Hydrometallurgy 185 (2019) 226–237

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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Processing anatase ores for pigment production T

a a b,⁎ b
Keith R. Barnard , Robbie G. McDonald , Mark I. Pownceby , Graham J. Sparrow ,
Wensheng Zhanga
a
CSIRO Mineral Resources, PO Box 7229, Karawara, WA 6152, Australia
b
CSIRO Mineral Resources, Private Bag 10, Clayton South, VIC 3169, Australia

A R T I C LE I N FO A B S T R A C T

Keywords: Compared with processing high-TiO2 concentrates such as ilmenite ores, processing an anatase ore to achieve
Anatase impurity levels acceptable for pigment production is more difficult because of the extensive number of accessory
Mineral dressing minerals present, the significant intergrowths between minerals and the fact that impurity elements may be
Roasting distributed in several different minerals. In this paper, conditions applicable to processing anatase ores are
Leaching
reviewed with an aim of identifying conditions that may produce a suitable feedstock for processing to titania
Solvent extraction
pigment by either the sulphate or chloride routes.
Pigment production
Anatase ores containing 25–35 wt% TiO2 currently are processed using mineral dressing techniques of
crushing and grinding, classification, magnetic separation and flotation to produce a concentrate with around
65 wt% TiO2. This concentrate is then typically upgraded to over 90 wt% TiO2 using combinations of heating and
leaching treatments, often with the addition of a fluxing reagent to assist in impurity removal. The suitability of
these products as a feedstock for the sulphate and chloride routes to pigment is discussed.

1. Introduction
Titanium minerals are widely distributed in the lithosphere with
major deposits existing in Australia, Canada, India, Norway, South
Africa, Ukraine, and the United States. Ilmenite (FeTiO3), its altered
forms such as pseudorutile, approximate formulae FeTi2O5(OH), and
leucoxene (a mixture of pseudorutile and rutile), and rutile (TiO2) are
the most economically important titanium minerals. Other titanium
minerals that may be concentrated in mineral deposits are anatase
(TiO2), perovskite, (CaTiO3) and sphene (CaTiSiO5), but these minerals
are not exploited commercially at present.
About 95% of titanium ores are processed into titanium dioxide
(titania) pigment with much smaller amounts going to the production
of various titanium chemicals and titanium metal. The commercial
production of titania pigment is by the sulphate or the chloride routes,
the choice depending on the composition of the titanium feedstock. In
the sulphate process the titaniferous feed is dissolved in concentrated
sulphuric acid, while in the chloride process it is converted to volatile
chlorides by reaction with chlorine gas in a fluidised bed reactor.
Schematic flowsheets for both processes have been presented by Fisher
(1997) and Zhang et al. (2011). Primary ilmenite concentrates, con-
taining 48–55 wt% TiO2, are converted to titania pigment by the sul-
phate route while weathered ilmenite concentrates with 55–60 wt%
TiO2, are processed by the chloride route, usually after some upgrading
treatment to remove iron and other impurities. A detailed overview of
the production, properties and applications of titania pigments has been
given by Lakshmanan et al. (2014).
Rutile, with its low impurity levels, is ideal for processing by the
chloride process, but resources of rutile are limited compared with il-
menite. Anatase, the low temperature polymorph of rutile, also has a
high titania content (95 wt% TiO2), making it an attractive potential
feedstock for pigment production. Weathering of alkali igneous rocks
leads to the formation of anatase deposits, primarily via the breakdown
of perovskite. Currently there are a number of large anatase deposits in
the world that have been characterised and potential processing con-
ditions investigated, but at present none have been developed com-
mercially to generate suitable feedstocks for the production of titania
pigment. Examples include Catalão, Salitre, Tapira, Serra Negro and
Serra de Maicuru, all located in Brazil (Force, 1991). In addition to
alkaline sourced deposits other major occurrences of anatase include
the metamorphosed Yangtizishan-Moshishan sedimentary anatase de-
posit in Inner Mongolia (Zhao et al., 2011), the large residual Shazi
anatase deposit in Qinlong, Guizhou Province, southwestern China
(Zhang et al., 2014a, 2014b), karst-type ores at Araxa and Morro dos
Seis Lagos in Brazil and the relatively unexplored Tomtor complex in
Russia (Laznicka, 2006). These deposits have only been subject to

⁎
Corresponding author.
E-mail address: Mark.Pownceby@csiro.au (M.I. Pownceby).

https://doi.org/10.1016/j.hydromet.2019.02.006
Received 10 September 2018; Received in revised form 30 January 2019; Accepted 15 February 2019
Available online 03 March 2019
0304-386X/ Crown Copyright © 2019 Published by Elsevier B.V. All rights reserved.
K.R. Barnard, et al. Hydrometallurgy 185 (2019) 226–237

Table 1 most abundant natural members are rutile, anatase, and brookite (Ding
Impurity levels for the sulphate and chloride pigment processesa. et al., 1996; Jamieson et al., 1969; Smith et al., 2009). Rutile is the
Maximum impurity levelsb (wt%) stable phase, with both anatase and brookite being metastable. Anatase
is polymorphous with rutile and has a tetragonal structure based on
Sulphate process Chloride process cubic close packing of anions with each Ti ion surrounded by six O2–
ions where every O2– ion lies between three Ti4+ ions (Cromer and
Al2O3 1.0 1.0
Cr2O3 0.1 0.2 Herrington, 1955; Horn et al., 1972). The structure can be viewed as
V2O5 0.15 0.4 double chains of octahedra with adjacent staggered double chains.
Nb2O5 0.20 0.5 Compared with the more common rutile, anatase has a lower density, is
P2O5 0.20 0.5 not as hard and has a lower refractive index (Deer et al., 2013).
SiO2 1.0 1.0
Anatase can be transformed to rutile upon heating. Pure anatase
ZrO2 2.0 0.5
MnO 3.0 1.0 transforms irreversibly to rutile in air at ~600 °C (Ghosh et al., 2003;
CaO 1.0 0.2 Hirano et al., 2003), although the reported transition temperatures vary
MgO 1.0 0.5 in the range 400–1200 °C (Carp et al., 2004; Hirano et al., 2003;
U + Th < 100 ppm < 100 ppm
Shannon and Pask, 1965) owing to the use of different methods of
a
Data from Fisher, 1997; McCoy et al., 2011.
determining the transition temperatures, the raw materials, and heating
b
Critical impurities are shown in bold typeface. methods. The anatase to rutile transformation is not instantaneous
being a time dependent reconstructive reaction (Jamieson et al., 1969;
preliminary exploration and processing but are likely to be of great Shannon and Pask, 1965). This topic has been reviewed more recently
importance in the near future (Woodruff et al., 2017). by Hanaor and Sorrell (2011).
Impurity elements can determine the suitability of a feedstock for
the sulphate and chloride processes (Table 1). In the sulphate process, 2.2. Anatase chemistry
iron has a negative effect on the colour and brightness of the final
pigment, and if in the ferric state, it must be removed prior to pre- The mechanism by which a mineral accepts different cations or
cipitation of titanyl sulphate from the leach solution. Silica and zircon anions into the crystal lattice is largely governed by the ionic charge
impurities are not soluble in sulphuric acid, and so are easily removed and radius of the element being replaced (known as solid solution).
in the leach residue. Since there are limited opportunities to purify the Under normal conditions, ions with the same charge and a difference in
intermediate titanyl sulphate, the presence of transition metal elements radius of < 15% may enter the same site in a lattice (Bramdeo and
in the feedstock is of concern. Chromium, vanadium, copper, nickel, Dunlevey, 1999), although smaller ions are preferentially accepted
manganese and niobium can impart colour to the titania pigment and (Mason, 1966). Ions with different charges and similar ionic size may
must be kept to a minimum. Phosphorus levels also are kept to a also be accepted provided the overall charge balance is maintained (e.g.
minimum because phosphate ions impact the anatase to rutile trans- Fe3+ and Nb5+ incorporation via the coupled mechanism
formation during calcination of the pigment. In the chloride process, Fe3++Nb5+↔2Ti4+).
calcium and magnesium affect the operation of the fluidised bed be- A number of elements may theoretically replace Ti4+ in the TiO2
cause their chlorides have low boiling points, chromium and vanadium lattice, depending on temperature and pressure. Under most geological
impact the colour of the final pigment, and uranium, thorium and their conditions V, Fe, Cr, Sn, Mo, Mn, Bi, Nb, Ta and Sb have the potential to
radionuclide daughters lead to environmental concerns (Fisher, 1997; substitute into the lattice. However, cations with a higher charge and/
Lakshmanan et al., 2014; McCoy et al., 2011). Similar to rutile, it will or smaller radius than Ti4+ (Fe3+, Cr3+, Mo4+, Mn4+, Nb5+, Ta5+,
be necessary for any anatase concentrate produced for pigment pro- and Sb3+) are preferentially accepted (Bramdeo and Dunlevey, 1999).
duction, by either the sulphate or chloride routes, to meet these im- Aluminium and lead are both considered to have size differences (23
purity requirements. and 25% respectively) that should preclude substitution into the lattice
In this paper, processing conditions for anatase ores are reviewed although the small ionic size and high abundance of aluminium in most
with an aim of identifying those that may produce a feedstock suitable geological environments appears to favour inclusion.
for processing to titania pigment by either the sulphate or chloride Published anatase compositions show a broad variation in contained
routes. Although new potential deposits of anatase have been found in impurities. Trivalent aluminium and iron are common impurity ele-
Inner Mongolia and China, and anatase is known to be associated with ments with up to 0.55 wt% Al2O3 and 1.6 wt% Fe2O3 reported. As well,
leucoxene in Russian alkaline deposits, much of the published works on V, Sn and Ca often substitute into the structure (Bowles et al., 2011).
the processing of anatase ores are related to the Brazilian deposits of The relatively large amounts of Nb and Ta that are known to enter the
Minas Gerais. The lack of information relating to processing of anatase rutile structure are not common in anatase. Data for anatase from
ores from outside Brazil means that this review is limited to information Brazilian deposits reported by Bowles et al. (2011) indicate that im-
for Brazilian deposits with much of the data contained in examples in purity levels are low with iron being the major impurity at < 1.5 wt%
the patent literature, with most being for small laboratory scale tests. Fe2O3.
The patents describe processing conditions to beneficiate anatase ores
using mineral dressing techniques to produce an initial intermediate 2.3. Paragenesis of anatase deposits
grade concentrate followed by further processing using combinations of
heating and leaching treatments, often with the addition of a fluxing The low temperature conditions required for the formation, and the
reagent to assist in impurity removal. The suitability of these products relative instability of anatase, mean it is rarely found as a primary
as a feedstock for the sulphate and chloride routes to pigment is dis- mineral phase in geological environments (most igneous and meta-
cussed. morphic ore-forming processes occur at significantly higher tempera-
tures outside the anatase stability range). Instead, anatase is usually
formed in sedimentary environments where low temperature alteration
2. Properties of anatase processes cause breakdown of titanium-rich precursor mineral phases
prior to its crystallisation. Biotite, hornblende, titanaugite, titanite
2.1. Anatase structure (sphene) and other titanium-bearing silicate minerals are among the
less stable minerals in the weathering environment (Dryden and
Titanium dioxide exhibits eight polymorphs, of which the three Dryden, 1946). When these minerals break down, the contained TiO2

227
K.R. Barnard, et al.
remains and commonly forms exceedingly fine-grained anatase. Ag-
gregates of these fine-grained anatase minerals may form pseudo-
morphs of the precursor silicates (Valeton, 1972).
Residual deposits containing anatase (associated with alkaline ig-
neous rocks and carbonatites which are igneous rocks containing >
50% carbonate minerals) are important formations in tropical areas
(Kapustin, 1980). These are the products of intense weathering and the
source of the titanium-rich material exerts a strong control on the
chemical composition of the anatase formed. For example, anatase ores
derived from the weathering of carbonatites tend to have high levels of
radionuclides, alkaline earth metals, rare earth metals, phosphates, and
silica. In contrast, anatase deposits in weathered overburden above ti-
tanium-rich alkali igneous rocks (without carbonatite) do not have this
disadvantage and are thus placed more favourably for commercial de-
velopment. The anatase-bearing mineral assemblage of these deposits is
reconstituted in the weathering zone and purged of detrimental trace
elements. The volume of some weathered overburden deposits of the
alkaline igneous‑carbonatite type rivals those of large magmatic ilme-
nite deposits with the largest anatase deposits in the world (e.g. Tapira
in the Minas Gerais region of Brazil) is an example of this type of de-
posit.
3. Processing anatase ores
The following discussion on processing anatase ores uses data from
examples in the patent literature that describe processing conditions to
beneficiate anatase ores initially containing 25–35 wt% TiO2. Mineral
dressing techniques are used to produce a concentrate containing
around 65 wt% TiO2, called a mechanical concentrate. Approaches used
to upgrade this concentrate to over 90 wt% TiO2 are also discussed.
It can be expected that processing an anatase ore to achieve im-
purity levels acceptable for pigment production will be more difficult
than processing an ilmenite feedstock from a mineral sand deposit. The
extensive number of minerals present in an anatase ore, with significant
intergrowths between minerals, and the fact that impurity elements
may be distributed in several different minerals, are likely to make it
more difficult to eliminate specific impurity elements or to achieve a
selective separation of a mineral to achieve acceptable impurity levels.
Published patent results usually involve samples from Brazilian
carbonatite-derived anatase deposits in the states of Minas Gerais and
Goias. Most of the published information is for samples from the Tapira
deposit in Minas Gerais. This deposit is a phosphate deposit as well as
an anatase deposit with zones rich in phosphate minerals and zones rich
in titanium minerals. Capponi et al. (2009) reported that the deposit
can be grouped into four zones, from top down, being overburden with
a thickness of 30–55 m, very weathered rock with titania levels over
10 wt% TiO2 with a thickness of 25–35 m, weathered rock with the
highest phosphate concentration that is 25–30 m thick (TiO2 < 10 wt
%), and bedrock of pyroxenites and carbonatites.
Minerals identified by Chao et al. (1993) in Brazilian anatase ores
are listed in Table 2 and analytical data for anatase ores are given in
Table 3. Iron-containing minerals (magnetite and maghemite) and ti-
tanium-containing minerals (anatase) are the major components of the
ore. Phosphorus and most of the impurity elements are present in more
than one mineral and several minerals contain more than one impurity
element.
Paixao and De Mendonca (1979) gave typical analytical data for a
Brazilian anatase ore as 28 wt% TiO2, 38 wt% Fe (54.3 wt% Fe2O3),
1 wt% CaO, < 1 wt% MgO, 2 wt% P2O5 and 1 wt% SiO2 with a miner-
alogical composition of 18% anatase, 25% hematite, 2% ilmenite, 2%
limonite and < 1% apatite. Note that Paixao and De Mendonca (1979)
report hematite as being the major iron mineral in their sample while
Chao et al. (1993) report that magnetite and maghemite are the major
iron minerals in their sample. This is likely to be because the samples
were from different deposits, or from different zones within a deposit.
228
Hydrometallurgy 185 (2019) 226–237
3.1. Beneficiation of anatase ores to 65 wt% TiO2
3.1.1. Mineral dressing of anatase ores
Chao (1989) beneficiated an anatase ore containing 26.2 wt% TiO2
to a concentrate with 62.5 wt% TiO2. The ore was ball milled, and de-
slimed to remove −20 μm material. The de-slimed ore was then sub-
jected to wet magnetic separation at ~600 G, giving a TiO2 recovery of
77.4 wt%. Analytical data for the ore and concentrate in Table 3 con-
firm that the magnetic separation removed magnetic iron minerals,
while the de-sliming removed gangue aluminium silicate (clay) mi-
nerals (although the SiO2 assay is higher than expected). However, no
appreciable amounts of other elements were removed, in particular
phosphorus, vanadium, niobium, the rare earth elements, uranium and
thorium, as these impurity levels are similar or higher in the con-
centrate than in the ore.
Magalhaes (1981b) crushed an anatase ore containing 24.4 wt%
TiO2 to −125 mm, de-slimed it and ground the oversize to −3 mm.
After magnetic separation, a non-magnetic fraction containing 65.7 wt
% TiO2 was obtained. In a pilot plant trial treating 2.5 t/h of an anatase
ore containing 27.3 wt% TiO2, Magalhaes (1981a) obtained a product
with 58.1 wt% TiO2, at a recovery of 60 wt%, with low and medium
intensity magnetic separations after de-sliming ore crushed to about
19 mm. Only TiO2 assays were reported for this work.
Calcada et al. (2009) processed anatase ore containing 32.5 wt%
TiO2 from the Serra do Salitre deposit in Brazil to remove aluminium
silicate minerals and magnetite (Table 3). The ore was de-slimed, dried
and subjected to a low intensity magnetic separation. The concentrate
containing 57.45 wt% TiO2 was digested in concentrated sulphuric acid
as described later.
De Almeida et al. (1987) and Harben (1984) summarised a 10 year
technological research program by Brazilian company Companhia Vale
do Rio Doce (CVRD), now Vale, to produce an anatase product from
titanium-containing ore in the Tapira deposit. In a 15,000 t/year pilot
plant, a 22 wt% TiO2 ore was crushed to 15 mm, de-aggregated and
screened at 0.635 mm, de-slimed in a spiral classifier, and magnetically
fractionated to remove mainly magnetite. The dried product contained
56 wt% TiO2. Further grinding, screening and a magnetic separation
gave a non-magnetic product with 64 wt% TiO2. No other assay data
was given for this concentrate, nor were any recovery values in the pilot
plant reported. This mechanical concentrate was processed further as
described later.
In a patent assigned to Ishihara Mining and Chemical Co (1975),
anatase ore containing 33.3 wt% TiO2 and 28.5 wt% Fe2O3 was crushed
to 2.38 mm, de-slimed and given several stages of classification at
74 μm and 37 μm and gravity concentration with a jig and spirals to
produce a concentrate with 41.9 wt% TiO2 and 29.7 wt% Fe2O3 at a
recovery of 77.1 wt%. Note that no magnetic separations were utilised
as the aim of this processing was to remove aluminosilicate gangue
minerals, but not the iron minerals, as the concentrate was prepared as
a feed for smelting in a laboratory arc furnace. A titania slag containing
71.3 wt% TiO2, 13.7 wt% FeO and 1.2 wt% Fe was produced in la-
boratory smelting tests. A higher grade slag can be expected in a
commercial operation where better separation and removal of the
metallic iron is likely to be achieved.
De Matos et al. (2002) also reported processing an anatase ore
containing 26.6 wt% TiO2 and 43.2 wt% Fe2O3 to produce a con-
centrate suitable for smelting to a titanium-rich slag. The ore was dis-
integrated, crushed and screened at 6 mm, classified at 300 μm and then
subjected to a low intensity magnetic separation (800 G) with a wet
drum separator to remove coarse magnetite. The non-magnetic fraction
was attritioned and deslimed at 74 μm to remove clay minerals. Next,
the mechanical concentrate with 43.5 wt% TiO2 and 38.9 wt% Fe2O3
was calcined at 1000 °C with sodium carbonate (80 kg Na2CO3/t con-
centrate) for 1 h and then leached with 5 wt% HCl at 70 °C for 1 h. The
resulting leach residue assayed 50.4 wt% TiO2 and 41.1 wt% Fe2O3
with a titanium recovery of 92 wt% and an iron recovery of 84 wt%.
K.R. Barnard, et al. Hydrometallurgy 185 (2019) 226–237

Table 2
Mineralogical composition of Brazilian anatase ores.
Majora Minora

Ti minerals Anatase TiO2 Ilmenite FeTiO3

Perovskite CaTiO3
Schorlomite Ca3(Fe,Ti)2(Si,Ti)3O12
Ti-pyroxene e.g. Ti-biotite
Fe minerals Magnetite Fe3O4 Goethite FeO(OH)
Maghemite γ-Fe2O3 Hematite Fe2O3
Ilmenite FeTiO3
Schorlomite Ca3(Fe,Ti)2(Si,Ti)3O12
Al minerals Wavellite Al6(PO4)4(OH)6.9H2O Phlogopite KMg3(Si3AlO10)(OH)2
Crandallite CaAl3(PO4)2(OH)5.H2O Clay minerals Aluminium silicates
P minerals Wavellite Al6(PO4)4(OH)6.9H2O
Crandallite CaAl3(PO4)2(OH)5.H2O
Hydroxyapatite Ca5(PO4)3(OH)
Ca minerals Crandallite CaAl3(PO4)2(OH)5.H2O Perovskite CaTiO3
Hydroxyapatite Ca5(PO4)3(OH) Pyroxene e.g. diopside
Calcite CaCO3
Rare earth Rhabdophane (La,Nd,Y)(PO4).H2O Brockite (RE,Th)(PO4).H2O
Minerals Florencite CeAl3(PO4)2(OH)6 Aeschynite (Cs,Ca,Fe,Th)(Ti,Nb)2(O,OH)6
U and Th mineralsb Crandallite CaAl3(PO4)2(OH)5.H2O Zirkelite (Ca,Fe,Th)2(Zr,Ti,Nb)2O7
Gorceixite BaAl3(PO4)2(OH)5.H2O Rhabdophane (La,Nd,Y)(PO4).H2O
Goyazite SrAl3(PO4)2(OH)5.H2O Calzirite CaZr3TiO9
Florencite CeAl3(PO4)2(OH)6
Gangue minerals Vermiculite Mg11Al5FeSi11O42.40H2O
Quartz SiO2
Wavellite Al6(PO4)4(OH)6.9H2O
Amorphous phases
Pyroxenes
Clay minerals Aluminium silicates

a
Data from Chao et al. (1993).
b
As lattice substitutions, interstitials or in solid solution.

Table 3 the kaolin industry may be applicable to beneficiating an anatase ore.

Analytical data (wt%) for anatase ores, and mechanical concentrates. The isoelectric point (IEP) for anatase is reported to be 6.2 which
Reference Chao, 1989 Calcada et al., 2009 De Matos et al., 2002
suggests that cationic collectors could be suitable at alkaline pH values
and anionic collectors with acidic pH values.
Sample Ore Conc. Ore Conc. Ore Final Conc.a The mineralogy of Brazilian anatase ores in Table 2 indicates there
are numerous minerals present and so it is likely to be difficult to
TiO2 26.2 62.5 32.5 57.45 26.6 50.4
Fe2O3 55.6 16.1 49.1 13.5 43.2 41.1
achieve selective flotation of anatase from such ores. However, Paixao
SiO2 1.38 3.06 3.39 2.66 3.14 0.68 and De Mendonca (1979) reported the beneficiation an anatase ore
Al2O3 5.02 3.75 7.67 6.60 8.72 3.96 containing 28 wt% TiO2 by a combination of slime removal, controlled
P2O5 3.79 3.88 3.02 4.98 4.56 0.88 grinding and magnetic separation, to give a product with 60–65 wt%
CaO 0.46 1.16 0.95 2.41 0.44 0.18
TiO2. Flotation (conditions not reported) after grinding (size not spe-
MgO n.r. n.r. 0.92 0.21 0.85 0.71
MnO 1.85 0.49 0.49 0.33 n.r. 0.51 cified), increased the grade of the product to 80 wt% TiO2. A dis-
Cr2O3 0.57 0.29 n.r. n.r. n.r. n.r. advantage of the flotation product as a feed to the chloride route to
ZrO2 0.12 0.24 0.11 0.27 n.r. n.r. pigment was given as being its finer size as this may result in loss of
V2O5 0.50 0.54 n.r. n.r. n.r. n.r. mineral from the fluidised bed chlorinator. However, it may be an
Nb2O5 0.15 0.61 0.23 0.51 n.r. n.r.
advantage if this material was to be digested in concentrated sulphuric
BaO 0.71 0.60 n.r. n.r. 0.77 0.10
SrO 0.30 0.43 0.18 0.41 n.r. n.r. acid.
La2O3 0.32 0.49 0.38 0.56 n.r. n.r. Flotation of anatase ore with fatty acids requires an activator (such
CeO2 0.66 0.99 0.87 n.d. n.r. n.r. as calcium ions), but since it can be expected that the activator will also
Y2O3 0.02 0.05 n.r. n.r. n.r. n.r.
activate some gangue minerals, low selectivity is expected.
Nd2O3 0.36 0.43 n.r. n.r. n.r. n.r.
U (ppm) 50 85 n.r. n.r. n.r. n.r.
Furthermore, since Bulatovic (2010) has shown that fatty acids (tall oil)
Th (ppm) 340 455 n.r. 300 n.r. n.r. can float apatite, the use of fatty acids as collectors could increase
phosphorus levels in the floated product.
n.r. = not reported. Hydroxymates are a class of chelating chemicals that chemisorb on
a
Mechanical concentrate calcined at 1000 °C with Na2CO3 and leached with anatase and so do not require an activator. The successful flotation of
5 wt% HCl at 70 °C. anatase from kaolin with a hydroxymate collector has been reported by
Mathur (2002) and Yoon et al. (1992). The flotation procedure de-
The composition of the final concentrate (Table 3) was considered to be scribed was to disperse the kaolin ore, add the collector at pH 8–10, and
similar to commercial ilmenite concentrates and it was calculated that a float the anatase. Yoon et al. (1992) reported results for flotation in
slag with 82.5 wt% TiO2 and 10.0 wt% FeO could be produced from it. Denver flotation cells that showed that longer chain collectors were
more effective, giving higher recoveries of anatase, and that hydro-
xymate flotation was superior to a fatty acid flotation with lower re-
3.1.2. Flotation of anatase
agent additions than those for tall oil flotation. However, Assis et al.
Anatase is a major coloured impurity that must be removed from
(1996) reported that apatite floated better than anatase in a sample
kaolin clay deposits to produce a white product. Since anatase is re-
composed of 90 wt% apatite and 10 wt% anatase prepared using
moved from kaolin by flotation (Mathur, 2002), the conditions used by

229
K.R. Barnard, et al. Hydrometallurgy 185 (2019) 226–237

Fosfertil ore from the Tapira deposit. Likewise a sulphosuccinamate is
another collector type that may be useful for flotation of anatase and De
Barros et al. (2001) used a sulphosuccinate and a sulphosuccinamate to
produce phosphate concentrates from ores from the Tapira deposit.
Many other reagents, or mixtures of reagents, have been suggested
as being suitable for the flotation of titanium-containing minerals
(Bulatovic, 2010) but their selectivity with an anatase ore would need
to be determined. It is likely that some pre-concentration of apatite in
Tapira ore, as carried out by Paixao and De Mendonca (1979), will be
necessary before flotation can be applied.
3.2. Upgrading to over 90 wt% TiO2
Several patents report processing conditions to upgrade mechanical
concentrates of 50–65 wt% TiO2 to over 90 wt% TiO2. The conditions
include leaching with an acid or alkali under various conditions, either
directly using the concentrate, or after a roasting treatment under
oxidising and/or reducing conditions, with and without the addition of
fluxing agents. A magnetic separation often is used after a reducing
roast. The processing conditions are discussed in the following sections.
3.2.1. Leaching of the concentrate
Chao and Senkler (1991, 1992) reported leaching an anatase flo-
tation concentrate (−74 μm) containing 74.45 wt% TiO2, with 20 wt%
HCl at 90 °C for 2 h. After filtering and drying the product it was sub-
jected to a second leach with 10 wt% NaOH at 180 °C for 1 h under a
pressure of 8–10 atm, to give a product with 90.3 wt% TiO2. By rever-
sing the order of the leaching steps a final product with 94.95 wt% TiO2
was obtained. Analytical data in Table 4 for the concentrate and lea-
ched products indicate that acid leaching before the alkali leach re-
moved appreciable amounts of aluminium, phosphorus and calcium,
and some of the rare earths. When the caustic leach was applied first,
good removal of all the impurity elements, including uranium and
thorium, was achieved. Little zirconium or niobium were removed in
the leaches and phosphorus levels were higher when the caustic leach
preceded the acid leach (Table 4). It was found for most ores that pre-
roasting at up to 700 °C was not beneficial.
Chao et al. (1993) leached an anatase mechanical concentrate
containing 64.5 wt% TiO2 with 20 wt% HCl at 190 °C for 1 h in a
titanium-clad steel bomb at a pressure that varied from 13.8–34 bar.
The product contained 91.0 wt% TiO2. Assay data in Table 4 for the
concentrate and the acid leached product show good removal of all
impurity elements except for silicon, zirconium and niobium, and to a
lesser extent for phosphorus. A subsequent leach with hot 20 wt%
NaOH removed further silicon, aluminium and phosphorus without
appreciably increasing the titania content. Both leached products con-
tained low levels of uranium and thorium.
Pressure leaching was also used by Smith Jr and De Castro Sheldon
(2007). An anatase concentrate containing 60.6 wt% TiO2 was leached
with 35 wt% H2SO4 and 5 wt% FeSO4 (with an anhydrous acid/ore
weight ratio of over 0.5) at 160 °C for 5 h at a pressure of 3.4 bar. The
product was de-slimed to give a coarse product that contained 88.5 wt%
TiO2. The impurity elements removed were similar, but not to the same
extent, as that achieved by Chao et al. (1993) as shown in Table 4. The
fines from the pressure leach were considered to be a suitable feedstock
for a sulphate pigment process while the coarse product was upgraded
further to 93.7 wt% TiO2, as described below, and was a preferred
feedstock to the chloride pigment process.
3.2.2. Reductive roasting of the concentrate
Paixao and De Mendonca (1979) beneficiated an anatase ore con-
taining 28 wt% TiO2 to a mechanical concentrate with 75.6 wt% TiO2.
This concentrate, ground to −74 μm, was roasted at 750 °C for 1 h
under CO2, and then at 600 °C in a reducing gas mixture of 60% N2,
14% CO2 and 24% CO for 45 min. A magnetic separation of the roasted
product at 800 G gave a non-magnetic product of 79.3 wt% TiO2 with a
titania recovery of 94.3 wt%. It was leached with HCl (200 g/L) at
104 °C for 4 h and the assay data in Table 5 indicate an upgrade to
89.9 wt% TiO2, although little silicon and phosphorus, and only a small
amount of aluminium, were removed. However a subsequent wash with
2 wt% NaOH did remove phosphorus and a final product with 93.3 wt%
TiO2 was obtained (Table 5). Note that only a limited number of ele-
ments were assayed but it is expected that little zirconium or niobium
were removed.
Chao et al. (1993) subjected an anatase mechanical concentrate
containing 62.9 wt% TiO2 to a reducing roast with carbon (under a
covering of argon) at 1100 °C for 1 h. The roasted product was mag-
netically separated at 500 G and the non-magnetic fraction (~80 wt%

Table 4
Analytical data (wt%) for upgraded anatase mechanical concentrates produced by leaching.
Reference Chao and Senkler (1992) Chao et al., 1993 Smith Jr and De Castro Sheldon, 2007

Conditions Anatase conc. HCl 90 °C/NaOH NaOH 180 °C/HCl Anatase conc. HCl 190 °C HCl 190 °C/NaOH Anatase conc. H2SO4 + FeSO4 160 °C
180 °C 90 °C 90 °C

TiO2 74.45 90.3 94.95 64.5 91.0 91.0 60.6 88.5

Fe2O3 4.74 4.95 1.61 14.4 2.43 2.25 16.2 2.38
SiO2 1.03 0.83 0.49 2.26 2.37 1.15 1.53 1.41
Al2O3 2.97 0.10 0.00 4.70 0.55 0.45 6.20 0.74
P2O5 4.35 0.15 0.80 6.00 2.54 1.66 7.40 2.32
CaO 3.60 0.42 0.20 1.72 0.05 0.10 1.53 0.16
MgO 0.00 0.00 0.00 0.01 0.00 0.00 n.r. n.r.
MnO n.r. n.r. n.r. n.r. n.r. n.r. 0.71 0.11
Cr2O3 0.00 0.00 0.00 0.00 0.00 0.00 n.r. n.r.
ZrO2 0.37 0.41 0.37 0.42 0.47 0.40 0.78 0.82
V2O5 0.13 0.10 0.06 0.11 0.06 0.06 n.r. n.r.
Nb2O5 0.82 1.01 1.16 0.74 1.16 1.16 n.r. n.r.
BaO 0.28 0.17 0.05 0.43 0.08 0.08 0.98 0.23
SrO 0.21 0.10 0.00 0.36 0.00 0.00 0.64 0.06
La2O3 0.47 0.31 0.06 0.53 0.00 0.01 n.r. n.r.
CeO2 0.94 0.64 0.08 1.08 0.07 0.07 n.r. n.r.
Y2O3 0.03 0.01 0.00 0.05 0.01 0.01 n.r. n.r.
Nd2O3 0.35 0.23 0.08 0.45 0.00 0.00 n.r. n.r.
REETOT n.r. n.r. n.r. n.r. n.r. n.r. 2.10 0.48
U (ppm) 150 120 20 127 77 71 202 109
Th (ppm) 300 170 35 350 57 59 544 176

n.r. = not reported.

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K.R. Barnard, et al. Hydrometallurgy 185 (2019) 226–237

Table 5
Analytical data (wt%) for upgraded anatase concentrates produced by leaching after a reducing roast.a
Reference Paixao and De Mendonca, 1979 Chao et al., 1993 Mineracåo Vale Do Paranaíba S.A., 1980 De Almeida et al., 1987

Conditions Anatase conc. HCl 104 °C NaOH RT Anatase conc. HCl 170 °C Anatase conc. HCl reflux CVRD pilot plant

TiO2 75.6 89.9 93.3 62.9 92.1 78.1 97.3 89.0

Fe2O3 11.7 2.87 2.85 17.4 0.52 1.09 0.21 4.3
SiO2 0.52 0.48 0.46 1.66 2.22 1.09 0.30 1.5
Al2O3 2.88 1.50 1.41 2.83 2.80 1.04 1.04 2.0
P2O5 2.11 2.10 0.22 5.25 0.44 1.74 0.98 1.5
CaO 1.12 0.25 0.27 2.75 0.07 0.70 0.11 0.2
MgO 0.50 0.08 0.05 0.10 0 0.84 0.80 0.05
MnO n.r. n.r. n.r. 0.47 0.09 n.r. n.r. 0.15
Cr2O3 n.r. n.r. n.r. 0 0 n.r. n.r. 0.15
ZrO2 n.r. n.r. n.r. 0.43 0.36 n.r. n.r. 0.30
V2O5 n.r. n.r. n.r. 0.27 0.11 n.r. n.r. 0.15
Nb2O5 n.r. n.r. n.r. 0.80 1.20 0.67 n.r. 0.9
BaO n.r. n.r. n.r. 0.20 0.07 n.r. n.r. 0.04
SrO n.r. n.r. n.r. 0.24 0.01 n.r. n.r. 0.03
a
La2O3 n.r. n.r. n.r. 0.52 0.02 n.r. n.r.
a
CeO2 n.r. n.r. n.r. 1.09 0.08 n.r. n.r.
a
Y2O3 n.r. n.r. n.r. 0.06 0.01 n.r. n.r.
a
Nd2O3 n.r. n.r. n.r. 0.58 0 n.r. n.r.
b
U (ppm) n.r. n.r. n.r. 110 68 n.r. n.r.
b
Th (ppm) n.r. n.r. n.r. 400 39 n.r. n.r.

n.r. = not reported.

a
Total rare earth oxides was 0.5 wt%.
b
Th + U < 400 ppm.

TiO2 recovery) was leached with 20 wt% HCl under pressure at 170 °C Table 6
for 1 h to give a product with 92.1 wt% TiO2. Assay data for the product Analytical data (wt%) for leached anatase concentrates after roasting treat-
in Table 5 indicate that good impurity removal was achieved except for ments with the addition of borax and/or NaCl in the final roast.
silicon, aluminium, zirconium and niobium. Comparison of results for a Reference Smith Jr and De Castro Sheldon, Horta et al., 2007
HCl pressure leach of a mechanical concentrate without roasting that 2007
gave a product with 91.0 wt% TiO2 (Table 4) show that the reducing
roast increased iron and phosphorus removal but removal of silicon and Conditions Anatase Oxdn/ Fluxa Anatase Oxidn/ Fluxb
conc. HCl Oxidn/ conc. Redn/ Oxidn/
aluminium were lower. reflux HCl HCl HCl
In a patent assigned to Mineracåo Vale Do Paranaíba (1980), an reflux 105 °C 105 °C/n-
anatase concentrate (78.1 wt% TiO2) was sulphidised under an atmo- mag
sphere of H2S or SO2 at 500–1300 °C for up to 2 h. The sulphidised
TiO2 60.6 89.9 93.7 51.6 81.9 91.6
material was leached with 20–30 wt% H2SO4, or 20 wt% HCl, for up to
Fe2O3 16.2 2.01 1.77 26.3 13.3 7.62
3 h under reflux to remove sulphides (e.g. of iron and other impurity SiO2 1.53 1.85 0.89 0.86 0.48 0.35
elements) formed during the heating. The product was water washed Al2O3 6.20 0.63 0.06 5.74 0.47 < 0.15
and given a wet magnetic separation with a high field intensity P2O5 7.40 1.42 0.18 4.85 2.49 0.43
CaO 1.53 0.08 0.03 1.05 0.29 0.07
(7000–25,000 G). After roasting at 1000 °C for 1 h, and leaching with
MnO 0.71 0.11 0.08 n.r. n.r. n.r.
HCl under reflux for 1 h, a product of 97.3 wt% TiO2 was obtained ZrO2 0.78 0.74 0.82 0.41 0.92 1.07
(Table 5). Only a limited number of elements were assayed but the data Nb2O5 n.r. n.r. n.r. 0.71 1.17 1.36
did show that little aluminium, phosphorus or magnesium were re- BaO 0.98 0.08 0.12 n.r. n.r. n.r.
moved. SrO 0.64 n.d. n.d. n.r. n.r. n.r.
REETOT 2.10 0.10 0.29 n.r. n.r. n.r.
In a 15,000 t/year pilot plant operation by CVRD, an anatase me-
U (ppm) 202 93 60 > 150 > 150 87
chanical concentrate containing 64 wt% TiO2 was produced from an ore Th (ppm) 544 104 91 > 500 256 119
with 22 wt% TiO2 (De Almeida et al., 1987; Harben, 1984). This con-
centrate was upgraded further to around 80 wt-% TiO2 with a magne- n.r. = not reported.
tising roast in a fluidised bed, using a carbon-based gas, to free more
a
NaCl (10 wt%) was added to the final roast.
b
iron (as magnetite) and other impurities which were removed in mag- Borax (Na2B4O7.10H2O) and NaCl (11:4 with a total of 15 wt%) were
netic separations with low and medium strength separators. Perovskite, added in the final roast.
silica and phosphate impurities were removed from the non-magnetic
fraction with electrostatic separators and finally the conductors were when NaCl (10 wt%) was added before the calcination, the final pro-
leached with sulphuric acid and washed with water and a caustic soda duct assayed 93.7 wt% TiO2 (Table 6). While significant amounts of
solution. Leaching conditions were not given but an acid consumption silicon, aluminium, phosphorus, calcium, uranium and thorium were
of 90 kg/t concentrate was reported. The final product contained removed, little zirconium or niobium were and final iron levels were at
around 90.0 wt% TiO2 (Table 5). 2 wt% Fe2O3. Other useful additives were suggested to include NaOH,
Na2CO3, KCl, KOH and KCO3. Addition of NaF in the final leach was
claimed to improve the removal of iron, aluminium, uranium and
3.2.3. Roasting with addition of fluxing agents thorium. The final product (a synthetic rutile) was considered to be a
When the pressure leached product of Smith Jr and De Castro suitable feedstock for a fluidised bed chlorinator.
Sheldon (2007) containing 88.5 wt% TiO2 (Table 4) was heated in air at Horta et al. (2007) submitted an anatase mechanical concentrate
950 °C for 5 h, and leached with boiling 20 wt% HCl under reflux for containing 51.6 wt% TiO2 to oxidation in air at 500 °C for 30 min,
5 h, it was further upgraded to only 89.9 wt% TiO2 (Table 6). However,

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K.R. Barnard, et al. Hydrometallurgy 185 (2019) 226–237

followed by reduction in H2 (or other reducing gas) for 30 min. The sodium aluminates, silicates, vanadates and chromates (Ephraim and
product was given a wet, low intensity (800 gauss), magnetic separa- Jha, 2015; Jha et al., 2008). The iron and other impurity phases, but not
tion followed by a dry, high intensity (20,000 G), magnetic separation the sodium titanates, were removed by washing with water followed by
and a leach with 25 wt% HCl at 105 °C for 4 h. The leached product an aeration leach in acidic chloride solutions or a reducing leach with
contained 81.9 wt% TiO2 (Table 6). Further upgrading, to 91.6 wt% ascorbic and oxalic acids, both at 50–80 °C (Cooke et al., 2011). A final
TiO2, was achieved by roasting this product with borax acid wash with HCl gave products with up to 96 wt% TiO2.
(Na2B4O7.10H2O) and NaCl (11:4 with a total addition of 15 wt%) at Jha and Tathavadkar (2005) mixed an anatase concentrate con-
950 °C, in air for 1 h, leaching the calcine with 25 wt% HCl at 105 °C for taining 57.8 wt% TiO2 with an alkali carbonate (Na2CO3 or K2CO3), at a
4 h, followed finally with a high intensity magnetic separation. The carbonate:ore ratio of > 1:1, and alumina (20 wt%), and roasted the
assay data in Table 6 indicate good removal of all elements except mixture in air at 950 °C for 2 h. The calcine was leached with water at
zirconium and niobium, although the iron levels, at 7.6 wt% Fe2O3, as 80 °C for 40 min. The fines generated in the leach were removed and the
still very high. When NaF and amorphous SiO2 (2:1 with a total addi- coarse material was leached with 5 wt% HCl at 70 °C for 10 min to give
tion of 10 wt%) were added in an oxidising roast at 1100 °C, the addi- a final product with 88.4 wt% TiO2. When iron in the water washed
tion of sodium fluoride in the final acid leach was necessary to remove product was removed as Fe(OH)3 with a catalytic aeration at pH 4, an
the silica added as flux. The addition of sodium fluoride also resulted in acid wash with 15 wt% HCl at 40–80 °C for 2 h gave a product con-
increased removal of uranium and thorium from the material to levels taining 95.9 wt% TiO2 (Jha et al., 2009). Results obtained by Jha et al.
of 50 ppm U and 50 ppm Th, levels that should be acceptable to a pig- (2008) for similar treatments are given in Table 7. By controlling the
ment plant. roasting time, temperature and with optimised leaching conditions, the
De Freitas et al. (2007) submitted an anatase mechanical con- particle size of the anatase grains was retained and the product was
centrate containing 53.8 wt% TiO2 to calcination in air at 500 °C for suitable for chlorination in a fluidised bed chlorinator (Ephraim and
15 min, followed by reduction in H2 (or other reducing gas) for 5 min. Jha, 2015).
The product was cooled under nitrogen and given a wet, low intensity
(800 G) magnetic separation, followed by a dry, high intensity (10,000 3.3. Summary
G) magnetic separation and a leach with 25 wt% HCl at 105 °C for 4 h.
The leached product contained 87.7 wt% TiO2 (Table 7). When mix- Processing Brazilian anatase ores with mineral dressing techniques
tures of Na2SO4/Na2CO3/H3PO4 (45:43:12 with a total addition of of crushing and grinding, concentration and separation by classifica-
15 wt%) were added to this acid leached product, calcined at 1000 °C tion, gravity and magnetic separations, and flotation, usually results in
for 1 h, a second leach with 25 wt% HCl at 105 °C for 4 h, followed by a the removal of magnetic iron minerals and aluminium silicate gangue
magnetic separation, gave a product with up to 94.7 wt% TiO2. Good minerals. However, the results indicate that this beneficiation by con-
removal of all elements was reported, although iron levels were around ventional mineral dressing techniques to 65 wt% TiO2 cannot achieve a
2 wt% Fe2O3 in the final leached products. Note that zirconium and significant upgrade without loss of appreciable amounts of mineral,
niobium were not analysed. Levels for both uranium and thorium were with recoveries of 60–80 wt% being reported.
around 50 ppm in the final product. Further upgrading to over 90 wt% TiO2 requires acid and caustic
Jha and co-workers roasted titanium-containing minerals, including leaching steps. Leaching was often preceded by a heat treatment under
anatase, at 750–950 °C with the addition of sodium and potassium conditions that convert iron oxides in the sample to more magnetic
carbonates, bi‑carbonates, sulphates, bi-sulphates and hydroxides, and magnetite that can be removed in one or two magnetic separation steps.
alumina to form alkali metal titanates. The equilibrium phases formed Under the leaching conditions used, little dissolution of niobium and
when anatase was roasted with sodium carbonate and alumina were zirconium occurred, while good silicon removal required an alkali
sodium titanates (e.g. Na2TiO3 and Na4TiO4), sodium ferrite, and leach. The poor removal of niobium and zirconium may indicate that
these elements are substituted in the anatase lattice. Leaching alone was
Table 7 effective in lowering phosphorus levels, although final levels of 1–2 wt
Analytical data (wt%) for leached anatase concentrates after roasting treat- % P2O5 can still be expected in the leached products.
ments. The additions of several different reagent combinations as fluxing
agents, such as sodium or potassium salts (e.g. chlorides, sulphates,
Reference De Freitas et al., 2007 Jha et al., 2008
carbonates, bicarbonates, hydroxides) and borax, at levels of up to
Conditions Anatase Oxidn/ a
Flux Anatase ore Roasted/ Roasted/ 20 wt%, in the heating treatment assisted impurity removal with good
conc. Redn/ Oxidn/ aeration aeration removal of all elements, except zirconium and niobium in an acid leach.
HCl HCl leach leach/ In particular, the levels of silicon, aluminium, phosphorus, calcium,
105 °C 105 °C acid wash
magnesium, the rare earth elements, uranium and thorium in the lea-
TiO2 53.8 87.7 94.7 54.3 69.6 88.3 ched products were the lowest achieved in the upgrading treatments.
Fe2O3 23.4 5.56 < 2.00 14.9 8.8 5.42 Conditions necessary to remove niobium and some zirconium required
SiO2 2.15 0.72 0.56 3.85 0.80 0.60 additions of sodium or potassium salts (e.g. carbonates, bicarbonates,
Al2O3 5.98 1.58 < 0.15 6.84 1.16 1.16
hydroxides) in the heating step in amounts equal or higher than the
P2O5 5.31 3.11 0.75 7.65 1.01 1.01
Na2O n.r. n.r. n.r. n.r. 15.9 3.87 amount of concentrate. These treatments formed alkali metal titanates
CaO 0.97 0.25 0.10 2.13 0.35 0.35 that were insoluble in a subsequent leach while the impurity elements
MnO 0.81 0.23 0.05 0.33 0.19 0.19 phases were soluble. However, the products from these treatments
BaO 1.13 < 0.10 < 0.10 n.r. n.r. n.r. contained residual sodium from the additives which could be detri-
SrO 0.44 < 0.05 < 0.05 n.r. n.r. n.r.
ZrO2 n.r. n.r. n.r. n.r. n.r. n.r.
mental in subsequent processing to pigment.
Nb2O5 n.r. n.r. n.r. n.r. n.r. n.r.
La2O3 0.44 0.10 0.04 0.61 0.04 0.04 4. Conversion to pigment
CeO2 1.01 0.30 < 0.08 1.62 0.28 0.28
U (ppm) 124 > 150 45 n.r. n.r. n.r.
The two commercial processes for production of titanium pigment
Th (ppm) 359 213 53 n.r. n.r. n.r.
from titaniferous feedstocks, the sulphate and chloride processes, both
n.r. = not reported. have limits on specific impurity elements that may affect the processing
a
A mixture of Na2SO4/Na2CO3/H3PO4 (45:43:12 with a total addition of or properties of the final titania pigment (Table 1). The processing of
15 wt%) was added in the final roast. anatase ores discussed above generally resulted in an initial upgrade of

232
K.R. Barnard, et al.
the ore by mineral dressing techniques to a mechanical concentrate of
60–65 wt% TiO2. This concentrate was processed further by heating
and leaching treatments to > 90 wt% TiO2.
Assay data for mechanical concentrates containing 60–65 wt% TiO2
(Table 3) indicate these still contain high amounts of impurity ele-
ments, in particular phosphorus, niobium, silicon and aluminium, and
so are expected to require further processing before use as a pigment
feedstock. Ishihara Mining and Chemical Co (1975) reported smelting a
mechanical concentrate to produce a titanium-rich slag with 71.3 wt%
TiO2 that was considered to be a suitable feed to the chloride process,
although the impurity levels were still high.
The analytical data for products upgraded to over 90 wt% TiO2 in
Tables 4–7 indicate that, except for niobium and zirconium, and silicon
and aluminium in some samples, the products should meet the re-
quirements for impurity levels in chlorination feedstock given in
Table 1.
It should be noted that, with any heat treatment above say 700 °C, it
can be expected that the anatase will be converted via solid-state re-
arrangement to rutile, similar to what occurs during ore formation and
in pigment production. This is likely to be a disadvantage if the up-
graded product is to be digested in sulphuric acid because rutile is less
soluble than anatase (Sinha, 1979). Also, with increasing heating times,
the rutile is likely to become more crystalline, have fewer defects,
making it even less soluble in sulphuric acid (Sinha, 1979).
4.1. Sulphate process
Rutile generally is considered to be insoluble under the conditions
of the sulphate process used for ilmenite, and it has been shown that the
digestion of roasted Murray Basin ilmenite samples from southeastern
Australia decreased as the rutile content of the samples increased.
However, there were indications that fine rutile (−10 nm) that formed
during the roasting treatment did dissolve to some extent under con-
ditions designed to simulate the sulphate digestion process (Fisher-
White et al., 2007). Consistent with this observation are reports that
fine grinding of anatase can increase its solubility in sulphuric acid.
Bade et al. (1971) digested finely divided rutile in concentrated sul-
phuric acid at 220–300 °C to form solid titanyl sulphate, and as well it
has been reported that mechanical activation (very fine milling) to alter
the crystal lattice structure of the rutile (to form non-stoichiometric
rutile, TiO2-x) enabled it to be dissolved in sulphuric acid in the same
way as ilmenite (Gock and Jacob, 1980).
Vorobeychik et al. (1979, 1983) examined the impact of mechanical
activation upon the leaching properties of altered ilmenite, rutile,
anatase and leucoxene. With increasing activation time the titanium-
containing minerals became more X-ray amorphous, but beyond a
certain time, the surface area did not increase, and in several instances,
decreased. For a leucoxene concentrate, the dissolution of titanium
increased from 29.3 wt% prior to milling to values in excess of 97 wt%
after milling. Details for the leaching step were not given. Dissolution of
titanium was generally lower with rutile and anatase in 87.5 wt% sul-
phuric acid, and only started to increase as the mineral became more
amorphous.
Leucoxene concentrates, containing about 90 wt% TiO2, are gen-
erally a mixture of pseudorutile and rutile. Their solubility in sulphuric
acid has been increased with a carbothermal reduction to form an an-
osovite phase (Ti3O5). For example, when Alekseev et al. (1993) roasted
a leucoxene concentrate in a graphite crucible (i.e. under reducing
conditions) at 1200–1350 °C for 20–150 min, the titanium oxides were
reduced to anosovite and, after milling to −75 μm, it had a higher
solubility in sulphuric acid. Similarly, it has been claimed that the re-
duction of leucoxene concentrate with petroleum coke at 1100–1150 °C
for 50–60 min, followed by sulphation with oleum (19–24 wt% free
SO3) at 150 °C for 50–60 min and leaching in water at 90–95 °C, were
effective for the dissolution of titanium (Maltsev and Radionov, 2010).
Use of a solid to liquid ratio of at least 1:5, and preferably 1:10, enabled
233
Hydrometallurgy 185 (2019) 226–237
the leaching of titanium to achieve levels of 97.8–98.0 wt% and
96.3–96.5 wt% after sulphation for 12 h with oleum and concentrated
sulphuric acid, respectively (Maltsev et al., 2010). A similar car-
bothermal reduction of anatase may increase its acid solubility.
Dvegubskii and Goryachev (1991) added anhydrous calcium sul-
phate to a leucoxene concentrate and digested the product with 70 wt%
or 92.5 wt% H2SO4 at 240 °C for 1–2 h, a temperature and time much
lower than necessary without addition of calcium sulphate. Extractions
of 93.5–94.1 wt% for Ti and 90–92 wt% for Ta and Nb were reported.
The additions of calcium sulphate (lime basis) and sulphuric acid were
0.70–0.76 t and 10.1–13.5 t per tonne of raw material, respectively.
Alekseev et al. (1996) added calcined limestone or perovskite and a
reducing agent (e.g. coke, petroleum coke) to a leucoxene concentrate
and roasted the mixture at optimum temperature of 1400 °C for 40 min.
After cooling and milling to −75 μm, the slag product was digested
with concentrated sulphuric acid at 200 °C for 1.5 h, cooled and lea-
ched. The degree of degradation of the slag was 93.5 wt% and 98.0 wt%
with the addition of 0.47 parts of lime and 5.84 parts of perovskite,
respectively, compared with 89.4–93.1 wt% without the addition of the
calcium compounds. Heating anatase with calcium compounds could
also increase its solubility in sulphuric acid.
The patent application of Pretorius (2001) describes a sulphation
method claimed to be suitable for industrial application to titanium-
containing materials generally. This process involved mixing −25 μm
material with 98 wt% sulphuric acid and the use of furnace tempera-
tures up to 600 °C, notwithstanding that sulphuric acid boils at 337 °C
and starts to decompose to H2O and SO3 above 300 °C. Typically,
however, the product temperature was 240–320 °C over about six hours
after which, the crust temperature was allowed to rise to 450 °C to re-
move any excess sulphuric acid (dead burn) before the furnace was
turned off. The gases generated during dead burning can be recycled.
The final cake was leached to remove the soluble sulphates and/or to
bring the titanium into solution.
Calcada et al. (2009) removed aluminium silicate gangue minerals
and magnetite from an anatase ore from Serra do Salitre to produce a
concentrate containing 57.45 wt% TiO2. This concentrate was milled to
−100 mesh (−150 μm) and digested in concentrated sulphuric acid
(concentration not specified) at 300 °C for 5 h. The resulting mass was
contacted with water at 90 °C for 2 h to produce liquor with 110–120 g/
L Ti and a free acidity of 1.33 mol/L with a titanium extraction of
94.5%.
Chaves (1992) described a process for the treatment of an anatase
concentrate containing 92.2 wt% TiO2, 1.61 wt% Fe2O3, 0.15 wt% P2O5
and 0.85 wt% Nb2O5 to bring the titanium into a black liquor with
subsequent treatment similar to that used in the ilmenite sulphate
process to produce titania pigment. The upgraded anatase concentrate
was ground to −44 μm and heated at 215 °C with sulphuric acid for
30 min. The sulphated cake was dissolved in water and sufficient scrap
iron was added to produce black liquor containing 200 g/L TiO2, 5 g/L
ferrous sulphate expressed as Fe2O3, 0.25 g/L P2O5, 1.4 g/L Nb2O5 and
traces of other impurities, including chromium and vanadium. Overall
titanium solubilisation by this approach was 95.8 wt%. A comparison of
the leach liquor composition with that described by Calcada et al.
(2009) is given in Table 8.
The higher levels of impurity elements in the black liquor from the
digestion of these anatase concentrates is likely to result in a con-
taminated titanyl sulphate being precipitated from the liquor. Recovery
of pure titanium species and the elimination of undesirable trace ele-
ments may be better achieved using solvent extraction techniques.
4.1.1. Titanium recovery by solvent extraction
The results of Calcada et al. (2009) and Chaves (1992) indicate that
digestion of an anatase concentrate with sulphuric acid can generate a
black liquor with a high titanium concentration (110 g/L Ti). In con-
trast most titanium solvent extraction studies have been conducted with
liquors obtained from ilmenite, titanomagnetite or bauxite red mud
K.R. Barnard, et al. Hydrometallurgy 185 (2019) 226–237

Table 8 SO3-H2O system (Baillon et al., 2008; Beukenkamp and Herrington,

Analytical data for two anatase concentrates (wt%) and the sulphuric acid leach 1960; Nabivanets, 1962; Szilágyi et al., 2009; Zhang et al., 2016).
liquor compositions (g/L) obtained from them. Certainly the nature of the species formed not only impacts the ability
Sample Anatase concentrate Digestion leach liquor to extract titanium but determines the amount of acid co-extracted. The
review of Reddy and Saji (2002) also discusses the impacts of acid
Reference Calcada Chaves, Calcada et al., Chaves, 1992 strength and compares the effectiveness of organophosphorus ex-
et al., 2009 1992 2009
tractants for titanium typically in the presence of impurities derived
Conditions Sulphation, Sulphation, 300 °C from the processing of ilmenite or other high iron-content titania
300 °C Water Water leach, 70 °C sources.
leach, 70 °C The solvent extraction of high strength titanium-containing liquors
Expt.b Calc.c was undertaken by Watanabe et al. (1991) who used TOPO and octyl
TiO2 57.45 92.2 196a 200 200 dioctylphosphinate to extract 94.1% Ti from a primary leach solution
Fe2O3 13.5 1.61 40.6 5.0 4.03 (PLS) containing 87.5 g/L TiO2, 28.6 g/L Fe and 780.6 g/L H2SO4 in
SiO2 2.66 6.68 3.68 n.r. 3.53 three primary extraction stages and 99.6% from the raffinate in three
Al2O3 6.60 0.51 18.3 n.r. 0.29 secondary extractions stages. There was some (15.5%) co-extraction of
P2O5 4.98 0.13 12.4 0.25 0.20
sulphuric acid in the primary extractions, with small (< 0.1%) co-ex-
Na2O 2.41 0.06 2.48 n.r. 0.15
CaO 0.21 0.01 0.01 n.r. 0.02 tractions of other elements. Six stages of stripping were employed to
MnO 0.33 0.16 0.49 n.r. 0.45 recover 99.6% Ti and generate a liquor of composition 191.9 g/L TiO2,
ZrO2 0.27 0.47 0.73 n.r. 1.24 421.4 g/L H2SO4, 8 mg/L Fe and 7 mg/L Cr. The work was, however,
Nb2O5 0.51 0.68 2.22 1.4 1.70
silent on the fate of Nb during solvent extraction though the Nb2O5
La2O3 0.56 0.05 2.08 n.r. 0.15
CeO2 n.r. 0.05 n.r. n.r. 0.16 content of the PLS was 2.9 g/L and it is expected this was co-extracted
U (ppm) n.r. n.r. n.r. n.r. n.d. with the titanium.
Th (ppm) 300 n.r. 400 n.r. n.d. A simulated ilmenite leach liquor containing ~78 g/L Ti, ~35 g/L
Fe and ~90 g/L sulphuric acid was extracted with Cyanex 923 (a
n.r. = not reported.
a
mixture of C6 and C8 trialkylphosphine oxides) in kerosene giving
The elemental data reported has been converted to oxides.
b 78.5% titanium extraction with 4% iron co-extraction while allowing
Experimental data.
c reasonable extraction and phase disengagement times to be achieved
Calculated from upgraded concentrate composition with 95.8% Ti extrac-
tion to give 200 g/L tenor. Assumes 95 wt% extraction of all other elements (Hao et al., 2012). This study also noted that it was necessary to de-
except Si at 30 wt%. crease the liquor concentration and increase its acidity to enable a ti-
tanium extraction of 96% with 7% iron co-extraction. Iron co-extraction
sources containing titanium at concentrations typically below 10 g/L Ti could be reduced to 1% under nitrogen atmosphere with a significantly
but more normally below 5 g/L Ti. The focus of this section is upon the reduced extraction time. Although stripping with low strength sul-
solvent extraction of titanium from high concentration liquors. phuric acid (1.7 wt%) was fast, the study indicated that multiple
Sole (1999a) reviewed the solvent extraction of titanium from sul- stripping stages were required and that there was potential for titanium
phate solutions and concluded that although di-2-ethylhexylphosphoric hydrolysis to occur given the low acidity of the strip liquor.
acid (DEHPA), and preferably tri-n-octylphosphine oxide (TOPO), were The use of Cyanex 923 with a modifier (e.g. 5% diisobutylketone)
suitable extractants, the extraction kinetics are slow. Laboratory (Sole, was shown to enrich titanium from feed solutions containing 32–34 g/L
1999b) and mini-plant (Sole et al., 1999) work with liquor from a Ti with extraction efficiency of ≥97.8% into the loaded organic phase
sulphuric acid leach of a titaniferous magnetite indicated that reason- relative to other impurities such as Fe, V and Zn (with no uptake of Cr,
able titanium extraction could be achieved with 10 vol% TOPO in an Mn, Ni and Mg) compared with the organic without modifier (Roche
aliphatic diluent, but titanium stripping was poor. Considerable co- et al., 2004). Extraction was undertaken for 45–60 min at 50 °C using an
extraction of iron also occurred. As the extraction kinetics were ex- organic phase to aqueous phase ratio (O/A) between 2/1 and 4/1, and
tremely slow this is potentially a severe limitation for a commercial followed by 15 min settling. For bench test work, the loaded organic
operation. was stripped with water for 60 min at 50 °C using a range of O/A be-
Da Silva et al. (2008) confirmed that high titanium extraction tween 1/3 and 30/1, followed by 20 min settling. The stripping effi-
(99.4% with ~16% Fe(III) co-extraction) could be obtained with ciency at O/A of 1/1 was 65%. It was noted that titanium hydrolysis
DEHPA over a long period (two steps of 8 h each) from a liquor con- occurred when the O/A was low (1/3). When the process was piloted
taining 25.5 g/L Ti. This study also demonstrated that the co-extracted with a single extraction stage and two stripping stages, the acidity of the
Fe(III) could be efficiently scrubbed with ~1% titanium loss and that strip liquor was consistent with significant co-extraction of sulphuric
titanium stripping with 50 g/L ammonium fluoride was both rapid and acid with the titanium.
efficient (96.6%). Subsequent work by Lasheen et al. (2012) demon- When the solution generated by Calcada et al. (2009) of composi-
strated that the acidity of the titanium-containing solution impacted tion given in Table 8 was diluted by 50% with water and employed as
extraction with DEHPA, that the use of a modifier was beneficial for solvent extraction feed, the purified organic, 2-ethylhexyl hydrogen-2-
acid stripping of loaded iron and that sodium carbonate was a more ethylhexyl phosphonate (PC88A), octanol and a tertiary amine were
efficient stripping agent for titanium than either sodium or ammonium demonstrated to give the greatest separation of titanium from iron.
fluoride. Fontana et al. (2005) also noted sulphate solution acidity After scrubbing with 4.5 M sulphuric acid, the loaded organic was
impact upon titanium extraction, and Seyfi and Abdi (2009) also re- stripped with ammonium fluoride acidified to pH 4 for 5 min and
ported improved titanium stripping kinetics using sodium carbonate thereafter hydrolysis with ammonia enabled the recovery of a purified
and a combination of sulphuric acid with hydrogen peroxide. titanium oxide hydrate.
That solution acidity from either sulphuric, or hydrochloric acid,
impacts titanium extraction was first overviewed by Kislik and Eyal 4.1.2. Impurity removal by solvent extraction
(1993) who proposed suitable families of extractants according to the The major impurities in the liquor from the digestion of an anatase
titanium species present. The behaviour the various extractants when concentrate upgraded to over 90 wt% TiO2 are likely to be niobium and
applied to sulphate solutions, for example, is dictated by the nature of phosphorus. The separation of niobium (and tantalum) from titanium is
the titanium complexes that have been reported to form in the TiO2- generally conducted in the co-presence of fluoride with sulphuric acid
(Zhu and Cheng, 2011) though it has recognised for some time that the

234
K.R. Barnard, et al.
addition of either HCl or HF to sulphuric acid solutions is necessary to
obtain high niobium extraction and separation (Bonsack, 1971). In the
absence of fluoride, Zaonegina et al. (1988) claimed the combined use
of tributyl phosphate (TBP) and tertiary amines with three extraction
stages removed 90–93% of the niobium from liquors derived from the
sulphation and subsequent water leaching of a perovskite concentrate
containing 102–141 g/L TiO2, 900–1000 g/L H2SO4 and 2.4–3.3 g/L
Nb2O5. Thus the purified liquors still had estimated contents of
170–330 mg/L Nb2O5. Fourcot and Sabot (1995) proposed the use of
phosphorus-based organics and provided examples that employed di-
butylbutylphosphonate (DBBP) as the extractant with multiple stages
for titanium and niobium extraction (8), scrubbing (6), washing (12),
separation (15) and recovery of niobium (2), applied to solutions con-
taining much lower niobium tenors. The examples indicate the gen-
eration of purified titanium-containing liquors with compositions of
120 g/L Ti, 32 mg/L Nb from feed containing 152 g/L Ti and 130 mg/L
Nb, and 143 g/L Ti and 35 mg/L Nb from feed containing 136 g/L Ti
and 115 mg/L Nb.
The issue of phosphate removal from black liquors does not seem to
have been addressed and it was shown in the work of Calcada et al.
(2009) that significant phosphorous (and niobium) follow with the
extracted titanium to end up in the purified TiO2 product.
4.2. Chloride process
Laboratory chlorination tests to determine the mechanism of the
chlorination of rutile have been reported (Dunn, 1979; Morris and
Jensen, 1976; Youn and Park, 1989) as has the application of the
conditions in a commercial plant (Lee, 1991). Since rutile concentrates
are sought after as a feedstock for the chloride process to titania pig-
ment due to their high TiO2 content, upgraded anatase concentrates
also should be suitable. Yang and Hlavacek (1998) have shown that
anatase can be chlorinated to produce titanium tetrachloride under the
same conditions as used for rutile and that the rate was slightly faster
than rutile at 1000 °C.
A major requirement on concentrates for the chloride process is the
level of impurities that can affect processing and consume chlorine. It is
expected that upgraded anatase concentrates with over 90 wt% TiO2
would be an acceptable feedstock for chlorination (Smith Jr and De
Castro Sheldon, 2007). A leucoxene-quartz concentrate (containing
both rutile and lesser anatase) produced from the Yaregskii oil‑titanium
field containing 49.5 wt% TiO2 and 45.2 wt% SiO2 appears to be an
exception to this conclusion since quartz is resistant to chlorine. The
recent study of Zanaveskin et al. (2016) demonstrated that hydro-
thermal activation of the concentrate using sodium hydroxide leached
some of the SiO2, Al2O3 and K2O content, creating channels that en-
abled better access of reagents during chlorination, enhancing the re-
covery of Ti, V, Nb and Ta. This novel process was proposed to re-
present a process that would enable development of the deposit.
A further requirement of a synthetic rutile for the chloride feedstock
is that its size should be > 115 μm to prevent blow-over and loss from
the fluidised bed reactor (McCoy et al., 2011). In many of the treat-
ments noted above, the anatase was ground prior to treatment which
could limit their suitability for the chloride process, but make them
acceptable for the sulphate process. Agglomeration of the titanium-
containing products, or the utilisation of a fluidised bed reactor that is
able to recover and recirculate the titanium fines, may be necessary.
Research is required to determine appropriate conditions. Reeves and
Reeves (1997) listed potential technology changes for the chloride
process, one being that anatase concentrates will be used in some form.
Anatase still is not widely used as a feedstock for the chloride route.
5. Conclusions
Anatase, with a similar TiO2 content to rutile, can be expected to be
a suitable feedstock for processing to titania pigment. However,
235
Hydrometallurgy 185 (2019) 226–237
processing an anatase ore to obtain a satisfactory anatase concentrate is
likely to be difficult due to significant intergrowths between minerals,
the numerous minerals present, and the fact that impurity elements
may be distributed in several different minerals. While grinding an
anatase ore to liberate the minerals, and then classification and mag-
netic separations to remove aluminium silicates and magnetite, can
yield a mechanical concentrate with 60–65% TiO2, this product is un-
likely to be suitable as a feedstock for either the sulphate or chloride
routes to pigment due to the high levels of impurity elements. Further
upgrading would be necessary to remove these impurity elements.
Upgrading of an anatase mechanical concentrate to over 90% TiO2
was often preceded by a heating treatment under conditions which
converted iron oxides in the sample to magnetite that was removed
with a magnetic separation before acid and caustic leaching steps to
remove other impurity-containing minerals. Good silicon removal re-
quired an alkali leach, but little zircon and niobium were removed. The
addition of sodium fluoride in the leach was reported to assist in the
removal of radionuclides from the sample.
The addition of fluxing agents, such as sodium or potassium salts,
borax, amorphous silica or sodium fluoride, in amounts up to a total of
20 wt%, in a heat treatment generally resulted in good removal of all
impurity elements except niobium and zirconium in a subsequent acid
leach. While impurities were removed, the products contained residual
sodium (or potassium) from the additives.
Digestion of anatase concentrates in 90% H2SO4 at temperatures of
250–300 °C has been reported. Mechanical activation can be expected
to be beneficial for the digestion of anatase. However, high impurity
levels in the digestion liquors may require the use of solvent extraction
to recover high grade titania.
Anatase concentrates upgraded to over 90% TiO2 have generally
been considered to be suitable for conversion to pigment by the
chloride process. However, as well as the requirement for low impurity
levels the process also has limits on the size of the feed. Some treatment
methods to produce high grade anatase concentrates may not meet this
requirement as the material is ground to < 100 μm for the treatment.
This finer size is expected to be advantageous for the sulphate process
in which fine grinding is beneficial for the dissolution of rutile and
anatase in sulphuric acid.
Acknowledgements
This work was supported by CSIRO Mineral Resources and Iluka
Resources Limited. Discussions with Warren Bruckard on the flotation
of anatase, and the assistance of librarians in CSIRO in obtaining nu-
merous patents and other publications for this review, are gratefully
acknowledged. Inna Donaldson is thanked for her assistance in trans-
lating articles written in Russian.
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