCl at 108
jC. The initial acid-to-ilmenite mole ratio used by
Sinha (1984) was 1:1.
1.5. Acid-to-ilmenite mole ratio
The initial acid-to-ilmenite mole ratio seems to
influence whether both iron and titanium goes into
solution or whether only iron goes into solution. In the
experiments conducted by Jackson and Wadsworth
(1976) at initial acid-to-ilmenite mole ratios ranging
from 300:1 to 700:1 both iron and titanium tended to
go into solution, while in the experiments conducted
by Sinha (1984) at initial acid-to-ilmenite mole ratios
of 1:1 to 1.1:1, mainly iron was dissolved.
1.6. Additives
The addition of certain additives to the leach
solution can either increase or decrease the rate of
ilmenite dissolution. Duncan and Metson (1982)
found that when they added bisulphate and fluoride
to the leach solutions, the dissolution rate of both iron
and titanium increased, but when they added phos-
phoric acid and Ti(IV) to the leach solution, the
dissolution rate of iron and titanium decreased dra-
matically. Girgin (1990) performed a similar experi-
 J.P. van Dyk et al. / Hydrometallurgy 65 (2002) 31–36
ment using methanol additions. He found that the rate
of iron and titanium dissolution increased dramatically
when methanol additions were used compared to
dissolution in the normal hydrochloric acid solution
(3 M HCl).
2. Mechanism of ilmenite leaching
The information presented in the previous section
suggests that under certain conditions, the rate of the
dissolution of ilmenite could be chemically controlled.
Under other conditions, it could be controlled by the
diffusion of the reacting species and the resulting
products to or away from the reaction interface or it
can be controlled by the diffusion of these species
through a product layer on the surface of the particles.
A mechanism for ilmenite leaching in hydrochloric
acid will now be proposed that will clarify under what
conditions each of these rate-determining steps oper-
ate.
Initially, as predicted by the chemical reaction
equation, when ilmenite comes into contact with the
hydrochloric acid leach solution, both iron and tita-
nium go into solution. At this point, the rate is
controlled by the rate of the chemical reaction.
The next step in the chain of events will be
determined by the titanium species that form in
solution. Ti(IV) polymerises in hydrochloric acid
Fig. 1. Ti(IV) – chloride speciation diagram for 0.1 Ti(IV) activity at 298 K as calculated by Cservenyák et al. (1996).
33
solutions. Nabivanets and Kudritskaya (1967) deter-
mined the following criteria to indicate when poly-
merisation of titanium would occur: [Ti(IV)] > 10  3
M and [H(I)]>0.5 M. Fig. 1 shows a Ti(IV) – chloride
speciation diagram as calculated by Cservenyák et al.
(1996). This confirms that the Ti(IV) species that form
are dependent on the Ti(IV) and Cl(-I) concentrations
in solution. The Cl(-I) concentration in the leach
solution is usually determined through the choice of
the initial acid strength. The Ti(IV) concentration on
the other hand increases as the leach reaction pro-
gresses. Once the Ti(IV) concentration in solution
exceeds the value of 10  3 M, polymerisation will
occur. The diffusion of the resultant polymer chains
away from the reaction interface will now become the
rate-limiting step in the leach reaction. The timing of
the change in the rate-limiting step will depend on the
initial acid-to-ilmenite ratio. At high acid-to-ilmenite
ratios such as those used by Jackson and Wadsworth
(1976), the Ti(IV) concentration in solution may never
reach the critical concentration required for polymer-
isation, while under the conditions used by some of
the other investigators, such as Sinha (1984), the
critical concentration in solution may be reached very
early in the leach test.
The next critical event that influences the rate of
the reaction is the eventual formation of the solid
species TiOCl2 as the Ti(IV) concentration in solution
increases. The TiOCl2 can precipitate in the pores of
34 J.P. van Dyk et al. / Hydrometallurgy 65 (2002) 31–36
the leached particle or as fines in the leach solution.
When a relatively low initial acid-to-ilmenite mole
ratio is used along with a high leach temperature, the
titanium polymerisation reaction proceeds very rap-
idly and this results in precipitation of TiOCl2 in the
pores of the particles. At lower temperatures or at
higher initial acid-to-ilmenite mole ratios, the poly-
merisation reaction does not proceed as rapidly and
this results in the formation of TiOCl2 fines in the
leach solution. When the precipitation occurs in the
pores of the particles, the particles retain their shapes
and a product layer is formed. The rate-determining
step in the leach reaction now changes to diffusion of
the reacting species through the product layer.
Any additives that are added to the leach solution
can influence the titanium species in solution and
consequently the rate-determining step. By stabilising
soluble species of iron and titanium, the rate of
dissolution can be maintained. On the other hand,
the rate of dissolution can decrease significantly if the
additives promote the formation of solid species of
iron and titanium that precipitate from solution to
form a product layer on the surfaces of the particles.
The final event that can influence the leach reaction
is a significant reduction in the hydrogen ion concen-
tration. This will occur when a low initial acid-to-
ilmenite mole ratio is used in a batch leach test. The
decrease in acid concentration and the resultant rise in
pH can lead to the formation of a TiO2H2O precip-
itate in the existing product layer. It will also result in
a change in the rate-limiting step. The diffusion of
hydrogen ions to the reaction interface will now
become the rate-limiting step.
3. Experimental
Selected experiments were conducted to evaluate
the proposed mechanism. A waste stream, containing
mainly ilmenite that is produced during the production
of crude ilmenite for smelting was used for the
purpose of the investigation. The chemical composi-
tion of the material is presented in Table 1. The  106
Am fraction of the material was removed prior to the
experiments.
The leach experiments were conducted in a 1-L
batch fluidised leach column, fitted with a reflux
condenser. The premixed acid solution (6 M HCl,
Table 1
Chemical analysis of the ilmenite feed material that was used for the
leach experiments (wt.%)
TiO2 FeO MgO Al2O3 CaO V2O5 Cr2O3 MnO SiO2
43.3 47.83 0.58 0.61 0.07 0.33 0.69 0.81 0.9
unless stated otherwise) was introduced into the
reactor and heated up to the required temperature with
a heating mantle. The ilmenite sample was then
introduced. This was taken as the start of the experi-
ment. Solution samples were taken at regular intervals
for analysis. After 8 h, the experiment was ended and
the leach residue was separated from the spent liquor
through filtration and washed until the pH of the wash
solution was neutral. The residue was then split into
two. One part was analysed by ICP to determine the
chemical composition, and the other was analysed
with a Malvern Mastersizer to determine its particle
size distribution.
4. Results and discussion
Fig. 2 shows the effect of leach temperature and
initial acid-to-ilmenite mole ratio on the amount of
dissolved titanium. A significant amount of titanium
was dissolved when an initial acid-to-ilmenite mole
ratio of 60:1 was used, up to 45% at 105 jC. In
comparison, very little dissolution of titanium
occurred when an initial acid-to-ilmenite mole ratio
of 4:1 was used. A higher leach temperature increased
the quantity of dissolved titanium in both cases but the
effect was much more pronounced when an initial
acid-to-ilmenite mole ratio of 60:1 was used.
This result fits in with the proposed mechanism as
higher initial acid-to-ilmenite mole ratios will delay
the polymerisation of titanium and this will allow
much more titanium to dissolve from the ilmenite.
The formation of a product layer is also enhanced
when low initial acid-to-ilmenite mole ratios are used;
consequently, very little titanium dissolved when a
ratio of 4:1 was used.
Fig. 3 shows the percentage of  106 Am material
that formed during the leach experiments. All the
 106 Am particles were removed from the feed
material prior to the experiment. The  106 Am
material that was present in the residue was therefore
 J.P. van Dyk et al. / Hydrometallurgy 65 (2002) 31–36 35

Fig. 2. The influence of initial acid/ilmenite mole ratio during leaching on the percentage of titanium that is lost to the leach solution.

taken to be fines formed during the leaching process.
Very few fines formed when a 4:1 initial acid-to-
ilmenite mole ratio was used. In contrast, up to 50%
of the leach residue was fines when an initial acid-to-
ilmenite mole ratio of 60:1 was used at 100 jC. A
higher leaching temperature also increased the quan-
tity of fines in the residue. This effect was much more
pronounced for the experiment performed with the
60:1 initial acid-to-ilmenite mole ratio.
This result also supports the proposed mechanism.
At low initial acid-to-ilmenite mole ratios, the Ti(IV)
rapidly polymerises and precipitates inside the pores
of the particles. This allows the particles to retain their
shape and prevents the formation of TiOCl2 fines. At
high initial acid-to-ilmenite mole ratios, the polymer-
isation reaction is delayed and this result in the
destruction of the ilmenite particles, and when TiOCl2
finally forms, it will precipitate as extremely fine

Fig. 3. The effect of initial acid/ilmenite mole ratio on the quantity of TiO2 fines produced during leaching.
36 J.P. van Dyk et al. / Hydrometallurgy 65 (2002) 31–36
particles in the leach solution. The higher leach
temperature increased the rate of the leach reaction,
and this allowed for the formation of more fines in the
same period of leaching.
5. Conclusion
The rate-determining step during the dissolution of
ilmenite is dependent on the titanium species in
solution. This is regulated by the leach conditions at
any point in time. The changes in the rate-controlling
step can be predicted by tracking the changes in leach
conditions as the leach reaction progresses. The pro-
posed mechanism could explain the reported exper-
imental results as well as previously published results
by other authors.
References
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species in aqueous sulfuric and hydrochloric acids: I. Titanium
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