Mineral Processing and Extractive Metallurgy Review

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A review on the recovery of titanium dioxide from

Ilmenite ores by direct leaching technologies

Thi Hong Nguyen & Man Seung Lee

To cite this article: Thi Hong Nguyen & Man Seung Lee (2018): A review on the recovery of
titanium dioxide from Ilmenite ores by direct leaching technologies, Mineral Processing and
Extractive Metallurgy Review, DOI: 10.1080/08827508.2018.1502668

To link to this article: https://doi.org/10.1080/08827508.2018.1502668

Published online: 30 Jul 2018.

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MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW
https://doi.org/10.1080/08827508.2018.1502668

A review on the recovery of titanium dioxide from Ilmenite ores by direct leaching
technologies
Thi Hong Nguyena,b and Man Seung Leea
a
Department of Advanced Materials Science & Engineering, Institute of Rare Metal, Mokpo National University, Mokpo, Jeollanamdo, Korea;
b
College of Natural Sciences, Can Tho University, Can Tho, Viet Nam

ABSTRACT KEYWORDS
Pretreatment of ilmenite are required to enhance leaching efficiency of ilmenite. Strong acid leaching is Ilmenite; hydrometallurgy;
promising in terms of the purity of the produced TiO2, low energy consumption and waste manage- leaching; TiO2
ment. The effect of several factors on the acid leaching kinetics in reported processes was reviewed.
Temperature, time and acid concentration significantly affect the dissolution of titanium and impurities
in ilmenite. The addition of either iron powder or chloride/sulfate salts affects significantly the leaching
rate of ilmenite. Either HCl leaching followed by solvent extraction or alkaline leaching followed by
hydrolysis-calcination is recommended for the production of pure TiO2 from ilmenite.

1. Introduction commonly employed as a material in the aerospace industry

1.1. Resources and application of titanium
Titanium is the ninth most abundant element making up
about 0.6% of the Earth’s crust (Das et al. 2013). Titanium
is found in the form of ilmenite (40–80% TiO2) and mineral
sand deposits, such as rutile (~95% TiO2), anatase (>95%
TiO2), leucoxene (>65% TiO2) and other titanium minerals
including brookite, perovskite, sphene, and geikielite (Kothari
1974; Kalinnikov and Nikolaev 2002; Zhu et al. 2011;
Haverkamp et al. 2016). Among these ores, ilmenite
(FeTiO3) is a major raw material for the manufacture of
titanium products and its physical and chemical properties
are shown in Table 1. Titanium products are widely used in
industry owing to their special properties (Nayl et al. 2009a;
Vásquez and Molina 2012; Awwad and Ibrahium 2013;
Gázquez et al. 2014; Razieh 2014; Nurul 2016). About 95%
of the produced titanium is used for the production of white
titanium dioxide as a pigment to scatter light (Gázquez et al.
2014). TiO2 pigments have high refractive index which gives
the potential for producing much greater opacity or hiding
power, making TiO2 a much better pigment than other pig-
ments (Gázquez et al. 2014). Other important features of TiO2
pigments are excellent resistance to chemical attack, good
thermal stability and resistance to ultraviolet degradation.
With these special properties, titanium dioxide pigments
become raw materials for the manufacture of paints, papers,
printing inks, rubber, floor covering, ceramics, pharmaceuti-
cals, and other areas of chemical industry (Awwad and
Ibrahium 2013; Gázquez et al. 2014; Razieh 2014). Metallic
titanium has excellent corrosion resistance in chloride envir-
onment and high temperature resistance and thus it is
(Awwad and Ibrahium 2013). Moreover, metallic titanium has
also important applications in the construction of water desa-
lination, chemical plants, and biomaterials (Nurul 2016).
Since the growing demand for TiO2 and titanium metal,
TiO2 pigment production is increasing to world production
capacity of 6.5 million tons and titanium metal sponge pro-
duction has also grown steadily to 214,000 tons in 2012
(Haverkamp et al. 2016). Adipuri et al. (2011) reported that
the high production cost of metallic titanium has rendered the
usage of metallic titanium in industry limited.
1.2 Treatment methods
Among titanium minerals, ilmenite is the most abundant one in
nature, but it contains a low-grade of TiO2 and high contents of
impurities such as SiO2, Al2O3, MgO, CaO, MnO, and V2O5
(Dang et al. 2015; Zhang et al. 2011b). Therefore, it is necessary
to develop suitable processes with less environmental burden to
produce titanium dioxide with high purity from ilmenite (Dang
et al. 2015). Titanium dioxide pigment is produced from tita-
nium ores by two traditional processes: sulfate process (40% of
total TiO2 production) and chloride process (60% of total TiO2
production) (Gázquez et al. 2014). The difference in these two
processes lies in both their chemistry and raw material require-
ments (Gázquez et al. 2014). In the sulfate process, low-grade
ilmenites are dissolved in concentrated sulfuric acid. After the
separation of the iron, the titanium liquor is hydrolyzed to result
in hydrated titanium dioxide (Guo et al. 2014). In chloride
process, either high grade rutile or titanium slag is chlorinated
in a fluidized bed reactor in the presence of coke to produce
TiCl4 vapor which is then converted to titanium dioxide in

CONTACT Man Seung Lee mslee@mokpo.ac.kr Department of Advanced Materials Science & Engineering, Institute of Rare Metal, Mokpo National
University, Jeollanamdo 534-729, Korea
Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/gmpr.
© 2018 Taylor & Francis Group, LLC
2 T. H. NGUYEN AND M. S. LEE

Table 1. Physical and chemical properties of ilmenite (based on Gázquez et al. 2016). Especially, the heavy mineral concentrates are treated via
2014; Nurul 2016).
a physical separation circuit to selectively separate ilmenite from
Formular Fe(II)TiO3 the remaining leucoxene, rutile, zircon, staurolite, monazite, and
Composition of TiO2 40–65% quartz which are produced as separate products (Nurul 2016).
Color Black
Hardness 5–6 on Mohs scale The low-grade titanium sands/hard rocks are first grounded and
Density 4.5–5 g/cm3 then processed by low-intensity magnetic separation and high
Crystal form Hexagonal
Transparency Opaque gradient magnetic separation to recover high-grade ilmenite
Major impurities Mg, Mn, V, Nb, Fe(III) together with titanomagnetite concentrate as a by-product
(Chen et al. 2013). Many conventional and the developed pro-
cesses are employed to produce titanium dioxide with high
presence of oxygen and AlCl3 (Middlemas et al. 2015). Although purity from the ilmenite concentrate and are shown in
the sulfate process is simple and can treat lower grade ores, the Figure 1 (Middlemas et al. 2015; Nurul 2016). Table 2 shows a
quality of the products is low and large amount of waste iron summary of the method of upgrading ilmenite to synthetic rutile
sulfate is generated from this process (Gázquez et al. 2014). by various processes. Solid state reduction involves several pro-
Chloride process has some advantages over the sulfate process cesses such as the Becher, the Benilite, the Murso, the Dunn, the
in terms of its production of higher-quality product, lower Kataoka and the Austpac process in which iron is converted to
impact on the environment and smaller amount of waste pro- soluble ferrous or elemental forms by reduction at high tem-
ducts but the requirements for high grade rutile in chloride perature followed by acid leaching to obtain synthetic rutile
process is a drawback (Guo et al. 2014). Since natural rutile (Nurul 2016; Zhang et al. 2011). According to the Table 2, direct
reserves constitute less than one-tenth of ilmenite, it is urgent hydrometallurgical processes such as the Altair and BHP Billiton
to develop alternative process to produce high quality TiO2 from process offer higher content of TiO2 and production of clean by-
low grade ores (Han 1992; Jia et al. 2014). The low grade product compared to redox pretreatment processes. Generally,
titanium ores are subjected to gravity, magnetic and electrostatic the hydrometallurgical processes of ilmenite fall into one of the
separation processes to produce an ilmenite concentrate (Nurul five classifications: (i) smelting process followed by either

Figure 1. Summary of existing and proposed processes for upgrading ilmenite to synthetic rutile (Nurul 2016).
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 3

sulfuric or hydrochloric acid leaching at elevated temperature;

(Verhulst et al. 2003)

(Zhang et al. 2011)

(Zhang et al. 2011)

(Zhang et al. 2011;

(Zhang et al. 2011;

(Roche et al. 2004;

Zhang et al. 2011)
(ii) reduction of ilmenite followed by acid leaching; (iii) diminu-
References

tion of the iron content in the ilmenite by oxygen and ammo-

Nurul 2016)

Nurul 2016)
nium chloride; (iv) oxidation of ilmenite followed by reduction
of oxidized ilmenite and hydrochloric acid leaching; (v) roasting
and magnetic separation followed by hydrochloric acid leaching
(Mahmoud et al. 2004). However, these processes are expensive
Multi step iron conversion and leaching; high

Increased process complexity; Recycling large

owing to multiple steps of energy intensive high temperature
Higher acidity need for leaching remaining

Recycling all chlorides; Small loss in iron oxide and Multi step metals leaching, conversion and
treatments (Mahmoud et al. 2004). Recently, direct acid/caustic
energy consumption emission of CO2

leaching processes in presence of additives attract attention on

Limited ilmenite type as the feed

Produce large iron sulfate waste

the light of production cost (Vásquez and Molina 2008; Wu et al.

volume of diluted acid solution

Similar to the Becher processes
Disadvantages

Handing highly corrosive Cl2

2011a, 2011b, 2013; Akhgar et al. 2013; Das et al. 2013;
Similar to Becher process

Wahyuningsih et al. 2013). Moreover, combined process con-

sisting acid leaching and solvent extraction (Zhu et al. 2011; Baba
magnetic iron form

et al. 2012; Hao et al. 2012; Awwad and Ibrahium 2013;

Middlemas et al. 2013) is considered to be promising for redu-
separation

cing energy requirement and enhancing the purity of final pro-

duct. In the production of titanium metal from TiO2, four
important processes such as the iodide process, the Kroll pro-
cess, a continuous process developed at Batelle Memorial
Improved efficiency by using fluidized beds; Easier

Reduced waste; Producing clean gypsum; better

Free of formation of fine TiO2 particles; Ease for

Institute and electrowinning of titanium are employed

90% TiO2; Allowing diverse ilmenite ores feed

(Hossein et al., 2017). Among these processes, the Kroll process

selectivity by SX to produce pure products
Cl2 recycle by oxidation of FeCl2 to Fe2O3

Less corrosive; Low leaching temperature

Magnetic separation for higher 97% TiO2

is currently used for commercial production of titanium metal

including three steps: (i) chlorination of rutile by Cl2 gas to
Simple one step conversion of iron
HCl recycle than sulfate systems

produce titanium chloride (TiCl4), (ii) reduction of TiCl4 by a

Advantages

magnesium reductant to produce titanium metal and magne-

sium chloride (MgCl2) and (iii) molten salt electrolysis to
(a) concentrated H2SO4 (Fe, Ti) Higher than 99% TiO2

recover MgCl2 as Mg and Cl2 (Hossein et al., 2017). Although

in digestion residue

pure titanium metal is obtained by the Kroll process, it suffers

leaching FeO
95–96% TiO2

from being a batch-type process (Hossein et al., 2017).

95% TiO2

95% TiO2

95% TiO2

1.3. The difference between reported and present review

(c) Solvent extraction (SX) of Ti

Some review papers have been published on the recovery and

Table 2. Summary of the method of upgrading ilmenite to synthetic rutile by various processes.
Leaching/solvent extraction

(b) Reduction iron to ferrous

production of titanium product from titanium resources

(a) HCl digestion (Fe, Ti)

(Gázquez et al. 2014; Nurul 2016; Zhang et al. 2011; Zhu

state by iron powder

(d) SX of impurities

et al. 2011). Hossein et al. (2017) reviewed on the production

(b) Ferrous sulfate
-
(b) 0.5M H2SO4

of titanium tetrachloride from titanium ores such as rutile and

crystallization
(a) NH4Cl/O2

18–20% HCl

(c) SX of Ti

ilmenite via different chlorination processes, which can be

20% HCl

Lower temperature for iron conversion to 18% HCl

25% HCl

reduced and oxidized to produce titanium sponge and tita-

H2SO4

nium oxide. Gázquez et al. (2014) reviewed on the production

cycle of titanium dioxide pigment by two main processes
Selective chlorination of iron in ilmenite

involving sulfate and chloride routes. The main content in

Iron oxidized to Fe2O3 and reduced to

this review is a summary of properties and different uses of

FeO with controlled CO2 pressure
Pre-oxidation step; hydrogen rich

the titanium dioxide pigment in industry. Development of

Magnetization at 800–1000°C
metallic Fe by coal at 1200°C
Pyro-treatment

hydrometallurgical processes including either acid or alkaline

Conversion to ferrous form
Cabone-thermo reduction

leaching for the production of synthetic rutile was summar-

ized by W. Zhang et al. (2011) and Nurul (2016). However,
weak acid and alkaline leaching of ilmenite ores and compar-
ison of the leaching performance between acid and alkaline
reductant

leaching are scarce in these reported literatures. Thermal

with Cl2

plasma processing of ilmenite was reviewed by Samal (2013).

None

None

In thermal plasma process, oxidants are not required to pro-

duce the heat necessary for the progress of the reaction. As no
improved sulfate

fuel is combusted, the volume of the gas stream produced is

Benelite process

Auspact process

Kataoka process
Laporte process
Becher process

Murso process

Dunn process

Altair process

much smaller than that from conventional combustion pro-

BHP Billiton

process

cesses and thus thermal plasma process is considered to be

Process

easier to operate and less expensive to manage (Samal 2013).

However, the main drawback of thermal plasma processing is
4 T. H. NGUYEN AND M. S. LEE
the requirement of intensive energy which renders the
upgrading of ilmenite to synthetic rutile via this technology
less economical. The comparison of the life cycle assessment
between traditional and emerging processes for the produc-
tion of titanium dioxide from titanium slag has been made on
the basis of the demand for the cumulative energy and the
evolution of CO2. According to this comparison, new process
consisting of alkaline roasting, leaching, solvent extraction,
hydrolysis and calcination and regeneration of alkaline and
acid is better than the tradition processes on the basis of the
generation of wastes (Middlemas et al. 2015).
In the separation of titanium and other impurities from
leach liquors of titanium minerals, solvent extraction is com-
monly employed due to high separation efficiency and simple
operation. However, few reviews have been reported on the
solvent extraction of titanium from acidic chloride and sulfate
solutions using acidic and neutral extractants (Sole 1999,
1999; Reddy and Saji 2002; Zhu et al. 2011). These works
reported that neutral extractants were effective to separate
titanium and iron from aqueous phase while the application
of acidic extractants is limited due to slow extraction kinetics
and difficulty in stripping.
Although traditional processes offer high recovery percen-
tage of titanium products from titanium resources, emerging
hydrometallurgical processes including strong/weak acid and
caustic leaching are still at an early stage of development in
terms of the enhancement in dissolution efficiency of ilmenite
and minimization of the waste generation. However, the fun-
damental understanding of these processes is still poor and
further work should be conducted to elucidate the reaction
mechanism. The main topic covered in this review includes:
pretreatment methods, kinetics of leaching and effect of fac-
tors on leaching efficiency of ilmenite. Moreover, hydrome-
tallurgical processes reported in the literatures were compared
in terms of product quality, process economics, and waste
disposal. Furthermore, emerging processes for the production
of titanium dioxide from ilmenite were pointed out in the
present review.
2. Pretreatment of ilmenite
2.1. Oxidation and reduction
In the recovery of titanium dioxide by leaching process, the
common treatment method is thermal reduction of the ilmenite
at high temperature to form TiO2 and elemental iron followed by
leaching to remove iron (Wang et al. 2014). Vacuum carbother-
mic reduction was also used to remove oxides of iron, magne-
sium, silicon, and manganese in ilmenite as gas by controlling
the temperature and carbon amount (Run et al. 2017). This
method can result in TiO2 with purity higher than 90% which
can be treated by chlorination process to produce pure titanium
oxide. Microwave which can heat dielectric materials rapidly is
proposed to be an alternative source of heat and can reduce
operation costs by 15–50% compared to conventional conduc-
tive heating (Wang et al. 2014).
The reactivity of ilmenite was found to be improved by
using pre-oxidation (Janssen and Putnis 2011; Sarker et al.
2006; Zhang et al. 2011a; Zhu et al. 2014). Oxidation of
ilmenite at 700°C for 12 h had little effect on the increase in
iron dissolution due to the lower solubility of ferric iron in
hydrochloric acid (Janssen and Putnis 2011). By contrast, the
oxidation of ilmenite at 950°C for 1 h increases both the
extent and the rate of leaching due to the formation of
micro-cracks during the oxidation process (Sarker et al.
2006). Zhu et al. (2014) explained the effect of oxidation on
leaching efficiency of iron through phase change. The leach-
ing efficiency of iron from hematite, ilmenite and pseudo-
brookite by HCl solution was in the following order: hematite
(ferric iron) >ilmenite (ferrous iron) » pseudo-brookite (ferric
iron) (Zhu et al. 2014). Oxidation at 600–700°C leads to a
slight increase in the leaching percentage of iron due to the
transformation of ilmenite into hematite, while the formation
of pseudobrookite at 900–1000°C results in a significant
decrease in the leaching percentage of iron (Zhu et al. 2014).
SEM images of the oxidized ilmenite at 800°C and 1050°C
indicated that the proportion and distribution of pseudo-
brookite phase changed with temperatures (Vásquez and
Molina 2012). Based on microchemical analysis combined
with X-Ray diffraction, Guéguin and Cardarelli (2007)
reported that titania-rich slags produced from the smelting
of hemo-ilmenite ore with anthracite coal and related pro-
ducts exhibit mineralogically unique characteristics among
other natural minerals. The metallurgical processing of
hemo-ilmenite ores at high temperature increased the content
of titania in the ores, resulting in the formation of titanate
phases with pseudobrookite-karrooite structure (Guéguin and
Cardarelli 2007). The XRD patterns of the ilmenite oxidized at
600–1000°C showed that strong peaks from ilmenite still exist
alongside the peaks from hematite and rutile, indicating only
partial oxidation of ilmenite during oxidation process (Zhu
et al. 2014). Thus, hydrogen reduction of pre-oxidized ilme-
nite was subsequently employed to form microcracks and
microholes which enhanced the leaching rate of iron by pro-
viding a path for HCl to penetrate (Grey et al. 2007; Zhu et al.
2014). In addition, the oxidation-reduction pretreatment not
only remarkably retards the initial hydrolysis time of titanium
ions but also significantly decreases the titanium extraction in
HCl solution (L. Zhang et al. 2011a).
In general, the ferric iron formed in oxidation treatment is
difficult to dissolve by acid solutions and thus reduction
treatment is subsequently employed to convert the ferric
iron into the ferrous iron which is more soluble in acid
solution (Ogasawara and Veloso De Araújo 2000; Mahmoud
et al. 2004). However, the main disadvantage of oxidation-
reduction treatment prior to acid leaching is high energy
consumption (Vásquez and Molina 2008). Therefore, reduc-
tive leaching of the oxidized ilmenite by hydrochloric acid
solution in the presence of iron particles which can reduce Fe
(III) to Fe(II) has been proposed (Vásquez and Molina 2008;
Wahyuningsih et al. 2014). The effect of iron particles on the
leaching of ilmenite will be mentioned in detail in Section 3.
2.2. Mechanical activation
Mechanical activation is one of the effective methods to accel-
erate leaching on account of the following aspects: (i) the
increase of specific surface area; (ii) the change in the

crystalline structure; and (iii) the occurrence of chemical
reactions (Sasikumar et al. 2007; Wei et al. 2009; Tao et al.
2012; Baba et al. 2013). Many researchers reported that all
peaks in the XRD patterns of activated ilmenite matched the
XRD patterns of the unactivated ilmenite, indicating no for-
mation of new phase during mechanical activation (Welham
and Llewellyn 1998; Sasikumar et al. 2004; Wei et al. 2009;
Zhang et al. 2010; Shojaei et al. 2014). However the diffraction
peaks of ilmenite were broadened and their intensity
decreased after mechanical activation, which was due to the
refinement of crystalline grain and the accumulation of lattice
strain associated with ball impacts and collisions (Shojaei et al.
2014). The crystalline size of ilmenite decreased as milling
time increased, resulting in the improvement of the leaching
efficiency of ilmenite (Wei et al. 2009; Shojaei et al. 2014).
Although there was some decrease in particle size during the
extended mechanical activation of ilmenite, the increase of the
lattice disorder might be responsible for the enhancement in
the leaching efficiency (Li et al. 2008a, 2008b; Zhang et al.
2010). Li et al. (2008b) also found that the increase of lattice
strain induced by energetic milling led to the acceleration of
iron dissolution and simultaneous titanium hydrolysis in HCl
solution. However, the milling significantly affected the filter-
ability of reactive slurries due to the rapid hydrolysis and thus
milling time should be controlled to prevent solid/liquid
separation problems (Li et al. 2008b). Mechanical activation
of oxidized-reduced ilmenite could accelerate the dissolution
of other impurities such as iron, calcium and magnesium by
HCl leaching solution, resulting in the recovery of a rutile
which meets the requirement of chlorination process (Tan
et al. 2011; Zhang et al. 2011a).
2.3. Hydrothermal conversion
Hydrothermal conversion of ilmenite by either alkaline or
acid solution was proposed to affect the decomposition pro-
cess by which iron and titanium can be separated (Nayl and
Aly 2009; Nayl et al. 2009a, 2009b; Manhique et al. 2011;
Xiong et al. 2013; Li et al. 2016; Meng et al. 2016). When
ilmenite was decomposed in concentrated KOH solution
under atmospheric pressure, potassium titanate, and iron
oxide were formed and the dissolution of titanium depended
on decomposition temperature (Liu et al. 2006; Nayl and Aly
2009; Yousef 2015). Baba et al. (2013) reported that alkaline
roasting of ilmenite led to the enhancement of the leaching
efficiency of titanium using H2SO4 solution. NaOH was more
effective as a roasting agent than Na2CO3 in terms of Na2O
generation capacity which would react with ilmenite to form
NaFeTiO4, Na2TiO3, NaFeO2, and NaFeTi3O8 (Baba et al.
2013). X-ray diffraction of the roasted ilmenite showed that
unreacted FeTiO3 and TiO2 phase were not observed, indicat-
ing complete decomposition of ilmenite (Baba et al. 2013).
Roasting of ilmenite with ammonium sulfate at 360°C led to
the decomposition of ilmenite to TiOSO4 and (NH4)2Fe(SO4)2
and then the roasted product was leached by two steps leach-
ing to remove water-soluble sulfates (Liu et al. 2017).
Sulfuric acid decomposition through either solid phase or
liquid phase was proposed to prepare titanium dioxide from
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 5
ilmenite (Xiong et al. 2013; Sui and Zhai 2014; Li et al. 2016).
Most of the titanium in ilmenite was recovered as titanium
sulfate solution by first decomposition with 80–85% H2SO4 at
150°C followed by water leaching of the products (Xiong et al.
2013). Although TiO2 with high purity could be obtained by
the solid phase sulfuric acid decomposition, the disadvantage
of this method lies in the requirement of higher H2SO4 con-
centration (Xiong et al. 2013) and temperature (Sui and Zhai
2014), and in the release of large amount of toxic gases such
as H2S, SO2, and SO3 (Baba et al. 2013). These disadvantages
of sulfuric decomposition of the solid phase can be overcome
by liquid phase method. Li et al. (2016) reported that most of
titanium from ilmenite was decomposed under optimum con-
ditions: 13.5M H2SO4, 160°C for 120 min.
3. Leaching
3.1. Strong acid leaching
3.1.1. Sulfuric acid leaching
3.1.1.1. Kinetics of sulfuric acid leaching. Dissolution of
ilmenite by sulfuric acid solution can be expressed by
Equation (1) (Nurul 2016).
FeTiO3 þ2H2 SO4 ¼ TiSO4 þFeSO4 þ2H2 O (1)
Dissolution kinetics of titanium from ilmenite by sulfuric
acid solution depends on several factors, such as particle size,
temperature, reaction time, solid/liquid ratio, and sulfuric acid
concentration (Barton and Mcconnel 1979; Welham and
Llewellyn 1998; Nayl et al. 2009a; Zhang and Nicol 2010;
Subagja et al. 2013). Welham and Llewellyn (1998) indicated
that the sulfuric acid leaching of ilmenite at 120°C for 8 h
consisted of two stages. The first stage was controlled by mass
transport, while the second stage was chemically controlled
(shrinking core model). Barton and Mcconnel (1979) reported
that the leaching rate of ilmenite by sulfuric acid in the
temperature range of 65–80°C was controlled by chemical
reaction. The leaching kinetics of ilmenite paste after KOH
treatment was better described by the chemical control model
(Nayl et al. 2009a). Recent kinetics study of titanium leaching
from ilmenite paste after KOH treatment also indicated the
chemical reaction takes place on the surface of the ilmenite
paste (Subagja et al. 2013). The leaching rate of ilmenite in
sulfuric acid without reducing agents was controlled by a slow
chemical reaction on the surface of the mineral, while the
dissolution rate of ilmenite is significantly enhanced in the
presence of titanous ions (Zhang and Nicol 2010). The shrink-
ing core model (diffusion of the reagent to the surface of the
mineral through a porous layer of reaction product) was
suitable for describing the leaching of ilmenite in the presence
of titanium (III) ions. A summary of the reported kinetic
parameters for ilmenite leaching in sulfuric acid solution is
shown in Table 3.
3.1.1.2. Factors affecting sulfuric acid leaching. In leaching
process, particle size, time, temperature, reagent concentra-
tion, and pulp density are important factors. The available
options for increasing leaching rate are either to decrease the
size of the particles or to increase the temperature and the
6 T. H. NGUYEN AND M. S. LEE

Table 3. Kinetic parameters for ilmenite leaching in sulfuric acid solution from reported literature.
Activation
energy,
Origin Pretreatment Conditions Models kJ mol−1 References
New Zealand None 4.7–12.5M H2SO4 M; 65–85°C Shrinking particle 90 (Barton and Mcconnel 1979)
Southern Thailand None 4.7–18.8M H2SO4; 88–115°C; S/L = 3/500 Shrinking particle 64.4 (Han et al. 1987)
Western Australia Mechanically 50% H2SO4; 80–120°C; S/L = 1/50 Shrinking particle/ 15/70 (Welham and Llewellyn
activated core 1998)
Panzhihua, China Mechanically 15.4M H2SO4; 100–198°C Shrinking core 72.6 (Liang et al. 2005)
activated S/L = 3/100
Manavalakurich, Mechanically 1.8–12.9M H2SO4; 70–100°C; S/L = 1/10 Shrinking core 68–70 (Sasikumar et al. 2007)
India activated
°
Panzhihua, China Mechanically 5–20% H2SO4; 70–100 C; S/L = 1/10 Shrinking core 38 (Li et al. 2007)
activated
Egypt KOH treatment 2–8M H2SO4; 75–175°C; S/L = 1/9 Shrinking particle 30.6 (Nayl and Aly 2009)
Australia None 450–600 g/L H2SO4; 85–100 oC; S/L = 1/ Shrinking particle/ 75/90 (Zhang and Nicol 2009)
45 core
Indonesia KOH treatment 7.1–12.8M H2SO4; 50–125°C; S/L = 1/6 Shrinking particle 59 (Subagja et al. 2013)
b:k:V:Cna :t
1
a) In the shrinking particle model, the rate of the leaching process is controlled by a chemical reaction
(1  ð1  xÞ3 ¼ ro of¼ ks :t, where is the fraction of metal dissolved at time t; ks is apparent rate
constant; b is stoichiometric coefficient; k is an intrinsic rate constants; V is the molar volume of reacted substance; C is concentration acid in bulk solution; r is initial particle radius; and n is reaction order in terms
a o
of acid concentration).
(b) In the case of shrinking core model, the rate of leaching process is limited by diffusion of the reagent to the surface of the mineral through a porous layer of reaction product
2 6:b:Dc :V:Ca :t
(1  3:ð1  xÞ3 þ 2:ð1  xÞ ¼ r2o
¼ kD :t, where k
D
is apparent rate constant; D is effective diffusivity in the product layer.
c
S/L is solid to liquid ratio.

concentration of reagent in leach solution (Habashi 1997; 125–200°C, resulting in a decrease in leaching efficiency
Nurul 2016). Pulp density also significantly affects the leach- of titanium (Jia et al. 2014).
ing rate. Namely, the leaching rate increases with a decrease in (iii) Acid concentration
pulp density, while high pulp density causes the equilibrium The leaching percentage of titanium increased with
to shift and reaction rates will decrease (Nurul 2016). Thus, in increase of acid concentration (Sasikumar et al. 2007; Nayl
order to improve leaching efficiency, the above-mentioned and Aly 2009; Nayl et al. 2009a; Zhang and Nicol 2010;
factors should be controlled. For this purpose, the factors Subagja et al. 2013; Yousef 2015). The increase in the dissolu-
affecting acid leaching of ilmenite were reviewed detail in tion of titanium was due to the formation of complexes
Section 3.1.1 and 3.1.2. between Ti(VI) and SO42–/HSO4–, such as, TiOSO4, TiO
(i) Particle size and time (SO4)22–, TiO(SO4)46–, and Ti(OH)3HSO4 (Nayl and Aly
Generally, the leaching rate increased with a decrease in 2009). Woranart and Theeraporn (2013) have found a signif-
particle size but the effect was weak at particle sizes less than icant decrease of titanium dissolution in the acid concentra-
105–74 μm (Nayl and Aly 2009; Nayl et al. 2009a, 2009b). Iron tion range of 12–18M at 90°C due to the formation of
dissolution increased as the time increases, while there was an titanium precipitates. Han et al. (1987) reported that a dis-
opposite trend in the case of titanium (Li et al. 2007, 2008a, tinctive product layer of TiOSO4 and FeSO4 was formed at
2008b; Jia et al. 2014). The difference in leaching behavior of higher than 16M H2SO4, which were soluble in water at 98°C.
titanium and iron is due to hydrolysis of the dissolved titanium, Li et al. (2008a), (2007)) studied the leaching of ilmenite using
which prevents further dissolution of titanium (Li et al. 2007). moderate sulfuric acid solution under 100°C.
(ii) Temperature The leaching percentage of titanium was very low in the
Leaching rate of ilmenite using sulfuric acid solution is acid concentration range of 10–40% because of hydrolysis of
extremely sensitive to reaction temperature. Both titanium the dissolved titanium (Li et al. 2007, 2008a). Jia et al. (2014)
and iron was simultaneously dissolved by concentrated reported that a compact layer on the surface of the unreacted
sulfuric acid solution and the leaching percentage of ilmenite was formed at high temperature when sulfuric acid
these metals increased as temperature increased (Barton concentration was higher than 40%, leading to hindrance of
and Mcconnel 1979; Sasikumar et al. 2007; Nayl et al. the leaching of iron.
2009a; Zhang and Nicol 2010; Subagja et al. 2013). (iv) Additives
Separation of titanium and iron was achieved in leaching The leaching efficiency of ilmenite using sulfuric acid solu-
process by controlling reaction temperature when low tion can be improved in the presence of reductants. The
H2SO4 concentration was used (Li et al. 2007; Jia et al. pressure leaching of ilmenite using the sulfuric acid solution
2014). The leaching percentage of iron increased with in the absence and presence of FeSO4 was investigated by Jia
temperature using 20% H2SO4, while that of titanium et al. (2014). The leaching percentage of iron decreased dra-
decreased because of the instability of titanium in the matically with increasing FeSO4 concentration, while that of
solution at high temperature (Li et al. 2007). Jia et al. titanium rose steadily (Jia et al. 2014). The presence of FeSO4
(2014) reported that most of iron from Panzhihua ilmenite promoted the hydration of iron ions, resulting in an increase
was selectively leached using 20% H2SO4 at 150°C, while in the effective H2SO4 concentration. This was the reason for
the leaching percentage of Ti was less than 1%. Hydrolysis the variation in the leaching percentage of titanium and iron
of the dissolved titanium ion appears simultaneously dur- (Jia et al. 2014). Zhang and Nicol (2010) found that the
ing the leaching process at high temperature range of presence Ti(III) ions and SO2 gas in sulfuric acid solution

reduced the iron (III) in the ilmenite by a redox reaction on
the surface and thus accelerated the dissolution rate of tita-
nium. However, the effect of SO2 on leaching efficiency of
titanium is significantly less than that of Ti(III) ions due to
the lower potential attainable with Ti(III) (Zhang and Nicol
2010).
3.1.2. Hydrochloric acid leaching
3.1.2.1. Kinetics of hydrochloric acid leaching. The overall
dissolution reaction of the ilmenite in hydrochloric acid solu-
tion can be represented as Equation (2) (Nurul 2016).
FeTiO3 þ4HCl ¼ TiOCl2 þFeCl2 þ2H2 O
A kinetic study on the leaching of a Nigerian ilmenite
using hydrochloric acid solution in the temperature range of
70–90°C was reported by Olanipekun (1999). The author
indicated that two diffusion processes occur during the reac-
tion: (i) diffusion of H+ and (ii) diffusion of Ti4+ and Fe2+
produced by the surface chemical reaction at the unreacted
core. Since the diffusion rate of H+ is faster than that of Ti4+
and Fe2+, the reaction rate is controlled by diffusion of tita-
nium (VI) and iron(II) through the product layer
(Olanipekun 1999). Ramadan et al. (2016) also reported that
the dissolution rate by hydrochloric acid solution is a diffu-
sion controlled and follows the shrinking core model with
apparent activation energy of 17 kJmol–1. Kinetic data analysis
on the leaching of rutile ore in HCl solution indicated that the
dissolution mechanism followed a diffusion controlled shrink-
ing core model (Baba et al. 2009). The shrinking core model
was also found to be fit to the leaching data of New Zealand
ilmenite in the reaction temperature range of 60–80°C and
85–90°C (Haverkamp et al. 2016). Tsuchida et al. (1982)
found that the dissolution rate of titanium from ilmenite
was well expressed by the rate equation based on the rate-
determining step of surface chemical reaction in the tempera-
ture range of 30–50°C, while the surface chemical reaction
became so fast and the dissolution rate was limited by diffu-
sion through the product layer at >60°C. However, the rates
after either 4 h at 70°C or 3 h at 80°C deviated from the rate
equation due to the precipitation of hydrous titanium (IV)
oxide on the surface of the ore (Tsuchida et al. 1982).
The rate determining step during hydrochloric acid leach-
ing of ilmenite was reported by Van Dyk et al. (2002). At an
Table 4. Kinetic parameters for ilmenite leaching in hydrochloric acid solution from reported literatures.
Origin Pretreatment
Jos Plateau, Nigeria None
Japan None
Nigeria None
Abu Ghalaga, Egypt None
Bangladesh Oxidation and
Reduction
Bangladesh None
a for low temperature; b for high temperature; S/L is solid to liquid ratio.
(2)
Conditions
7.2–9.6M HCl;
70–90°C; S/L = 0.5/150
11.3–11.6M HCl; 30–80°C; S/L = 5/200
2M HCl; 80°C; S/L = 1/100
20% HCl; 40–110°C; S/L = 1/6
5–15% HCl; 30–75°C; S/L = 1/100
6 M HCl +0.5M CH3-H2O; 45–110°C; S/
L = 2/100
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 7
early stage, both titanium and iron is dissolved in hydrochlo-
ric acid solution so that the leaching rate follows a chemical
reaction controlled mechanism. Next steps are controlled by
the formation of titanium species. Ti(IV) polymerizes in
hydrochloric acid solutions when titanium concentration in
the solution exceeds 10–3M and then the diffusion of polymer
chains away from the reaction interface becomes the rate
limiting step in leaching. After a certain period, titanium
concentration in the leaching solution increases to a certain
level, resulting in the formation of TiOCl2 in the pores of the
particles as a form of fine particles. Therefore, the rate deter-
mining step changed to the diffusion of the reacting species
through the product layer (Van Dyk et al. 2002). The author
also found that the diffusion of hydrogen ions to the reaction
interface became the rate-limiting step at high solid to acid
ratio because the decrease in acid concentration led to the
formation of a TiO2.H2O precipitate in the existing product
layer. A summary of the reported kinetic parameters for
ilmenite leaching in hydrochloric acid solution is shown in
Table 4.
3.1.2.2. Factors affecting hydrochloric acid leaching. (i)
Particle size and time
Dissolution rates of titanium and iron were inversely pro-
portional to the average initial diameter of the particles (El-
Hazek et al. 2007; Samal 2011; Mehdilo and Irannajad 2012;
Abdou et al. 2015; Ramadan et al. 2016). The increase in
leaching percentage of ilmenite by a decrease in particle size
is due to the larger surface area exposed to the leaching
solution (Abdou et al. 2015; Ramadan et al. 2016). By con-
trast, Van Dyk et al. (2002) found that most of titanium and
iron were dissolved in HCl solution for all particle sizes. The
indifference of leaching efficiency to the particle size may be
due to the fact that finer particles appear to offer faster
leaching kinetics (Nurul 2016).
Reaction time significantly affected the leaching efficiency
of ilmenite. As reaction time increased to 2 h, the dissolution
efficiency of titanium and iron from ilmenite steadily
increased using concentrated HCl solution (El-Hazek et al.
2007; Nayl and Aly 2009; Samal 2011; Abdou et al. 2015;
Yousef 2015). The enhancement of leaching efficiency with
the increase in time is related to prolonged contact time
between ilmenite and hydrochloric acid solution (Gireesh
Activation
energy,
Models kJ mol−1 References
Shrinking core 67.1 (Ti) (Olanipekun 1999)
62.4 (Fe)
Shrinking particle/core 81.2 (Ti) (Tsuchida et al.
73.2 (Fe) 1982)
Shrinking particle 38.4 (Ti) (Baba et al. 2012)
Shrinking core 17.6 (Ti) (Ramadan et al.
2016)
First order reaction/Shrinking 30 (Fe) (Sarker et al. 2006)
particle
Shrinking particle/core 16.5a (Ti), 21.8a (Habib et al. 2006)
(Fe)
66b (Ti), 90b (Fe)
8 T. H. NGUYEN AND M. S. LEE
et al. 2013). However, there was a slight adverse effect upon
the dissolution of titanium and iron at extending the leaching
time from 2 to 5 h owing to the hydrolysis of titanium (L.
Zhang et al. 2011a). Large amount of H+ was produced in the
apparent hydrolysis of titanium ions after 3 h leaching, result-
ing in an increase of ionic strength and enhancement of the
reactivity of hydrochloric acid, and thus iron in ilmenite can
be rapidly leached (Zhang et al. 2010, 2011a). The selective
leaching of iron over titanium using moderate HCl solution
was investigated as a function of reaction time in some litera-
tures. The leaching percentage of iron and the content of TiO2
in the residue slightly increased with time (Mahmoud et al.
2004; Li et al. 2008b; Razieh 2014; Ramadan et al. 2016).
(ii) Temperature
The leaching percentage of titanium and iron in ilmenite
increased significantly with the increase of temperature from
25°C to 80°C (Lasheen 2005; El-Hazek et al. 2007; Baba et al.
2009, 2012; Das et al. 2013; Abdou et al. 2015; Yousef 2015).
At higher temperatures (>80°C), high leaching efficiency of
ilmenite was obtained but there were several drawbacks under
these conditions such as increased loss of HCl vapor and the
hydrolysis of dissolved titanium (Baba et al. 2009; Tao et al.
2012; Das et al. 2013). El-Hazek et al. (2007) and Lasheen
(2005) reported that low leaching efficiency of iron and tita-
nium at room temperature was due to the low reactivity of
ilmenite, while leaching percentage of iron increased more
rapidly than that of titanium with the increase of temperature
from 20°C to 50°C owing to the partial hydrolysis of titanium.
The increase in reaction temperature led to an increase of the
mobility of ions, thereby enhancing the interaction between
reactants in solids and liquids (Gireesh et al. 2015). However,
increase of reaction temperature higher than 100°C affects the
leaching of titanium due to high polymerization and hydro-
lysis of titanium without affecting iron (El-Hazek et al. 2007;
Abdou et al. 2015; Yousef 2015).
Leaching temperature is quite important for the produc-
tion of TiO2 with high purity from ilmenite using moderate
HCl solution (Mahmoud et al. 2004; Lasheen 2005; Tao et al.
2012; Guo et al. 2014; Razieh 2014; Liu et al. 2015; Ramadan
et al. 2016). The leaching percentage of iron rapidly increased
with increase of temperature up to 90°C using 4M HCl,
leaving most TiO2 in the residue at any temperature
(Lasheen 2005). The hydrolysis reaction of TiOCl2 is known
to be much enhanced at higher temperature so that the
recovery percentage of TiO2 from the residue of ilmenite
using moderate HCl solution increased with the increase of
temperature to a certain level (Mahmoud et al. 2004; Guo
et al. 2014; Razieh 2014; Liu et al. 2015; Ramadan et al. 2016).
Middlemas et al. (2013) reported that the dissolved titanium
can react with water to form insoluble hydrates such as
orthotitanic acid, Ti(OH)4 or TiO2.2H2O (at low temperature)
and metatitanic acid, Ti(OH)2 or TiO2.H2O (at high tempera-
ture). In order to reduce leaching time and temperature, the
leaching of titanium-bearing minerals obtained from chloride
processes can be carried out using ultrasonic vibrations due to
reduction of particle size during leaching (Swamy et al. 1995;
Narayana et al. 1997). Other advantage of ultrasound is to
reduce the chlorine content in leaching of titanium-bearing
minerals (Narayana et al. 1997).
(iii) Acid concentration
Equation (2) shows that hydrochloric acid concentration
promotes iron dissolution and could dissolve titanium by
controlling acid concentration (Liddell 1988; Swanepoel
et al. 2011; Wahyuningsih et al. 2013; Woranart and
Theeraporn 2013). Nayl and Aly (2009) found that the leach-
ing percentage of titanium and iron from pretreated ilmenite
increased with an increase of acid concentration to 9M HCl.
Samal (2011) also found that the leaching percentage of tita-
nium was lower than that of iron at low acidity due to the
precipitation of TiOCl2 which does not occur at high acidity.
El-Hazek et al. (2007) suggested that leaching with high acid
concentration (12M) at 80°C was needed to suppress the
hydrolysis of titanium at a high solid to liquid ratio (S/L).
Other researchers also found that dissolution of titanium and
iron was enhanced in high acid concentration and the max-
imum leaching percentage of these metals was obtained at a
specific HCl concentration depending upon other conditions
(Olanipekun 1999; El-Hazek et al. 2007; Baba et al. 2012; Das
et al. 2013; Middlemas et al. 2013; Abdou et al. 2015; Yousef
2015). The leaching solution of pretreated titanium slag was
quite turbid and difficult to filter in the HCl range of 0.75–
1.5M at 50°C (Middlemas et al. 2013). The author reported
that the filtrate became clear and had less finely suspended
particles when HCl concentration was higher than 1.5M but
the precipitation occurred in this solution after few days
(Middlemas et al. 2013). It is apparent that the hydrolysis of
dissolved titanium occurs at either low acidity or low
temperature.
The effect of HCl concentration on selective leaching of
iron over titanium from ilmenite has been reported in some
literatures (Mahmoud et al. 2004; Lasheen 2005; Guo et al.
2014; Gireesh et al. 2015; Liu et al. 2015; Ramadan et al. 2016).
Mahmoud et al. (2004) found that the almost iron was dis-
solved at 30 wt.% HCl under reducing conditions, while that
of titanium was negligible. Guo et al. (2014) and Ramadan
et al. (2016) also suggested that 20 wt.% HCl was a suitable
acid concentration for selective leaching of iron and thus
enhanced the contents of TiO2 in the residue. Liu et al.
(2015) indicated that the recovery percentage of TiO2 in the
residue increased with the increase of aid concentration from
200 to 240 g/L. According to this literature, higher than 220 g/
L HCl should be used in the leaching to obtain a product with
more than 92% of TiO2. Other researchers also found that the
leaching efficiency of iron increased as the acid concentration
increased from 2 to 12M but the solubility of TiO2 seemed to
be negligible in this acid concentration range (Lasheen 2005;
Gireesh et al. 2015).
(iv) Additives
The difficulty in the leaching of ilmenite is ascribed to the
intimate intergrowth of hematite in ilmenite and a reducing
medium is needed to enhance the dissolution efficiency of
hematite. The presence of metallic iron powder in the leach-
ing medium as a reductant results in an increase of dissolu-
tion efficiency of ilmenite via reduction of Fe(III)
(Wahyuningsih et al. 2013). However the addition of a large
amount of iron powder led to the adverse effect on the
leaching of ilmenite because iron dissolution increases the
acid consumption (El-Hazek et al. 2007; Wahyuningsih et al.

2013, 2014) and thus control of the amount of iron powder is
important in reductive leaching. Lasheen (2005) found that
the addition of 6% iron powder to hydrochloric acid solution
progressively accelerated the iron dissolution, resulting in an
increase in the TiO2 content of the residue. During reductive
leaching process, a small excess of a reductant could reduce Ti
(IV) to Ti(III) which decreased the tendency for Fe(II) ions to
be oxidized to Fe(III) (Mahmoud et al. 2004). The reductive
dissolution of ferric iron increased the reactivity of ilmenite
ore because of breaking up of the grain structure, causing
further diffusion of acid protons to pores created in the ore
particles (Mahmoud et al. 2004). In this process, dissolved Ti
(IV) is hydrolyzed and precipitated, leaving mainly ferrous
chloride in the leaching solution and resulting in TiO2 of high
purity in the residue of ilmenite.
It was found that the leaching of ilmenite in HCl solution
also depends on the chloride and sulfate ion concentration in
the leaching solution (Das et al. 2013; Gireesh et al. 2013). The
study on the leaching of ilmenite ores by HCl solution in the
presence of chloride salts such as CaCl2, MgCl2, and NaCl
indicated that the leaching efficiency of titanium and iron was
in the order of CaCl2 >MgCl2 ≫ NaCl (Das et al. 2013). Since
CaCl2 has very high solubility, it was the most effective salt in
HCl leaching process (Das et al. 2013). The presence of sulfate
salts in the HCl solution was also found to be more effective
in the leaching of iron in the ilmenite. The leaching percen-
tage of iron increased with an increase of the amount of
sulfates, such as CaSO4, MgSO4, NaSO4 and K2SO4 and thus
the titanium content and its purity in the leached residue was
enriched (Gireesh et al. 2013). The author reported that diva-
lent metal sulfates (Ca and Mg) have better performance than
monovalent metal sulfates (Na and K). The leaching efficiency
of iron from ilmenite using HCl solution in the presence of
H2O2 was also enhanced by the presence of ultraviolet (UV)
(Jayaweera et al. 2011). The improvement of leaching effi-
ciency by UV light might be related to photo dissociation
and consequent nondeposition of polymeric titanium species
in the pores of ilmenite particles which cause the chemical
reaction of FeTiO3 and HCl to be the rate determining step.
The authors also reported that the addition of H2O2 in leach-
ing solution further enhanced iron leaching rate, generating
more radical species (Jayaweera et al. 2011).
3.2. Weak acid leaching
Oxalic and citric acids are used for leaching of ilmenite and
the reactions between ilmenite and these acids are shown
below (Woranart and Theeraporn 2013):
C2 H2 O4 þH2 O ¼H3 Oþ þC2 HO4  (3)
C6 H8 O7 þH2 O ¼H3 Oþ þC6 H7 O (4)
þ
FeTiO3 þ4H3 O ¼ TiO þFe þ6H2 O
2þ 2þ
(5)
Woranart and Theeraporn (2013) reported that both oxalic
and citric acid had a significant positive influence on titanium
leaching but the leaching efficiency of ilmenite using oxalic
acid was less than that by citric acid at the same conditions. In
the citric acid leaching, the leaching percentage of titanium
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 9
was much higher than that of iron at the optimum leaching
conditions (Woranart and Theeraporn 2013). The author
explained that low leaching percentage of iron in citric acid
solution was explained by the precipitation of Fe(III) and Fe
(II) at 90°C. Therefore, citric acid was suggested for leaching
of ilmenite in terms of separation efficiency of titanium and
iron and low acid concentration (Woranart and Theeraporn
2013). The leaching of the KOH-treated ilmenite with oxalic
acid as a function of acid concentration, liquid to solid ratio,
time and temperature was investigated by Nayl and Aly
(2009). The leaching efficiency of titanium and iron was
enhanced in high acid concentration and liquid to solid
ratio (Nayl and Aly 2009). On the other hand, at higher
temperature than 150°C, the leaching percentage of titanium
using 80 wt.% oxalic acid decreased steadily due to hydrolysis
of titanium, while that of iron increased (Nayl and Aly 2009;
Nayl et al. 2009a). The leaching reaction of titanium was
controlled by the chemical reaction taking place on the sur-
face of ilmenite paste and oxalic acid with activation energy of
22 kJ mol–1 (Nayl et al. 2009a).
3.3. Caustic leaching
Alkaline pressure leaching was developed by Amer (2002) to
dissolve titanium from mechanically activated Rosetta ilme-
nite. At least 90% of titanium was leached in the form of
sodium titanate under the optimum conditions: 0.3M NaOH,
90 min, 200°C and an oxygen partial pressure of 10 bar (see
Equation (6)) (Amer 2002). Alkaline leaching is used com-
monly for dissolution of titanium from raw ilmenite or the
hydrolyzed titania residue after removal of iron (Wu et al.
2011a, 2011b). The mixture of NH3.H2O and H2O2 was used
for dissolving titanium from hydrolyzed titania residue (Wu
et al. 2011a, 2011b). In this medium, H2O2 was used to
provide O22 – ions which react with titanium to form titanate
peroxide groups (TiO32–) and pertitanate group (TiO62–),
while NH3 was added to change TiO2.H2O into ammonium
salt with high solubility (Wu et al. 2011b). Although most
titanium was leached by the mixture of NH3.H2O and H2O2
under the optimum condition, final product of TiO2 was not
uniform and the purity was not high owing to high content of
SiO2 (Wu et al. 2011b). The purity of TiO2 with special
nanowire structure can be improved by leaching with the
mixture of sodium hydroxide and hydrogen peroxide (Wu
et al. 2013). The author reported that precipitation of titanium
dioxide hydrate was formed by heating the leaching solution
of sodium titanium peroxide solution, while a minor amount
of dissolved silica remained in the alkaline solution. Wang
et al. (2010) also found that most of silicon from the residue
of ilmenite after acid leaching was removed by two step alka-
line leaching in order to obtain pure titanium-containing
precursor.
4FeTiO3 þ8NaOHþO2 ¼ 4Na2 TiO3 þ2Fe2 O3 þ4H2 O (6)
3.4. Comparing leaching efficiency
The recovery efficiency of TiO2 and leaching efficiency of
Fe2O3 from the Quara-aghaj ilmenite using HCl and H2SO4
10 T. H. NGUYEN AND M. S. LEE

solution was compared by Mehdilo and Irannajad (2012). disadvantage of caustic leaching is the consumption of a
Under the optimum conditions, the contents and purity of large amount of alkaline solution and high energy require-
titanium oxide concentrate obtained from HCl leaching were ment (Wu et al. 2011b). Table 6 lists the advantages and
higher than those from H2SO4 leaching (Mehdilo and disadvantage of acid and caustic leaching of ilmenite from
Irannajad 2012). The author reported that an easy recovery reported literatures.
of HCl from waste was another advantage of HCl leaching for
TiO2 pigment production from ilmenite. Razieh (2014) also
agreed that the recovery efficiency of TiO2 from H2SO4 leach- 4. Hydrometallurgical process for the production
ing system was slightly lower than that from HCl leaching. titanium dioxide from ilmenite
The dissolution kinetics of ilmenite in HCl appears to be
Hydrometallurgical process for the recovery of titanium from
marginally favorable compared to that in H2SO4 (Sasikumar
ilmenite as a form of titanium dioxide has been developed as
et al. 2004). However, the enhanced dissolution of titanium in
an alternative to conventional processes in the last decades. A
HCl is affected by the hydrolysis and precipitation reactions at
summary of processes for the production of titanium dioxide
higher temperature, low acid concentration for prolonged
from ilmenite with/without pretreatment by hydrometallurgi-
periods of leaching (El-Hazek et al. 2007; Middlemas et al.
cal process is shown in Table 7. Generally, the production of
2013). Jia et al. (2014) also reported that H2SO4 leaching was
titanium dioxide from ilmenite by hydrometallurgical process
less efficient in removing impurities from ilmenite than HCl
is commonly conducted by two different ways: (i) selective
leaching but H2SO4 corrodes the production equipment to a
leaching of iron and other impurities from ilmenite by acid
lesser degree than HCl.
leaching with low acid concentration, leading to upgrade of
A comparison in the leaching efficiency of titanium and
TiO2 content in the residue; (ii) selective leaching of titanium
iron from ilmenite between strong and weak acid is shown in
and small amount of impurities from ilmenite by acid leach-
Table 5. Compared to strong acids like hydrochloric and
ing with high acid concentration or caustic leaching and
sulfuric acid, oxalic acid was the most favorable leaching
subsequent purification by solvent extraction/ion exchange/
reagent for the leaching of pretreated ilmenite due to the
hydrolysis.
highest and lowest leaching percentage of titanium and iron,
A proposed process using KOH treatment followed by
respectively (Nayl et al. 2009a). A reasonable L/S ratio and less
oxalic acid leaching, hydrolysis and precipitation was devel-
corrosive action of oxalic acid is another advantage of oxalic
oped by Nayl et al. (2009a). A crystalline anatase type TiO2
acid leaching but the drawback is high cost of oxalic acid and
was obtained after calcination, washing, and drying of the
high energy requirement compared to HCl and H2SO4 (Nayl
titanium precipitates (Nayl et al. 2009a). TiO2 pigment with
et al. 2009a). Woranart and Theeraporn (2013) found that
high purity was produced using a unique combination of
sulfuric and citric acid offered higher leaching efficiency of
metallurgical processes, including NaOH roasting of tita-
titanium than hydrochloric and oxalic acid. Although the
nium slag followed by HCl leaching, solvent extraction,
highest leaching percentage of titanium was obtained from
hydrolysis and calcination (Middlemas et al. 2013). The
sulfuric acid leaching, citric acid was suggested for leaching of
process of oxidation-reduction-mechanical activation-
titanium and iron from ilmenite in terms of low leaching
hydrochloric acid leaching was developed by L. Zhang
percentage of iron and low acid consumption (Woranart
et al. (2011a). After leaching of the oxidized-reduced-
and Theeraporn 2013).
mechanically activated ilemnite, the leached product was
Production of TiO2 from ilmenite by combining acid
filtrated, washed, and calcinated to produce a synthetic
and alkaline leaching has been reported in some literatures
rutile containing 90.5% TiO2 (Zhang et al. 2011a).
(Wu et al. 2011b, 2013; Guo et al. 2014). Hydrochloric acid
Furthermore, Palliyaguru et al. (2017) indicated that most
leaching process has been considered as the primary tech-
iron was removed by ion exchange from the HCl leaching
nology to produce titanium-rich materials from ilmenite
solution of ilmenite after oxidative conversion of Fe(II) to
because it has advantage in the removal of impurities
Fe(III), resulting an iron-free solution of titanium oxychlor-
such as iron, magnesium and calcium, in fast leaching
ide. The main drawback of this method is the high content
rate and in acid regeneration technology (Wu et al.
of other impurities such as SiO2 and Al2O3 in final product.
2011a). Subsequently, alkaline leaching in the presence of
Liu et al. (2017) proposed a new process for preparing
a coordination agent was employed for the dissolution of Ti
synthetic rutile from ilmenite by two major steps including
from the residue of ilmenite (Wu et al. 2013, 2011b). The
selectively sulfating ilmenite, which was realized by roasting

Table 5. A summary on the optimum conditions for the leaching of paste ilmenite by strong and weak acids.
Parameter % Leaching References
Agitation, rpm Time, h L/S T°C Acid media Ti Fe (Nayl et al. 2009a; Nayl and Aly 2009)
375 2 4/1 125 9M HCl 92 76
375 2.5 9/1 150 6M H2SO4 89 91
500 3 5/1 150 70% H2C2O4 93 73
250 2 3.5M HCl 1.8 6.7 (Woranart and Theeraporn 2013)
750 10 20/1 90 8M H2SO4 68 63.5
750 20 1M C6H8O7 63 11
750 5 2M H2C2O4 34.2 3.1
L/S is liquid to solid ratio

Table 6. Advantages and disadvantages of acid and caustic leaching of ilmenite in reported literatures.
Process Advantages
HCl leaching High efficiency; Easy regeneration and recyclability of
HCl
Both cost and waste management
Regeneration of acid through pyrohydrolysis
Excellent impurities removal capability; high leaching
speed; acid regeneration technology
H2SO4 leaching Less corrodes the production equipment; reusing the
discharge of H2SO4 waste
Use of low grade ilmenite
Low capital investment and low energy consumption
Weak acid leaching Requires low acid concentration; high selective
leaching of Ti over Fe; reasonable liquid to solid ratio;
less corrosive action
Caustic leaching Higher leaching selectivity for Ti over Fe; mild leach Need for transformation of titanate to hydrous TiO2 in acidic
condition at low temperature and atmosphere
ilmenite with (NH4)2SO4 followed by selective thermal
decomposition of sulfated ilmenite, and leaching of impu-
rities. The leaching consisted of water, diluted acid and
alkaline leaching to remove the water-soluble sulfate,
Fe2O3 and SiO2, respectively (Liu et al. 2017). Wu et al.
(2013) and Wang et al. (2010) reported a process to pro-
duce anatase TiO2 nanowires from ilmenite. The process
consisted of (i) leaching of the mechanically activated
Panzhiua ilmenite by HCl to generate high titanium residue
and iron-rich filtrate, (ii) leaching of the hydrolyzed tita-
nium residue with hydrogen peroxide solution under alka-
line condition or sodium solution to dissolve Ti and Si, (iii)
boiling of the leaching solution to obtain titanium precipi-
tates, and (iv) calcination of the product to produce ana-
ntase TiO2 nanowires. The advantages of this process are
that the iron rich filtrate obtained from HCl leaching was
used as a starting material to produce metal-doped LiFePO4
and HCl used for leaching process was regenerated (Wang
et al. 2010). The flow chart of the process is shown in
Figure 2. Similar environment-friendly process based on
mechanical activation-hydrochloric acid leaching was used
for the preparation of TiO2 from ilmenite (Xiong et al.
2013). However, the hydrolyzed titanium residue obtained
in this process was digested with concentrated sulfuric acid
and subsequently leached in water to prepare titanium
sulfate solution. The author found that the addition of
EDTA suppressed the precipitation of the ferric ion during
hydrolysis of the titanium sulfate solution, resulting in the
synthetic rutile TiO2 with high purity (Xiong et al. 2013).
5. Conclusion
Pretreatment of ilmenite by mechanical activation, oxidation-
reduction, and thermal decomposition prior to leaching process
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 11
Disadvantages References
Corrodes the production equipment (Jia et al. 2014)
Requires a high-grade titanium raw materials (Yousef 2015)
Pyrohydrolysis requires quite energy intensive; High capital (Middlemas
cost for process equipment due to the use of the concentrated et al. 2013)
HCl (Zhang et al.
Problem in solid/liquid separation 2011a; Zhang
et al. 2010)
Less efficiency in removing impurities (Jia et al. 2014)
Difficulty for treatment of crude iron (II) sulfate and of the (Tsuchida et al.
waste acid solution 1982)
Large volume of waste; requiring proper treatment and (Wu et al. 2013)
disposal; slow leaching rate (Zhang and
Large quantities of waste iron sulfate process and diluted Nicol 2009)
sulfate acid
Requires high energy; high cost of acid (Nayl et al.
2009a)
(Zhang et al.
solution; recycling of large amount of alkaline solution and 2011b)
energy consumption
resulted in a change in phase, particle size, the crystalline struc-
ture, disorder in the crystalline structure, and chemical reaction
which accelerated the leaching rate of ilmenite. Both acid leaching
and caustic leaching is interactively used for leaching of titanium
and impurities from ilmenite. Caustic leaching and weak acid
leaching offered high selective leaching of titanium over iron
from ilmenite but the application of these methods was limited
in industry due to low purity of final product, high cost of acid,
and energy consumption. By contrast, strong acid leaching was
found to be acceptable from industrial point of view.
The leaching efficiency of titanium by acid leaching was
enhanced in high acid concentration, while there was an
opposite trend in leaching rate at high temperature, prolonged
period of time and low acid concentration due to the hydro-
lysis. The acid leaching of ilmenite was controlled by shrink-
ing core which depended on leaching conditions and types of
ilmenite ores. The recovery of titanium from ilmenite as
titanium dioxide by HCl and H2SO4 leaching was conducted
by two possible methods: (i) upgrading of TiO2 from ilmenite
by removing impurities using low acid concentration or add-
ing additives to acid solution; (ii) production of TiO2 by
selective leaching of titanium from ilmenite using high acid
concentration. It was noticed that HCl leaching with low acid
concentration was commonly used for the production of TiO2
in terms of minimizing waste management and acid con-
sumption. Hydrometallurgical process has been developed to
produce TiO2 of high purity from pretreated ilmenite, con-
sisting of either HCl leaching and purification by solvent
extraction or alkaline leaching, hydrolysis and calcination.
Especially regeneration of HCl and recovery of valuable iron
by-product is main advantage to reduce operation cost and to
solve environmental hazards. The present review focused on
the emerging hydrometallurgical processes in either labora-
tory or small scale with high production efficiency of titanium
 12

Table 7. Processes for production of titanium dioxide from ilmenite with/without pretreatment using acid leaching or combination of acid leaching and alkaline leaching.
Methods Processes Leaching efficiency, % Product composition, wt.% Waste management References
Removal impurities Ilmenite,44.62 wt.% TiO2 Fe: 98.93 Ti: 2.6 TiO2: 90.5 HCl (Tan et al. 2011; Zhang et al. 2011a)
from ilmenite * Oxidation-reduction-mechanical activation Fetotal: 1.37 Fe2O3
using low acid * Acid leaching: 20% HCl, 105°C, 10 h, L/S = 3.5 SiO2: 6.66
concentration * Calcination CaO +MgO: 1.0
(upgrading of Ilmenite,47.25 wt.% TiO2 Fe: 94 TiO2: 92.3 HCl (Li et al. 2008b)
ilmenite) * Mechanical activation Ti: 1 Fe2O3: 2.1 Fe2O3
* Acid leaching:20% HCl, 100°C,  6h, L/S = 5.5 SiO2: 5.21
* Calcination Al2O3:0.064
MnO2: 0.026
CaO +MgO: 0.28
Ilmenite,55.47 wt.% TiO2 - Purity of TiO2 > 99.4 HCl and iron (Zhang et al. 2009)
T. H. NGUYEN AND M. S. LEE

* NaOH decomposition
* Acid leaching: HCl (pH = 2.0); 110°C, L/S = 150
Ilmenite,46.86 wt.% TiO2 Fe: 95 TiO2: 92.86 Fe(OH)2 (Liu et al. 2017)
* (NH4)2SO4 roasting Ti: 0.2 Fetotal: 1.73 Mg(OH)2
* Water leaching (FeSO4, MgSO4, CaSO4): 50°C, L/S: 10 SiO2: 3.23
* Acid leaching: 2.5% HCl, 98°C, 2h, L/S = 10 Al2O3:0.25
* Alkaline leaching: 1.32M NaOH, 102°C, 1h CaO +MgO: 1.37
Ilmenite,41.1 wt.% TiO2 Fe: 99.4 TiO2: 89.45 HCl (Mahmoud et al. 2004)
* Reductive leaching: 20% HCl, Fe stoichiometry: 1.1, 110°C added Ti: 2 Fe2O3: 0.77 Fe2O3
after 30 min, 5 h SiO2: 5.8
* Calcination Al2O3:0.03
MnO2: 0.02
V2O5: 0.1
Cr2O3: 0.01
CaO +MgO: 0.05
Ilmenite,72 wt.% TiO2 Fe: 97.4 TiO2: 97 (Lasheen 2008)
*Soda ash roasting Ti: 0.65 Fet: 0.055
* Water leaching (V, Cr) SiO2: 1.9
* Acid leaching: 20% HCl, 30 min; L/S = 3 Al2O3:0.25
* NaOH leaching (silica): CaO +MgO: 0.45
* Calcination
Ilmenite,72.43 wt.% TiO2 Fe: 95.3 TiO2: 95.34 (Guo et al. 2014)
* H3PO4 roasting Mg:98.7, Ca: 87.7 P2O5: 0.12
* Acid leaching: 20% HCl, 110°C, 2 h, L/S = 5 Al: 95.44 SiO2: 0.97
* NaOH leaching (Si, P) CaO +MgO: 0.37
* Calcination
Ilmenite,47.6 wt.% TiO2 Fe, Mg, Ca, Mn, Al: ~99 TiO2: 90.8 HCl (Wu et al. 2010)
* Mechanical activation Ti: 1.07 Fe2O3: 2.21 LiFePO4
* Acid leaching: 20% HCl, 100°C, 2 h, L/S = 1.2 Al2O3:0.105
* Calcination MnO2: 0.052
SiO2: 6.421
CaO +MgO: 0.23
Ilmenite,72.7 wt.% TiO2 Fe: 95 TiO2: 91 (Mehdilo and Irannajad 2012)
* Acid leaching: 8% HCl, 95°C, 2 h, L/S = 4 Fe2O3: 0.61
SiO2: 0.58
CaO +MgO: 3.5
Ilmenite,53.66 wt.% TiO2 Fe~100 TiO2 > 90 Fe2O3 (Palliyaguru et al. 2017)
Acid leaching: 20% HCl Ti:18
Chlorination: Conversion Fe(II) to Fe(III)
Ion exchange: IRA 410 Cl resin (Fe)
Hydrolysis-calcination
(Continued )
Table 7. (Continued).
Methods Processes Leaching efficiency, % Product composition, wt.% Waste management References
Dissolution of Ilmenite,41.3 wt.% TiO2 Fe:93.2 Purity of TiO2 > 99.4 HCl (Abdou et al. 2015)
titanium from * Acid leaching: 12 M HCl, 80°C, 1 h, L/S = 12 Ti: 95.1 Sugar and FeCl2
ilmenite using * Precipitation: 6 g/L Cellulose.
high acid * Calcination
concentration or Ilmenite,64.4 wt.% TiO2 Fe: ~15 TiO2: 99.9 (Middlemas et al. 2013)
alkaline solution * Alkaline roasting Ti: ~90 Fetotal <0.1
* Acid leaching: 5M HCl, 50°C; 4 h, L/S = 10
* Solvent extraction: Alamine 336 (Fe)
* Hydrolysis-calcination
Ilmenite,46.38 wt.% TiO2 Fe: 73 TiO2: 98 (Nayl and Aly 2009)
* KOH decomposition Ti: 93 Fe2O3: 1.3
* Acid leaching: 70% C2O4H2, 150°C, 3 h, L/S = 5 SiO2: 0.04
*Hydrolysis-calcination MnO: 0.3
Ilmenite,30 wt.% TiO2 Fe: 96–97 Iron piment (Das et al. 2013)
* Acid leaching: 9.8M HCl; 240 g/L CaCl2; 70°C; 4 h Ti: 98–99 HCl+impurities
* Solvent extraction (Fe)
* Solvent extraction (Ti)
* Ti hydrolysis
Ilmenite,47.6 wt.% TiO2 Fe: 100 HCl (Xiong et al. 2013)
* Mechanical activation Ti: 98.5 LiFePO4
* HCl leaching (Fe)
* H2SO4 decomposition: 80–85% H2SO4, 150°C, S/L = 2.7
* Water leaching
* Hydrolysis in the presence of ethylenediaminetetraacetic acid
(EDTA)
* Calcination
Ilmenite,47.6 wt.% TiO2 Ti: 98 TiO2: 97.81 HCl (Wu et al. 2011b)
* Mechanical activation SiO2: 2.19 LiFePO4
* HCl leaching (Fe)
* NH3 +H2O2 leaching: 5% H2O2, H2O2/solid mass ratio of 6/1, pH = 9,
40°C, 20min
* Hydrolysis-calcination
Ilmenite,47.6 wt.% TiO2 Ti: 96.39 TiO2: 99.53 HCl (Wu et al. 2013)
* Mechanical activation Si: 67.9 SiO2: 0.47 LiFePO4
* HCl leaching (Fe, Al, Mn, Ca)
* NaOH + H2O2 leaching: Na+/Ti4+ molar ratio of 8/1, O22–/Ti4+ molar
ratio of 6/1, pH = 9, 30°C, 30min
* Hydrolysis-calcination
Ilmenite,46.38 wt.% TiO2 Ti: 80 TiO2: 95.55 (Yousef 2015)
* KOH decomposition Fe: 17 Fe2O3: 0.799
* Acid leaching: 6M HCl, 80°C, 2 h, L/S = 6 SiO2: 0.55
* Hydrolysis-calcination Al2O3: 0.97
L/S is liquid to solid ratio
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW
13
14 T. H. NGUYEN AND M. S. LEE

Ilmenite

Ball milling
HCl

Leaching and hydrolysis

S/L separation Filtrate

HCl
NaOH High-titanium residue H2O2 Boil

H3PO4 Solution H2O2 Waste HCl

Leaching

S/L separation Residue Precipitation Evaporation

NaOH

Sodium titanium peroxide solution S/L separation Solution

LiCO3 FePO4.xH2O H2C2O4.2H2O

Boiling

Titanium dioxide hydrate Ball milling

Washing Calcination

Drying LiFePO4

Calcination

Anatase TiO2 nanowires

Figure 2. The flow-chart of the synthesis process (Wu et al. 2013).

dioxide from ilmenite. Life cycle assessment should be com-
pared among various processes on the basis of production
efficiency, energy demand, and waste generation.
Disclosure statement
The authors report no conflicts of interest. The authors alone
are responsible for the content and writing of the article.
Funding
This work was supported by the Global Excellent Technology Innovation
of the Korea Institute of Energy Technology Evaluation and Planning
(KETEP), granted financial resource from the Ministry of Trade,
Industry & Energy, Republic of Korea [No.20165010100880].
References
Abdou, A. A., Manaa, E. A., and Zaki, S. A., 2015, “Synthetic rutile
preparation from Egyptian Ilmenite using hydrochloric acid in the
presence of cellulose as reducing agent.” International Journal of
Multidisciplinary Research and Development, 2. pp. 443–451.
Adipuri, A., Li, Y., Zhang, G., and Ostrovski, O., 2011, “Chlorination of
reduced ilmenite concentrates and synthetic rutile.” International
Journal of Mineral Processing, 100. pp. 166–171.
Akhgar, B. N., Pazouki, M., Akhgar, B. N., Ranjbar, M., and Hosseinnia,
A., 2013, “Preparation of micro and nanostructured titania com-
pounds from ilmenite concentrates.” International Journal of
Mineral Processing, 124. pp. 138–140.
Amer, A. M., 2002, “Alkaline pressure leaching of mechanically activated
Rosetta ilmenite concentrate.” Hydrometallurgy, 67. pp. 125–133.
Awwad, N. S., and Ibrahium, H. A., 2013, “Kinetic extraction of titanium
(IV) from chloride solution containing Fe(III), Cr(III) and V(V) using
the single drop technique.” Journal of Environmental Chemical
Engineering, 1. pp. 65–72.
Baba, A. A., Adekola, F. A., Arodola, O. A., Ibrahim, L., Bale, R. B.,
Ghosh, M. K., and Sheik, A. R., 2012, “Simultaneous recovery of total
iron and titanium from ilmenite ore by hydrometallurgical proces-
sing.” Association Metallurgical Engineering Serbia, 18. pp. 67–78.
Baba, A. A., Adekola, F. A., Toye, E. E., and Bale, R. B., 2009, “Dissolution
kinetics and leaching of rutile ore in hydrochloric acid.” Journal of
Minerals and Materials Characterization and Engineering, 8. pp. 787–801.
Baba, A. A., Swaroopa, S., Ghosh, M. K., and Adekola, F. A., 2013,
“Mineralogical characterization and leaching behavior of Nigerian
ilmenite ore.” Transactions of Nonferrous Metals Society of China,
23. pp. 2743–2750.
Barton, A. F. M., and Mcconnel, S., 1979, “Rotating disc dissolution rates
of ionic solids. Part 3.—natural and synthetic ilmenite.” Journal of the
Chemical Society, Faraday Transactions, 75. pp. 971–983.

Bordbar, H., Yousefi, A. A., and Abedini, H., 2017, “Production of
titanium tetrachloride (TiCl4) from titanium ores: A review.”
Polyolefins Journal, 4. pp. 313–324.
Chen, L., Wen, S., Xu, G., and Xie, H., 2013, “A novel process for
titanium sand by magnetic separation and gravity concentration.”
Mineral Processing and Extractive Metallurgy Review, 34. pp. 139–150.
Dang, J., Zhang, G. H., and Chou, K. C., 2015, “Kinetics and mechanism
of hydrogen reduction of ilmenite powders.” Journal of Alloys and
Compounds, 619. pp. 443–451.
Das, G. K., Pranolo, Y., Zhu, Z., and Cheng, C. Y., 2013, “Leaching of ilmenite
ores by acidic chloride solutions.” Hydrometallurgy, 133. pp. 94–99.
El-Hazek, N., Lasheen, T. A., El-Sheikh, R., and Zaki, S. A., 2007,
“Hydrometallurgical criteria for TiO2 leaching from Rosetta ilmenite
by hydrochloric acid.” Hydrometallurgy, 87. pp. 45–50.
Gázquez, M. J., Bolívar, J. P., Garcia-Tenorio, R., and Vaca, F., 2014, “A
review of the production cycle of titanium dioxide pigment.”
Materials Sciences and Applications, 05. pp. 441–458.
Gireesh, V. S., Vinod, V. P., Krishnan Nair, S., and Ninan, G., 2015,
“Catalytic leaching of ilmenite using hydrochloric acid: A kinetic
approach.” International journal of mineral processing, 134. pp. 36–40.
Gireesh, V. S., Vinod, V. P., Nair, S. K., and Ninan, G., 2013, “Effect of
sulphate ions on leaching of ilmenite with hydrochloric acid.” Journal
of Academia and Industrial Research, 2. pp. 402–404.
Grey, I., McDonald, K., Fisher-White, M., and De Vries, M., 2007,
“Hydrogen reduction of preoxidised ilmenite in fluidised bed and
packed bed reactors.” Mineral Processing and Extractive Metallurgy,
116. pp. 209–216.
Guéguin, M., and Cardarelli, F., 2007, “Chemistry and mineralogy of titania-
rich slags. Part 1 - hemo-ilmenite, sulphate, and upgraded titania slags.”
Mineral Processing and Extractive Metallurgy Review, 28. pp. 1–58.
Guo, Y., Liu, S., Jiang, T., Qiu, G., and Chen, F., 2014, “A process for
producing synthetic rutile from Panzhihua titanium slag.”
Hydrometallurgy, 147–148. pp. 134–141.
Habashi, F., 1997, Handbook of Extractive Metallurgy, New York: Wiley-
VCH ISBN 3-527-28792-2.
Habib, M. A., Biswas, R. K., Ali, M. R., and Hasan, A. K. M., 2006,
“Leaching of non-treated ilmenite by HCl-CH3OH-H2O mixture and
its kinetics.” Indian Journal of Chemical Technology, 13. pp. 53–59.
Han, K. N., 1992, “New trends and challenges in leaching process.”
Mineral Processing and Extractive Metallurgy Review, 8. pp. 57–72.
Han, K. N., Rubcumintara, T., and Fuerstenau, M. C., 1987, “Leaching
behavior of ilmenite with sulfuric acid.” Metallurgical Transactions B,
18. pp. 325–330.
Hao, X., Lü, L., Liang, B., Li, C., Wu, P., and Wang, J., 2012, “Solvent
extraction of titanium from the simulated ilmenite sulfuric acid leachate
by trialkylphosphine oxide.” Hydrometallurgy, 113–114. pp. 185–191.
Haverkamp, R. G., Kruger, D., and Rajashekar, R., 2016, “The digestion
of New Zealand ilmenite by hydrochloric acid.” Hydrometallurgy, 163.
pp. 198–203.
Janssen, A., and Putnis, A., 2011, “Processes of oxidation and HCl-
leaching of Tellnes ilmenite.” Hydrometallurgy, 109. pp. 194–201.
Jayaweera, P. M., Jayaweera, P. V. V., Jayasundara, U. L., Jayaweera, C. D.,
Peiris, G. S., and Premalal, E. V. A. P., 2011, “Photo induced reductive
leaching of iron from ilmenite in hydrochloric acid solutions.” Mineral
Processing and Extractive Metallurgy, 120. pp. 191–196.
Jia, L., Liang, B., Lü, L., Yuan, S., Zheng, L., Wang, X., and Li, C., 2014,
“Beneficiation of titania by sulfuric acid pressure leaching of
Panzhihua ilmenite.” Hydrometallurgy, 150. pp. 92–98.
Kalinnikov, V. T. T., and Nikolaev, A. I. I., 2002, “Titanium-rare metal
minerals of the Kola Peninsula – a source of both conventional and
new materials.” Mineral Processing and Extractive Metallurgy Review.
An Internation Journal, 22. pp. 453–462.
Kothari, N. C., 1974, “Recent developments in processing ilmenite for
titanium.” International Journal of Mineral Processing, 1. pp. 287–305.
Lasheen, T. A., 2008, “Soda ash roasting of titania slag product from
Rosetta ilmenite.” Hydrometallurgy, 93. pp. 124–128.
Lasheen, T. A. I., 2005, “Chemical benefication of Rosetta ilmenite by
direct reduction leaching.” Hydrometallurgy, 76. pp. 123–129.
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 15
Li, C., Liang, B., and Guo, L.-H., 2007, “Dissolution of mechanically
activated Panzhihua ilmenites in dilute solutions of sulphuric acid.”
Hydrometallurgy, 89. pp. 1–10.
Li, C., Liang, B., Song, H., Xu, J.-Q., and Wang, X.-Q., 2008a,
“Preparation of porous rutile titania from ilmenite by mechanical
activation and subsequent sulfuric acid leaching.” Microporous and
Mesoporous Materials, 115. pp. 293–300.
Li, C., Liang, B., and Wang, H. Y., 2008b, “Preparation of synthetic rutile
by hydrochloric acid leaching of mechanically activated Panzhihua
ilmenite.” Hydrometallurgy, 91. pp. 121–129.
Li, Z., Wang, Z., and Li, G., 2016, “Preparation of nano-titanium dioxide
from ilmenite using sulfuric acid-decomposition by liquid phase
method.” Powder Technological, 287. pp. 256–263.
Liang, B., Li, C., Zhang, C., and Zhang, Y., 2005, “Leaching kinetics of
Panzhihua ilmenite in sulfuric acid.” Hydrometallurgy, 76. pp. 173–179.
Liddell, K. C., 1988, “A model for the recovery of titanium from mixtures
of ilmenite and hematite by hydrochloric acid leaching.” Separation
Science and Technology, 23. pp. 2005–2014.
Liu, S., Zhu, K., Xiang, J., and Huang, P., 2015, “Upgrading ilmenite by
an oxidation-magnetic separation-pressure leaching process.” Bulg
Chemical Communicable, 47. pp. 1118–1123.
Liu, W., Wang, X., Lu, Z., Yue, H., Liang, B., Lü, L., and Li, C., 2017,
“Preparation of synthetic rutile via selective sulfation of ilmenite with
(NH4)2SO4 followed by targeted removal of impurities.” Chinese
Journal Chemical Engineering, 25. pp. 821–828.
Liu, Y., Qi, T., Chu, J., Tong, Q., and Zhang, Y., 2006, “Decomposition of
ilmenite by concentrated KOH solution under atmospheric pressure.”
International Journal Miner Processing, 81. pp. 79–84.
Mahmoud, M. H. H., Afifi, A. A. I., and Ibrahim, I. A., 2004, “Reductive
leaching of ilmenite ore in hydrochloric acid for preparation of syn-
thetic rutile.” Hydrometallurgy, 73. pp. 99–109.
Manhique, A. J., Focke, W. W., and Madivate, C., 2011, “Titania recovery
from low-grade titanoferrous minerals.” Hydrometallurgy, 109. pp.
230–236.
Mehdilo, A., and Irannajad, M., 2012, “Iron removing from titanium slag
for synthetic rutile production.” Physicochem Problems Miner
Processing, 48. pp. 425–439.
Meng, F.-C., Xue, T.-Y., Liu, Y.-H., Zhang, G.-Z., and Qi, T., 2016,
“Recovery of titanium from undissolved residue (tionite) in titanium
oxide industry via NaOH hydrothermal conversion and H2SO4 leach-
ing.” Transactions Nonferrous Met Social China, 26. pp. 1696–1705.
Middlemas, S., Fang, Z. Z., and Fan, P., 2013, “A new method for
production of titanium dioxide pigment.” Hydrometallurgy, 131–132.
pp. 107–113.
Middlemas, S., Fang, Z. Z., and Fan, P., 2015, “Life cycle assessment
comparison of emerging and traditional Titanium dioxide manufac-
turing processes.” Journal Clean Products, 89. pp. 137–147.
Narayana, K. L., Swamy, K. M., Sarveswara Rao, K., and Murty, J. S.,
1997, “Leaching of metals from ores with ultrasound.” Min Pro Ext
Met Reviews, 16. pp. 239–259.
Nayl, A. A., and Aly, H. F., 2009, “Acid leaching of ilmenite decomposed
by KOH.” Hydrometallurgy, 97. pp. 86–93.
Nayl, A. A., Awwad, N. S., and Aly, H. F., 2009a, “Kinetics of acid leaching of
ilmenite decomposed by KOH. Part 2. Leaching by H2SO4 and C2H2O4.”
Journal of hazardous materials, 168. pp. 793–799.
Nayl, A. A., Ismail, I. M., and Aly, H. F., 2009b, “Ammonium hydroxide
decomposition of ilmenite slag.” Hydrometallurgy, 98. pp. 196–200.
Nurul, A., 2016, Chemical and Electrochemical Leaching Studies of
Synthetic and Natural Ilmenite in Hydrochloric Acid Solution, Perth
Western Australia: Murch University.
Ogasawara, T., and Veloso De Araújo, R. V., 2000, “Hydrochloric acid
leaching of a pre-reduced Brazilian ilmenite concentrate in an auto-
clave.” Hydrometallurgy, 56. pp. 203–216.
Olanipekun, E., 1999, “A kinetic study of the leaching of a Nigerian
ilmenite ore by hydrochloric acid.” Hydrometallurgy, 53. pp. 1–10.
Palliyaguru, L., Arachchi, N. D. H., Jayaweera, C. D., and Jayaweera, P.
M., 2017, “Production of synthetic rutile from ilmenite via anion-
exchange.” Miner Processing Extr Metall, 9553. pp. 1–7.
16 T. H. NGUYEN AND M. S. LEE
Ramadan, A. M., Farghaly, M., Fathy, W. M., and Ahmed, M. M., 2016,
“Leaching and kinetics studies on processing of Abu-Ghalaga ilmenite
ore.” International Researcher Journal Engineering Technical, 3. pp. 46–53.
Razieh, R., 2014, “Production of nanosized synthetic rutile from ilmenite
concentrate by sonochemical HCl and H2SO4 Leaching.” Iran Journal
Chemical Chemical Engineering, 33. pp. 29–36.
Reddy, M. L. P., and Saji, J., 2002, “Mineral processing and extractive
metallurgy review: An international Journal.” Miner Processing Extr
Reviews, 23. pp. 199–227.
Roche, E. G., Stuart, A. D., and Grazier, P. E., 2004, “Production of
Titania,” WO2004035841-A1.
Run, H., Pengsheng, L., Yuehui, Y., and Jinzhu, Z., 2017, “Vacuum
carbothermic reduction of Panzhihua ilmenite concentrate: A thermo-
dynamic study. miner.” Processing Extr Metall Reviews, 38. pp. 193–198.
Samal, S., 2011, “The dissolution of iron in the hydrochloric acid leach of
titania slag obtained from plasma melt separation of metalized ilme-
nite.” Chemical Engineering Researcher Design, 89. pp. 2190–2193.
Samal, S., 2013, “Preparation of synthetic rutile from pre-treated ilme-
nite/Ti-rich slag with phenol and resorcinol leaching solutions.”
Hydrometallurgy, 137. pp. 8–12.
Sarker, M. K., Rashid, A. K. M. B., and Kurny, A. S. W., 2006, “Kinetics of
leaching of oxidized and reduced ilmenite in dilute hydrochloric acid
solutions.” International Journal Miner Processing, 80. pp. 223–228.
Sasikumar, C., Rao, D. S., Srikanth, S., Mukhopadhyay, N. K., and
Mehrotra, S. P., 2007, “Dissolution studies of mechanically activated
Manavalakurichi ilmenite with HCl and H2SO4.” Hydrometallurgy, 88.
pp. 154–169.
Sasikumar, C., Rao, D. S., Srikanth, S., Ravikumar, B., Mukhopadhyay, N.
K., and Mehrotra, S. P., 2004, “Effect of mechanical activation on the
kinetics of sulfuric acid leaching of beach sand ilmenite from Orissa,
india.” Hydrometallurgy, 75. pp. 189–204.
Shojaei, V., Schaffie, M., Mohebbi, A., and Ranjbar, M., 2014, “Upgrading of
ilmenite using KOH sub-molten salt process assisted by mechanical activa-
tion.” Materials Manuf Processing, 29. pp. 1284–1288.
Sole, K. C., 1999, “Recovery of titanium from the leach liquors of
titaniferous magnetites by solvent extraction. Part 2. Laboratory-
scale studies.” Hydrometallurgy, 51. pp. 263–274.
Subagja, R., Andriyah, L., and Lalasari, L. H., 2013, “Titanium
Dissolution from Indonesian Ilmenite.” International Journal Basic
Applications Sciences IJBAS-IJENS, 13. pp. 97–103.
Sui, L. L., and Zhai, Y. C., 2014, “Reaction kinetics of roasting high-
titanium slag with concentrated sulfuric acid.” Transactions
Nonferrous Met Social China, 24. pp. 848–853.
Swamy, K. M., Sarveswara Rao, K., Narayana, K. L., Murty, J. S., and Ray,
H. S., 1995, “Application of Ultrasound in Leaching.” Miner Processing
Extr Metall Reviews, 14. pp. 179–192.
Swanepoel, J. J., Van Vuuren, D. S., and Heydenrych, M., 2011,
“Leachability of nitrided ilmenite in hydrochloric acid.” Journal
Southern African Institute Min Metall, 111. pp. 137–140.
Tan, P., Hu, H. P., and Zhang, L., 2011, “Effects of mechanical activation
and oxidation-reduction on hydrochloric acid leaching of Panxi ilme-
nite concentration.” Transactions Nonferrous Met Social China, 21. pp.
1414–1421.
Tao, T., Chen, Q. Y., Hu, H. P., Yin, Z. L., and Chen, Y., 2012, “TiO2
nanoparticles prepared by hydrochloric acid leaching of mechanically
activated and carbothermic reduced ilmenite.” Transactions
Nonferrous Met Social China, 22. pp. 1232–1238.
Tsuchida, H., Narita, E., Takeuchi, H., Adachi, M., and Okabe, T., 1982,
“Manufacture of high pure titanium(IV) oxide by the chloride pro-
cess. I. Kinetic study on leaching of ilmenite ore in concentrated
hydrochloric acid solution.” Bulletin of the Chemical Society of
Japan, 55. pp. 1934–1938.
Van Dyk, J. P., Vegter, N. M., and Pistorius, P. C., 2002, “Kinetics of ilmenite
dissolution in hydrochloric acid.” Hydrometallurgy, 65. pp. 31–36.
Vásquez, R., and Molina, A., 2008, “Leaching of Ilmenite and Pre-
Oxidized Ilmenite in Hydrochloric Acid to Obtain High Grade
Titanium Dioxide.” International Journal of Mineral Processing, 68.
pp. 13–21.
Vásquez, R., and Molina, A., 2012, “Effects of thermal preoxidation on
reductive leaching of ilmenite.” Miner Engineering, 39. pp. 99–105.
Verhulst, D., Sabacky, B., Spitler, T., and Prochazka, J., 2003, “New
developments in the altair hydrochloride TiO2 pigment process.”
Proceedings TMS Fall Extr Processing Conference, 1. pp. 565–575.
Wahyuningsih, S., Pramono, E., Firdiyono, F., Sulistiyono, E., Rahardjo,
S. B., Hidayattullah, H., and Anatolia, F. A., 2013, “Decomposition of
ilmenite in hydrochloric acid to obtain high grade titanium dioxide.”
Asian Journal of Chemistry, 25. pp. 6791–6794.
Wahyuningsih, S., Ramelan, A. H., Pramono, E., and Djatisulistya, A.,
2014, “Titanium dioxide production by hydrochloricacid leaching of
roasting ilmenite sand.” International Journal of Scientific and
Research Publications, 4. pp. 2250–3153.
Wang, X., Li, W., Yang, B., Guo, S., Zhang, L., Chen, G., Peng, J., and
Luo, H., 2014, “Microwave-absorbing of carbothermic reduced pro-
ducts of ilmenite and oxidized ilmenite.” Journal of Microwave Power
and Electromagnetic Energy, 48. pp. 192–202.
Wang, X., Li, X., Wang, Z., Wu, L., Yue, P., Guo, H., Wu, F., and Ma, T.,
2010, “Preparation and characterization of Li4Ti5O12 from ilmenite.”
Powder Technology, 204. pp. 198–202.
Wei, L., Hu, H., Chen, Q., and Tan, J., 2009, “Effects of mechanical
activation on the HCl leaching behavior of plagioclase, ilmenite and
their mixtures.” Hydrometallurgy, 99. pp. 39–44.
Welham, N. J., and Llewellyn, D. J., 1998, “Mechanical enhancement
of the dissolution of ilmenite.” Minerals Engineering, 6875. pp.
827–841.
Woranart, J., and Theeraporn, R., 2013, “Titanium and iron dissolutions
from ilmenite by acid leaching and microbiological oxidation techni-
ques.” Asia-Pacific Journal of Chemical Engineering, 8. pp. 323–330.
Wu, F., Li, X., Wang, Z., Guo, H., Wu, L., Xiong, X., and Wang, X.,
2011a, “Preparation of TiO2 nanosheets and LiTi5O12 anode material
from natural ilmenite.” Powder Technology, 213. pp. 192–198.
Wu, F., Li, X., Wang, Z., Wu, L., Guo, H., Xiong, X., Zhang, X., and
Wang, X., 2011b, “Hydrogen peroxide leaching of hydrolyzed titania
residue prepared from mechanically activated Panzhihua ilmenite
leached by hydrochloric acid.” International Journal of Mineral
Processing, 98. pp. 106–112.
Wu, F., Li, X., Wang, Z., Xu, C., He, H., Qi, A., Yin, X., and Guo, H.,
2013, “Preparation of high-value TiO2 nanowires by leaching of
hydrolyzed titania residue from natural ilmenite.” Hydrometallurgy,
140. pp. 82–88.
Wu, L., Li, X., Wang, Z., Guo, H., Wang, X., Wu, F., Fang, J., Wang, Z.,
and Li, L., 2010, “A novel process for producing synthetic rutile and
LiFePO4 cathode material from ilmenite.” Journal of Alloys and
Compounds, 506. pp. 271–278.
Xiong, X., Wang, Z., Wu, F., Li, X., and Guo, H., 2013, “Preparation of
TiO2 from ilmenite using sulfuric acid decomposition of the titania
residue combined with separation of Fe3+ with EDTA during hydro-
lysis.” Advanced Powder Technology, 24. pp. 60–67.
Yousef, L. A., 2015, “Upgrading of TiO 2 separated from ilmenite
mineral, Rosetta, black sands of Egypt.” Arab Journal of Nuclear
Sciences and Applications, 48. pp. 33–43.
Zhang, L., Hu, H., Liao, Z., Chen, Q., and Tan, J., 2011a, “Hydrochloric
acid leaching behavior of different treated Panxi ilmenite concentra-
tions.” Hydrometallurgy, 107. pp. 40–47.
Zhang, L., Hu, H., Wei, L., Chen, Q., and Tan, J., 2010, “Hydrochloric
acid leaching behaviour of mechanically activated Panxi ilmenite
(FeTiO3).” Separation and Purification Technology, 73. pp. 173–178.
Zhang, L., Li, G. Q., and Zhang, W., 2011b, “Synthesis of rutile from high
titania slag by pyrometallurgical route.” Transactions of Nonferrous
Metals Society of China, 21. pp. 2317–2322.
Zhang, S., and Nicol, M. J., 2009, “An electrochemical study of the
reduction and dissolution of ilmenite in sulfuric acid solutions.”
Hydrometallurgy, 97. pp. 146–152.
Zhang, S., and Nicol, M. J., 2010, “Kinetics of the dissolution of ilmenite
in sulfuric acid solutions under reducing conditions.”
Hydrometallurgy, 103. pp. 196–204.
Zhang, W., Zhu, Z., and Cheng, C. Y., 2011, “A literature review of
titanium metallurgical processes.” Hydrometallurgy, 108. pp. 177–188.
Zhang, Y., Qi, T., and Zhang, Y., 2009, “A novel preparation of titanium
dioxide from titanium slag.” Hydrometallurgy, 96. pp. 52–56.
 MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 17

Zhu, Q., Zhang, J., and Li, H., 2014, “Influence of phase and micro- Zhu, Z., Zhang, W., and Cheng, C. Y., 2011, “A literature review of
structure on the rate of hydrochloric acid leaching in pretreated titanium solvent extraction in chloride media.” Hydrometallurgy, 105.
Panzhihua ilmenite.” Particuology, 14. pp. 83–90. pp. 304–313.