processes

Article
Mechanism, Thermodynamics and Kinetics of Rutile
Leaching Process by Sulfuric Acid Reactions
Anastasiia V. Dubenko 1 , Mykola V. Nikolenko 1 , Eugene V. Aksenenko 2 ,
Andrii Kostyniuk 3, * and Blaž Likozar 3,4
1 Faculty of Chemical Technologies and Ecology, Ukrainian State University of Chemical Technology, Gagarin
Avenue 8, 49005 Dnipro, Ukraine; [email protected] (A.V.D.); [email protected] (M.V.N.)
2 Department of Electrochemistry and Adsorption on Mineral Sorbents, Institute of Colloid Chemistry and
Chemistry of Water, Vernadsky Boulevard 42, 03680 Kyiv, Ukraine; [email protected]
3 Department of Catalysis and Chemical Reaction Engineering, National Institute of Chemistry, Hajdrihova 19,
1001 Ljubljana, Slovenia; [email protected]
4 Faculty of Chemistry and Chemical Technology, University of Ljubljana, Večna pot 113,
1000 Ljubljana, Slovenia
* Correspondence: [email protected]




Received: 27 April 2020; Accepted: 25 May 2020; Published: 27 May 2020


Abstract: Rutile decomposition by sulfuric acid, including the formation of two salts, Ti(SO4 )2 /TiOSO4 ,
is thermodynamically modelled. It is shown that TiO2 can spontaneously dissolve in H2 SO4 solutions.
However, titania is considered as an inert (ballast) phase component of titanium-containing raw
materials due to the decelerated separate nature of such chemical transformations. It is concluded
that the hampered related kinetics of dissolution can be attributed to the lability of Ti(IV) cations/the
specific engineered features of the hierarchical crystalline structure. It is suggested that the breaking
of Ti–O–Ti bonds without additional mechanical strains in crystal lattice geometry becomes more
advantageous when smaller negative anions/fluoride ions can be used. The analysis of sulfate-fluoride
extraction leaching of titanium confirmed that a decrease in the Gibbs energy in the presence of F
occurs. It is indicated by kinetic research studies that the addition of corrosive sodium reagent (NaF)
reduces the activation by 45 kJ/mol, which results in intensification. A mechanism is proposed for the
interactions involving the Ti–O–Ti cleavage on the surface/the H2 SO4 -induced Ti dioxide degradation
on the sites of defects. Moreover, F acts as a homogeneous/heterogeneous bifunctional catalyst.

Keywords: altered ilmenite; titanium dioxide; rutile; sulfuric acid; fluoride ions; equilibrium Gibbs
free energy; thermodynamic parameter evaluation; homogeneous–heterogeneous catalysis; chemical
kinetics; leaching

1. Introduction
Currently, the global yearly production of titanium dioxide is approximately 6 million tons,
and its demand grows continuously by an average of 2.5% per year [1]. Ilmenite is a widespread
raw material for the production of titanium dioxide by both the chloride [2–4] and sulfate methods.
Sulfuric acid leaching of mineral rocks and concentrates containing titanium is a common method
for the production of a pigment titanium dioxide. Presently, ways to intensify this leaching method
are sought for using three activation methods: mechanical, thermal and chemical. The mechanical
activation of raw materials significantly increases the rate of dissolution of solid minerals, as reported
in a number of works [5–13]. It was shown in several publications that the mechanical dispersion
of raw material can either change or remain constant, depending on various factors—among them,
the ore grinding method (“dry” or in a solution medium), different process duration, etc.

Processes 2020, 8, 640; doi:10.3390/pr8060640 www.mdpi.com/journal/processes

Processes 2020, 8, 640 2 of 15

Studies investigating the thermal activation of raw materials have shown that the degree of
titanium extraction increases with an increase in temperature [14–17]. The degree of titanium leaching
rapidly increases with an increase in temperature, with a maximum value at 160 ◦ C during processing
of a titanium-containing feed [17].
At higher temperatures, titanium salt undergoes hydrolysis in the solution, which results in the
decrease in its content therein. In the reaction mixture, at 200 ◦ C, agglomerates are formed and cannot
be leached. These agglomerates are presumably the products of the polymerization of hydrolysis
forms of titanium. The formation of agglomerates insoluble in 5% sulfuric acid was observed in a few
works [18,19].
Nowadays, the chemical activation of raw materials with sulfuric acid solutions is also debatable.
The influence of the concentration and mass module of sulfuric acid on the decomposition of ilmenite
was investigated repeatedly [8,15,20–28]. The degree of titanium extraction into solution was found to
increase with increasing sulfuric acid concentration [18]. However, when using H2 SO4 solutions with
a concentration above 14 M, reduced efficiency of the leaching process was observed. According to
the literature, maximum efficiency was found to be within a sulfuric acid concentration of 9–17 M.
This can be attributed to the fact that ore raw materials taken from different deposits have different
chemical compositions and, therefore, different optimal leaching process conditions.
Most of the works have dealt with the processing of ilmenite concentrates with FeTiO3 content
above 90%, which are almost completely leached by concentrated sulfuric acid. However, the content
of TiO2 can increase in the geochemical transformation (leukoxenization) of ilmenite ores with the
formation of the so-called altered ilmenite. The content of ilmenite FeTiO3 decreases and the proportion
of pseudorutyl Fe2 Ti3 O9 increases due to the removal and oxidation of ferrous iron to the trivalent
state in ore rocks. The rutile content can exceed 65 wt% in altered ilmenites. It was experimentally
proved that the leaching degree of titanium from altered ilmenites barely reaches 15% with a leaching
process duration of 5 h, even when 90–95% sulfuric acid solutions are used [29]. Leaching with sulfuric
acid cannot ensure complete recovery of titanium from this ore due to the chemical inertness of rutile
with respect to concentrated sulfuric acid. The undissolved rutile in the composition of the sludge
after processing of ilmenite ores moves into dumps, which leads to accumulation of waste products in
the production area, environmental degradation and losses of the target component (titanium).
In our opinion, it is possible to improve the technological parameters of sulfuric acid leaching of
titanium from the rutile fraction of altered ilmenites by adding a fluorinating reagent to the reaction
mixture. As is known, fluoride ions can bind titanium (IV) ions to fairly strong complexes. Fluorides
are assumed to be able to “activate” a rutile surface due to the destruction of its crystal lattice and,
thereby, fluorides shift the equilibrium of the reaction of rutile dissolution with sulfuric acid towards
the formation of soluble titanium salts. Obviously, the fluoride ions will be bound to hydrogen ions in
acidic media, because hydrogen fluoride is a weak acid and, due to its volatility, HF must continuously
evaporate from the reaction mixture. The efficiency of such sulfate-fluoride processing of ilmenite
ores is expected to be determined by the ratio of the rates of at least three processes: the diffusion
of hydrogen fluoride molecules into the reaction zone on the surface of rutile particles, the chemical
decomposition of titanium dioxide due to interaction with sulfuric and hydrofluoric acids, and the
evaporation of HF from the reaction mixture at the interface between the reaction mixture and air.
Fluorination of ilmenite ores is described in the literature [30–35]. Fluorination reactions with
F2 [31] are governed by successive substitution of oxygen atoms by fluorine atoms on the surface of
ore particles in a temperature range of 298–1800 K.

TiO2 + F2 = TiOF2 + 0.5O2 , (1)

TiOF2 + F2 = TiF4 + 0.5O2 , (2)

FeO + 1.5F2 = FeF3 + 0.5O2 , (3)

SiO2 + F2 = SiOF2 + 0.5O2 , (4)

Processes 2020, 8, 640 3 of 15

SiOF2 + F2 = SiF4 + 0.5O2 . (5)

The literature also describes a method for indirect fluorination of ilmenites using solutions of
hydrogen fluoride [36,37]. It is interesting to note that fluorination of TiO2 with anhydrous HF is
impossible and the presence of water is necessary for reactions to occur. This was concluded by the
authors [31] based on thermodynamic calculations. In our opinion, an explanation of this effect is
possible from the standpoint of the dissociation of HF (H2 O + HF = H3 O+ + F− ), with subsequent
participation of fluorine ions in the substitution reaction. Obviously, fluoride ions can also be considered
as an “activator” of ore decomposition in this case. A method for indirect fluorination of ilmenites
by using saturated aqueous solutions of hydrodifluoride or ammonium fluoride at boiling point was
proposed [32,38]. Such a fluoride method is considered quite promising not only due to the possibility
of efficient processing of altered ilmenites, but also due to recycling of the main components [39–42].
Significant disadvantages include the relatively high consumption of a leaching reagent (fluorides are
consumed in reactions not only by titanium (IV), but also by iron (III)) and the large number of process
steps. These disadvantages lead to an increase in costs compared to the sulfuric acid leaching method.
In our opinion, the combination of fluoride and sulfuric acid methods will overcome these
disadvantages due to possible synergies in the simultaneous interaction of sulfuric and hydrofluoric
acids with titanium dioxide, as the main source of titanium losses remaining in the sludge during
sulfuric leaching of altered ilmenites. In order to verify this hypothesis, we studied the thermodynamic
probability of possible reactions in the TiO2 –SO3 –H2 O system in the absence and presence of fluoride
ion additives. A comparative analysis of the thermodynamic probability of possible chemical
transformations is the first stage of research. The efficiency of this approach was demonstrated by
the authors earlier, in the publications [43–45]. The second stage of research is the kinetic analysis of
patterns that occur when titanium is leached [46]. It is of interest to study the effect of fluorides on
the rate of sulfuric acid dissolution of titanium oxide compounds. Thus, thermodynamic and kinetic
modeling of the decomposition of rutile by sulfuric acid in the absence and presence of fluoride ion
additives was the aim of this work.

2. Materials and Methods

2.1. Calculation Methods

Titanium dioxide as the main component of the sludge, 100 and 85 wt% solutions of sulfuric acid
and crystalline sodium fluoride, as a source of fluoride ions, were considered as initial materials for
thermodynamic modeling of the leaching process. It was assumed that the reactants and reaction
products are in the form of pure phases, i.e., in the standard conditions. The necessary thermodynamic
data for the participants of the chemical transformation were taken from the reference literature [47–49].
The change in standard Gibbs energies during chemical transformations was determined by the
Temkin–Schwartzman method [50] according to the formula:

ZT ZT
0 0 dT
∆G = ∆H298 − T∆S0298 −T ∆CP dT, (6)
T2
298 298

where ∆CP is the change in heat capacity during the transition from pure reagents to reaction products.
The change in heat capacity is determined by the equation ∆CP = ∆a + ∆b·T + ∆c·T−2 , where
writing heat capacity is represented in the form of an interpolation expression CP = a + b·T + c·T−2 .
The last term in the right side of Equation (6) was calculated by the formula:

ZT ZT
dT
∆CP dT = ∆aM0 + ∆bM1 + ∆cM−2 , (7)
T2
298 298
Processes 2020, 8, 640 4 of 15

where M0 , M1 and M−2 are temperature-dependent coefficients:

T 298.16
M0 = ln + − 1, (8)
298.16 T
1
M1 = (T − 298.16)2 , (9)
2T
1 1 1
 
M−2 = − . (10)
2 298.16 T2

2.2. Experimental Methods and Procedures

Titanium dioxide (for optical glass melting) was used in the experiments. Titanium dioxide was
preliminarily crushed in a drum mill under the following conditions: sample mass 100 g, mass of
cylindrical grinding bodies (40 × 40 mm) 3 kg, container volume of drum mill 2 L, rotation speed
60 rpm, grinding time 1 h, and dry grinding process. Afterwards, titanium oxide was calcined in a
muffle furnace at 900 ◦ C for 3 h. The phase composition of the oxide was confirmed by X-ray diffraction
(100% rutile phase was detected).
A powder fraction < 40 µm, at a mass ratio of TiO2 /H2 SO4 = 0.5 and TiO2 /NaF = 1, was used in
the sulfuric acid leaching process. The weight samples (0.50 g) of rutile were put into heat-resistant
tubes, and then the same weight sample of NaF (analytical grade, Reachem supplier) and 0.70 mL
of 85 wt% sulfuric acid (analytical grade, Reachem supplier) were added into tubes. The tubes were
placed into a glycerin bath, which was heated to the necessary temperature. The tubes were cooled
under running water in order to stop the leaching process; the contents of the tubes were quantitatively
transferred to a volumetric flask, using a 5 wt% H2 SO4 solution to prevent the hydrolysis of titanium
salts. The solutions were adjusted to the mark, stirred and left for a day to completely dissolve
the titanium salts and precipitate the unreacted part of rutile. The aliquots of these solutions were
transferred to heat-resistant glasses to evaporate traces of hydrogen fluoride and then the aliquots
were quantitatively transferred to volumetric flasks. The titanium concentration was determined by
the spectrophotometric peroxide method with a wavelength of 410 nm.
Each individual tube is a separate point on the kinetic curves. Each tube was taken out from a
glycerin bath at a specific time. Measurements at each point are the result of at least three experiments,
and therefore error markers are plotted for each point.

3. Results and Discussion

3.1. Model Selection for Thermodynamic Modeling

It is known [51] that in the TiO2 –SO3 –H2 O system, the formation of six titanium sulfate
salts is possible. The composition of these salts is determined by the SO3 content and the
temperature range (indicated in brackets): Ti(SO4 )2 (90–100%, below 250 ◦ C), TiOSO4 (60–90%,
150–250 ◦ C), TiOSO4 ·H2 SO4 ·H2 O (70–90%, below 150 ◦ C), TiOSO4 ·H2 SO4 ·2H2 O (60–70%, below 100 ◦ C),
TiOSO4 ·H2 O (45–60%, below 180 ◦ C) and TiOSO4 ·2H2 O (30–45%, below 80 ◦ C).
High concentrations of sulfuric acid (85–90%) are used to increase the efficiency of leaching
processes. At the same time, the temperature in the reaction mixture rises to a temperature range of
200–220 ◦ C due to the exothermic reactions of the leaching process and the interaction of concentrated
acid with sharp water steam. The composition of titanium sulfates does not remain constant in sulfuric
acid leaching of altered ilmenites; this was experimentally proved by the authors in the previous
work [52]. At the first stage, the salt of Ti(SO4 )2 is the dominant form when the temperature of the
reaction medium reaches 200 ◦ C. As compared to all other sulfate salts, this titanium salt is the most
soluble in the dilute acid solutions. A decrease in the acid concentration and in the temperature from
the moment of sludge formation (solidification of the reaction mixture) during the chemical reaction
leads to the formation of TiOSO4 salt, which also becomes crystallized when the titanium content
Processes 2020, 8, 640 5 of 15

increases in the reaction medium. This salt does not contain crystallization water. It is well explained
by the fact that water, which remains unevaporated before the solidification of sludge, is bound into
relatively strong hydrates of sulfuric acid H2 SO4 ·nH2 O.
It is known that the solubility of TiOSO4 becomes decreased after ageing of precipitate.
This property is important for the next stage of the process, the dissolution of the sludge in the
5 wt% solution of sulfuric acid. From the standpoint of the chemistry of coordination compounds,
the difference in the solubility of TiO(HSO4 ) and TiOSO4 salts can be explained by the difference
in the properties of monodentate HSO− 2−
4 ions and bidentate SO4 ions. These last ones can act as
bridging ligands which bind titanyl cations to the polymer structure. The formation of bridging bonds
between TiO2+ cations in titanium sulfate solutions has been experimentally proved by IR and Raman
spectroscopy [27,53]. The ligand exchange rate in the coordination sphere of Ti(IV) ions becomes
increased at high temperatures, which promotes the transition of the TiO2 –SO3 –H2 O system from a
metastable to an equilibrium state, with formation of less soluble products of TiOSO4 .
Therefore, we considered Ti(SO4 )2 and TiOSO4 as the main products of the reaction between
sulfuric acid and titanium dioxide in model calculations in order to thermodynamically substantiate
sulfuric acid leaching of titanium in industrial conditions.

3.2. Leaching of Titanium from Rutile with Sulfuric Acid

The dissolution of titanium dioxide in sulfuric acid with the formation of two products, Ti(SO4 )2
and TiOSO4 , was considered at the first stage of thermodynamic modeling. It is generally accepted to
consider such reactions in the most simplified form, as the reactions which are accompanied by the
release of water:
TiO2 + 2H2 SO4 = Ti(SO4 )2 + 2H2 O (11)

TiO2 + H2 SO4 = TiOSO4 + H2 O (12)

Obviously, water cannot be considered as a pure phase in concentrated solutions of sulfuric acid,
i.e., in the standard state, due to the formation of relatively strong hydrates H2 SO4 ·nH2 O. Therefore,
reactions (11) and (12) were rewritten taking into account the formation of sulfuric acid hydrate:

TiO2 + 4H2 SO4 = Ti(SO4 )2 + 2(H2 SO4 ·H2 O) (13)

TiO2 + 2H2 SO4 = TiOSO4 + H2 SO4 ·H2 O (14)

Similarly, it is possible to write the equations for the dissolution of titanium dioxide in 85%
sulfuric acid (the molar ratio H2 SO4 /H2 O = 1). The number of moles of sulfuric acid in such equations
should generally depend on the degree of conversion of titanium dioxide and excess sulfuric acid.
We considered one of the possible options which involve two acid hydrates with n = 1 and 2:

TiO2 + 6(H2 SO4 ·H2 O) = Ti(SO4 )2 + 4(H2 SO4 ·2H2 O) (15)

TiO2 + 3(H2 SO4 ·H2 O) = TiOSO4 + 2(H2 SO4 ·2H2 O) (16)

Table 1 shows the calculated values of ∆H298

0 , ∆S0 , ∆G0 and the coefficients ∆a, ∆b and ∆c in
298 298
the expression for change in heat capacity (∆CP = ∆a + ∆b·T + ∆c·T−2 ) during transformations in the
TiO2 –SO3 –H2 O system according to Equations (13)–(16).
Processes 2020, 8, 640 6 of 15

Table 1. Thermodynamic data for chemical transformations in the TiO2 –SO3 –H2 O system.

Reaction ∆H0298 [kJ/mol] ∆S0298 [kJ/mol·K] ∆G0298 [kJ/mol] ∆a ∆b·103 ∆c·10−5

TiO2 + 4H2 SO4 =
−235.2 −79.9 −211.3 −226.7 −58 56.9
Ti(SO4 )2 + 2(H2 SO4 H2 O)
TiO2 + 6(H2 SO4 ·H2 O) =
−178.8 −38.7 −167.2 −226.7 −58 56.9
Ti(SO4 )2 + 4(H2 SO4 ·2H2 O)
TiO2 + 2H2 SO4 =
−157.3 20.4 −163.4 −69.8 −30 33.4
TiOSO4 + H2 SO4 ·H2 O
TiO2 + 3(H2 SO4 ·H2 O) =
−129.1 41.0 −141.3 −69.8 −30 33.4
TiOSO4 + 2(H2 SO4 ·2H2 O)
Ti(SO4 )2 + H2 SO4 ·H2 O =
77.9 100.3 48.0 156.9 28 −23.5
TiOSO4 + 2H2 SO4

It was found that the largest decrease in the standard Gibbs energy is observed for the reaction of
Ti(SO4 )2 formation as a result of the dissolution of rutile in 100% sulfuric acid. The standard formation
energy of Ti(SO4 )2 decreases by almost 50 kJ/mol in 85% sulfuric acid. However, this salt is the most
thermodynamically stable sulfate compound of titanium (IV) even in this case. To confirm this general
property, it can be shown that the value of ∆G0298 (48 kJ/mol) for the reaction of the transformation of
Ti(SO4 )2 to titanium oxysulfate TiOSO4 is positive:

Ti(SO4 )2 + H2 SO4 ·H2 O = TiOSO4 + 2H2 SO4 (17)

This reaction also shows that the spontaneous dehydration of H2 SO4 ·H2 O with the formation of
100% sulfuric acid is impossible. The dissolution of titanium dioxide in sulfuric acid with the formation
of TiOSO4 oxysulfate is also characterized by negative values of the standard Gibbs energy (Equations
(14) and (16). The Ti(SO4 )2 →TiOSO4 transition according to reaction (17) is thermodynamically
impossible, and therefore the formation of both salts should be considered as two independent
reactions of the dissolution of rutile in sulfuric acid with the formation of Ti(SO4 )2 and TiOSO4 .
Temperature dependences of the change in standard Gibbs energies for the reactions (13)–(16)
are presented in Figure 1. The calculations were made for a temperature range of 298–510 K. The
upper temperature value is limited by the boiling point of 85 wt% sulfuric acid solution at 237 ◦ C.
Such a temperature range makes it possible to disregard the thermal effects of the evaporation and
decomposition of sulfuric acid onto water and sulfur oxide(VI). In addition, temperatures above 500 K
are not used in sulfuric acid leaching of ilmenites. The thermal effects of water evaporation and an
additional hydration of sulfuric acid were neglected in the calculations because of the presence of
water, which is formed upon dissolution of TiO2 and remains in the reaction mixture upon evaporation.
In fact, it is impossible to estimate the ratio of evaporated water to the water which remains bound to
hydrates with sulfuric acid.
It can be seen from the obtained data that temperature dependences of Gibbs energies for the
reactions of Ti(SO4 )2 formation according to reactions (13) and (15) are characterized by positive slopes.
This general property is explained by the fact that reactions (13) and (15), unlike all other considered
reactions, proceed with a decrease in entropy. Obviously, such ∆S0298 values are caused by a higher
degree of ordering of Ti(SO4 )2 crystal lattice as compared to TiO2 or TiOSO4 .
For reactions (14) and (16), the plot of the ∆G(T) dependence exhibits a monotonous decrease with
increasing temperature. It is well explained by the fact that the crystal lattice of the reaction product of
TiOSO4 is less ordered as compared to TiO2 .
In the case of reaction (17), the change in the Gibbs energy remains positive throughout the
entire studied temperature range. It shows that the spontaneous conversion of Ti(SO4 )2 to TiOSO4 is
impossible. At the same time, extrapolation of the ∆G(T) curves for reactions (13)–(17) into the area of
higher temperatures shows the fundamental possibility of shifting the equilibrium of the reaction (17)
towards the formation of TiOSO4 as the least soluble sulfate titanium salt.
K are not used in sulfuric acid leaching of ilmenites. The thermal effects of water evaporation and an
additional hydration of sulfuric acid were neglected in the calculations because of the presence of
water, which is formed upon dissolution of TiO2 and remains in the reaction mixture upon
evaporation. In fact, it is impossible to estimate the ratio of evaporated water to the water which
Processes
remains 2020, 8, 640to hydrates with sulfuric acid.
bound 7 of 15

Figure 1. Temperature
Figure 1. Temperature dependences
dependences of
of changes
changes in
in the
the Gibbs
Gibbs energy.
energy. Each
Each curve
curve corresponds
corresponds to
to the
the
individual reaction.
individual reaction.

The obtained results of thermodynamic calculations of the interaction between rutile and sulfuric
It can be seen from the obtained data that temperature dependences of Gibbs energies for the
acid confirm the widespread opinion that titanium dioxide can be dissolved in concentrated sulfuric
reactions of Ti(SO4)2 formation according to reactions (13) and (15) are characterized by positive
acid with the formation of tetravalent titanium salts. However, in cases where the dissolution of rutile
slopes. This general property is explained by the fact that reactions (13) and (15), unlike all other
is considered, it is usually indicated that such dissolution is rather slow (even in concentrated sulfuric
considered reactions, proceed with a decrease in entropy. Obviously, such ∆ values are caused
acid at the temperature of its decomposition onto SO3 and H2 O). Such slow dissolution of rutile shows
by a higher degree of ordering of Ti(SO4)2 crystal lattice as compared to TiO2 or TiOSO4.
that it can be considered as a chemically inert (ballast) component of the raw material in the sulfuric
For reactions (14) and (16), the plot of the ΔG(T) dependence exhibits a monotonous decrease
acid decomposition of altered ilmenites.
with increasing temperature. It is well explained by the fact that the crystal lattice of the reaction
In our opinion, the kinetic hampering of reactions (13)–(16) should be explained by the features of
product of TiOSO4 is less ordered as compared to TiO2.
the properties of Ti(IV) cation and the crystal structure of rutile. It is known that Ti(IV) ions belong to a
In the case of reaction (17), the change in the Gibbs energy remains positive throughout the entire
group of cations with a low degree of lability in coordination chemistry. The large positive charge of
studied temperature range. It shows that the spontaneous conversion of Ti(SO4)2 to TiOSO4 is
the titanium cation and its relatively small radius is believed to increase the activation energy of the
impossible. At the same time, extrapolation of the ΔG(T) curves for reactions (13)–(17) into the area
substitution reaction, which reduces the rate of exchange of intrasphere ligands (oxygen ions in rutile)
for other ligands from the solution (in our case, these are sulfuric acid ions whose concentrations in
H2 SO4 concentrated solutions are rather small).
Each titanium ion is surrounded by six oxygen ions, located at the angles of the octahedron
in the rutile crystal lattice. The octahedrons are connected by two common edges and form chains
parallel to the layers of the densest hexagonal packing. Although the tetragonal structure is typical for
many other oxides, rutile possesses some features different from those characteristic for close-packed
structures such as corundum. The layers of the densest packing of oxygen ions in the crystal structure
of corundum are perpendicular to the triple axis, while these layers are parallel to the faces of the
octahedron in the spinel structure; on the contrary, in the rutile structure, the layers of the densest
packing are parallel to the main (quadruple) axis of rutile crystals. Obviously, a local widening of the
crystal lattice would occur if oxygen ions in such layers are replaced by larger anions of sulfuric acid.
This process is associated with the additional energy consumption. The −Ti−O−Ti− bond breaking
without additional deformation of the crystal lattice is also obviously more advantageous with smaller
anions, the fluoride ones in this case. In fact, the reference data indicate the sequence of ionic radii
−
SO2− 2−
4 –0.295; O –0.136; F –0.133 nm.
Therefore, it is interesting to consider the effect of fluorides on the efficiency of the rutile
dissolution process.
 Processes 2020, 8, 640 8 of 15

3.3. Sulfate-Fluoride Leaching of Titanium from Rutile

Hydrochloric acid, calcium fluoride and sodium fluoride were used as a fluoride precursor.
The best results were obtained using sodium fluoride, which can be explained by the rapid evaporation
of HF from the reaction area and differences in the solubilities of CaF2 , NaF and the products of its
reactions with sulfuric acid.
Figure 2 shows the results of the effect of sodium fluoride addition on the efficiency of the
dissolution of rutile in sulfuric acid for 1.5 h, under isothermal conditions at a temperature range of
70–165 ◦ C.
It was found that the rutile does not completely dissolve in 85% sulfuric acid solution in the
absence of fluoride ions even at 100 ◦ C. NaF additives at a mass ratio of TiO2 /NaF = 1 dramatically
accelerate the dissolution of rutile. Curves 2–6 in Figure 2 have the shape of convex curves at the
Processes 2020, 8,of
beginning x FOR
the PEER REVIEW
leaching process. 8 of 15

Figure
Figure 2. The
2. The kinetics
kinetics of leaching
of leaching of rutile
of rutile during
during processing
processing in H
in H2SO 2 SO
4 (85 4 (85 at
wt%) wt%) at aratio
a mass mass ofratio
Ti/F of
Ti/F = 1/1 at temperatures: 70, 85, 100
= 1/1 at temperatures: 70, 85, 100 and 165 °C.and 165 ◦ C.

AsAscan canbe be seen

seen fromfromFigure
Figure 2, the highest
2, the degree
highest of titanium
degree leachingleaching
of titanium with increasing temperature
with increasing
is achieved during the leaching process at 100 ◦ C. The low degree of titanium leaching in the solution
temperature is achieved during the leaching process at 100 °C. The low degree of titanium leaching
◦ C can be explained by the fact that HF quickly evaporates from the reaction mixture at this
in at
the165
solution at 165 °C can be explained by the fact that HF quickly evaporates from the reaction
temperature.
mixture It is known that
at this temperature. an azeotropic
It is known that anmixture with
azeotropic a HF concentration
mixture of 37.5% and
with a HF concentration ofa37.5%
boiling
point ◦
of 109 pointC is formed
and a boiling of 109on °Cheating
is formed of HFonsolutions.
heating Therefore, increasing
of HF solutions. the temperature
Therefore, increasing to above
the
100 ◦ C increases the evaporation of HF, leading to a decrease in fluoride ion concentration in the
temperature to above 100 °C increases the evaporation of HF, leading to a decrease in fluoride ion
reaction mixture.
concentration in the reaction mixture.
Data
Data onon
thethe leaching
leaching kinetics
kinetics at different
at different temperatures
temperatures forfor
thethe initial
initial sections
sections of the
of the kinetic
kinetic curves
curves
X(t) made it possible to calculate the activation energy of this process: 45.0 kJ/mol. The values of of
X(t) made it possible to calculate the activation energy of this process: 45.0 kJ/mol. The values
activation
activation energiesare
energies are important
important data datatoto determine
determine thethe
mechanisms
mechanisms of leaching processes.
of leaching The literature
processes. The
gives rather
literature givesdifferent values of
rather different activation
values energiesenergies
of activation for sulfuric acid leaching
for sulfuric of ilmenite
acid leaching and its altered
of ilmenite and
its form.
alteredFor example,
form. as reported
For example, earlier [8,13],
as reported earlierthe activation
[8,13], energiesenergies
the activation are in the arerange
in theofrange
28–48ofkJ/mol,
28–
whereas other authors list activation energies as 75.0 [54], 72.6 [17] and
48 kJ/mol, whereas other authors list activation energies as 75.0 [54], 72.6 [17] and 64.4 [18] kJ/mol. 64.4 [18] kJ/mol. Further,
activation
Further, energies
activation in the ranges
energies of 52–62ofkJ/mol
in the ranges 52–62 [13–15]
kJ/mol and 80–100
[13–15] andkJ/mol
80–100[28] were[28]
kJ/mol alsowere
mentioned
also
by different authors. The different activation energies are explained
mentioned by different authors. The different activation energies are explained by the difference by the difference in the chemical
in
compositions of the researched ilmenite ores. According to our research
the chemical compositions of the researched ilmenite ores. According to our research [52], the first [52], the first stage of sulfuric
acidofleaching
stage sulfuricof ilmenite
acid leaching concentrates
of ilmenite is characterized
concentrates isbycharacterized
activation energies of 62.5 kJ/mol
by activation energiesforoftitanium
62.5
kJ/mol for titanium and 63.1 kJ/mol for iron. These activation energies, calculated according to thethe
and 63.1 kJ/mol for iron. These activation energies, calculated according to the kinetic data on
accumulation
kinetic data on the of titanium
accumulationand ironof salts in solutions,
titanium and ironindicate
salts inthat the parallel
solutions, extraction
indicate that theof Ti(IV)
paralleland
extraction of Ti(IV) and Fe(II, III) ions from ilmenite takes place. Therefore, one can compare the
dissolution of ilmenite and rutile in sulfuric acid based on a comparison of the magnitude of the
activation energies required for these chemical reactions. The addition of NaF into the reaction
mixture reduces the activation energy required from 63 to 45 kJ/mol; therefore, fluorides can be
considered as activators of the process which accelerate the interaction of rutile with sulfuric acid.
Processes 2020, 8, 640 9 of 15

Fe(II, III) ions from ilmenite takes place. Therefore, one can compare the dissolution of ilmenite and
rutile in sulfuric acid based on a comparison of the magnitude of the activation energies required for
these chemical reactions. The addition of NaF into the reaction mixture reduces the activation energy
required from 63 to 45 kJ/mol; therefore, fluorides can be considered as activators of the process which
accelerate the interaction of rutile with sulfuric acid. Thus, the process can be represented as a series
of stages:
xF− +TiO2 → [TiO2 Fx ]x− , (18)

[TiO2 Fx ]x− +H2 SO4 → TiOSO4 +H2 O+xF− , (19)

xF− +H2 SO4 → xHF +(1 − x)HSO−

4. (20)

The dissolution of titanium dioxide begins with the breaking of –Ti–O–Ti– bonds on its surface due
to the addition of fluoride ions. This initiates the subsequent sulfuric acid decomposition of titanium
dioxide on the sites of surface “defects” that are formed in the rutile lattice. The stage of gradual
Processes 2020, 8, x FOR PEER REVIEW 9 of 15
removal of fluorides from the reaction system due to the formation of low-dissociating hydrogen
fluorideinis TiO(OH)
absent also added because it was shown by additional experiments that fluorides are absent in
2 precipitates. The precipitates were obtained by ammonia deposition from
TiO(OH) precipitates.
titanium 2salt solutions after Thethe
precipitates were obtained
sulfate-fluoride by ammonia
decomposition deposition from titanium salt
of rutile.
solutions
Figure after the sulfate-fluoride
3 shows a photographdecomposition
of the sludgeofobtained
rutile. during leaching of ilmenite ore by the
sulfate-fluoride method in a hermetically sealed RVD-200 during
Figure 3 shows a photograph of the sludge obtained leachingHoles
Teflon reactor. of ilmenite ore by the
and recesses are
sulfate-fluoride method in a hermetically sealed RVD-200 Teflon reactor. Holes and
visible on the sample surface, which, in our opinion, can be explained by the formation of recesses aregaseous
visible
on the
HF sample surface, which, in our opinion, can be explained by the formation of gaseous HF bubbles.
bubbles.

3. A A
Figure 3.
Figure photograph
photograph of the
of the sludge
sludge afterafter sulfuric
sulfuric leaching
leaching of ilmenite
of ilmenite in the presence
in the presence of
of sodium
sodium fluoride.
fluoride.

Therefore, for thermodynamic modeling of the sulfate-fluoride leaching process, we used reactions
Therefore, for thermodynamic modeling of the sulfate-fluoride leaching process, we used
which involve the formation of hydrogen fluoride.
reactions which involve the formation of hydrogen fluoride.
TiO2 + 3H2SO4 + 2NaF = Ti(SO4)2 + Na2SO4 + 2H2O + 2HF↑ (21)
TiO2 + 3H2 SO4 + 2NaF = Ti(SO4 )2 + Na2 SO4 + 2H2 O + 2HF↑ (21)
TiO2 + 3H2SO4 + NaF = Ti(SO4)2 + NaHSO4 + 2H2O + HF↑ (22)
TiO
TiO2 + 2H2SO4 + 2NaF = TiOSO4 + Na2SO4 + H2O + 2HF↑
2 + 3H2 SO4 + NaF = Ti(SO4 )2 + NaHSO4 + 2H2 O + HF↑
(23)
(22)
TiO2 + 2H2SO4 + NaF = TiOSO4 + NaHSO4 + H2O + HF↑ (24)
As was mentioned 2 + 2H2water
TiOabove, SO4 +cannot
2NaF =beTiOSO 4 + Naas
considered 2 SO + H2phase
a 4pure O + 2HF↑ (23)
(in the standard state) in
concentrated solutions of sulfuric acid due to the formation of hydrates
TiO2 + 2H2 SO4 + NaF = TiOSO4 + NaHSO4 + H2 O + HF↑ H 2SO4·nH2O. Therefore,
(24)
reactions (21)–(24) were rewritten taking into account the formation of sulfuric acid hydrates:
(a) For 100% acid:
TiO2 + 5H2SO4 + 2NaF = Ti(SO4)2 + Na2SO4 + 2(H2SO4·H2O) + 2HF↑ (25)
TiO2 + 5H2SO4 + NaF = Ti(SO4)2 + NaHSO4 + 2(H2SO4·H2O) + HF↑ (26)
TiO2 + 3H2SO4 + 2NaF = TiOSO4 + Na2SO4 + H2SO4·H2O + 2HF↑ (27)
TiO2 + 3H2SO4 + NaF = TiOSO4 + NaHSO4 + H2SO4·H2O + HF↑ (28)
Processes 2020, 8, 640 10 of 15

As was mentioned above, water cannot be considered as a pure phase (in the standard state)
in concentrated solutions of sulfuric acid due to the formation of hydrates H2 SO4 ·nH2 O. Therefore,
reactions (21)–(24) were rewritten taking into account the formation of sulfuric acid hydrates:

(a) For 100% acid:

TiO2 + 5H2 SO4 + 2NaF = Ti(SO4 )2 + Na2 SO4 + 2(H2 SO4 ·H2 O) + 2HF↑ (25)

TiO2 + 5H2 SO4 + NaF = Ti(SO4 )2 + NaHSO4 + 2(H2 SO4 ·H2 O) + HF↑ (26)

TiO2 + 3H2 SO4 + 2NaF = TiOSO4 + Na2 SO4 + H2 SO4 ·H2 O + 2HF↑ (27)

TiO2 + 3H2 SO4 + NaF = TiOSO4 + NaHSO4 + H2 SO4 ·H2 O + HF↑ (28)

(b) For 85% acid:

TiO2 + 8(H2 SO4 ·H2 O) + 2NaF = Ti(SO4 )2 + Na2 SO4 + 5(H2 SO4 ·2H2 O) + 2HF↑ (29)

TiO2 + 8(H2 SO4 ·H2 O) + NaF = Ti(SO4 )2 + NaHSO4 + 5(H2 SO4 ·2H2 O) + HF↑ (30)

TiO2 + 5(H2 SO4 ·H2 O) + 2NaF = TiOSO4 + Na2 SO4 + 3(H2 SO4 ·2H2 O) + 2HF↑ (31)

TiO2 + 5(H2 SO4 ·H2 O) + NaF = TiOSO4 + NaHSO4 + 3(H2 SO4 ·2H2 O) + HF↑ (32)

The possible formation and decomposition of an intermediate product (a titanium (IV) fluoride
compound) was disregarded in the calculations.
The calculated values of ∆H298 0 , ∆S0 , and ∆G0 and the coefficients ∆a, ∆b and ∆c of the heat
298 298
capacity change equations for reactions (25)–(32) are listed in Table 2. Figures 4 and 5 for these reactions
show the results of calculations of the change in Gibbs energies of the rutile in a temperature range of
298–510 K.

Table 2. Thermodynamic data for chemical transformations in the TiO2 –NaF–SO3 –H2 O system.

Reaction ∆H0298 , [kJ/mol] ∆S0298 , [kJ/mol·K] ∆G0298 , [kJ/mol] ∆a ∆b·103 ∆c·10−5

TiO2 + 5H2 SO4 + 2NaF =
Ti(SO4 )2 + Na2 SO4 + 2HF↑ −206.4 157.8 −253.4 −334.5 43 85.3
+ 2(H2 SO4 ·H2 O)
TiO2 + 5H2 SO4 + NaF =
Ti(SO4 )2 + NaHSO4 + HF↑ −251.2 11.2 −254.6 −317.9 55 82.8
+ 2(H2 SO4 ·H2 O)
TiO2 + 3H2 SO4 + 2NaF =
TiOSO4 + Na2 SO4 + 2HF↑ + −128.5 258.1 −205.4 −177.6 71 61.8
H2 SO4 ·H2 O
TiO2 + 3H2 SO4 + NaF =
TiOSO4 + NaHSO4 + HF↑ + −173.4 111.5 −206.6 −161.0 84 59.4
H2 SO4 ·H2 O
TiO2 + 8(H2 SO4 ·H2 O) +
2NaF = Ti(SO4 )2 +Na2 SO4 −135.9 209.3 −198.3 −334.5 43 85.3
+ 2HF↑ + 5(H2 SO4 ·2H2 O)
TiO2 + 8(H2 SO4 ·H2 O) +
NaF = Ti(SO4 )2 + NaHSO4 –180.7 62.7 –199.4 –631.7 55 82.8
+ HF↑ + 5(H2 SO4 ·2H2 O)
TiO2 + 5(H2 SO4 ·H2 O) +
2NaF = TiOSO4 + Na2 SO4 + –86.2 289.0 –172.4 –177.6 71 61.8
2HF↑ + 3(H2 SO4 ·2H2 O)
TiO2 + 5(H2 SO4 ·H2 O) +
NaF = TiOSO4 + NaHSO4 + –131.1 142.4 –173.5 –161.0 84 59.4
HF↑ + 3(H2 SO4 ·2H2 O)
 –180.7 62.7 –199.4 –631.7 55 82.8
NaHSO4 + HF↑ + 5(H2SO4·2H2O)
TiO2 + 5(H2SO4·H2O) + 2NaF = TiOSO4 +
–86.2 289.0 –172.4 –177.6 71 61.8
Na2SO4 + 2HF↑ + 3(H2SO4·2H2O)
TiO2 + 5(H2SO4·H2O) + NaF = TiOSO4 +
Processes 2020, 8, 640 –131.1 142.4 –173.5 –161.0 84 59.4
11 of 15
NaHSO 4 + HF↑ + 3(H2SO4·2H2O)

Figure 4. Temperature dependences of the change in the Gibbs energy in rutile dissolution reactions in
Figure
Processes 2020,4.
8, Temperature dependences of the change in the Gibbs energy in rutile dissolution reactions
x FOR PEER REVIEW 11 of 15
100% sulfuric acid, with NaF as the activator reagent. Each curve corresponds to the individual reaction.
in 100% sulfuric acid, with NaF as the activator reagent. Each curve corresponds to the individual
reaction.

Figure 5. Temperature dependences of the change in the Gibbs energy in rutile dissolution reactions in
Figure 5. Temperature dependences of the change in the Gibbs energy in rutile dissolution reactions
85% sulfuric acid, with NaF as the activator reagent. Each curve corresponds to the individual reaction.
in 85% sulfuric acid, with NaF as the activator reagent. Each curve corresponds to the individual
reaction.
The calculated values of the change in the Gibbs energy show that reactions (25)–(32) are
thermodynamically possible because the change in the Gibbs energy is negative throughout the whole
Thetemperature
studied calculated range.
values The
of the change
addition in the Gibbs
of sodium fluorideenergy
leads toshow that reactions
a decrease (25)–(32)
in the standard are
Gibbs
thermodynamically
energy by approximately possible because
30 kJ/mol, andthethischange in the
difference Gibbsdoubled
is almost energy with is negative throughout
increasing temperaturethe
whole studied temperature range. The addition of sodium fluoride leads to a
to 500 K. The exceptions are reactions (26) and (30). The temperature dependences of Gibbs energies decrease in the standard
Gibbs energy
for these by approximately
reactions pass through a 30 kJ/mol,
small minimumand this
and difference is almostdecrease
then monotonically doubledinwith increasing
absolute value.
temperature to 500 K. The exceptions are reactions (26) and (30). The temperature
Despite the nature of the curves, the ∆G values remain negative. The ∆S298 values for these reactions
0 dependences of
Gibbs energies for these reactions pass through a small minimum and then
are positive, although their orders of magnitude are lower than those for other reactions. Therefore,monotonically decrease
in absolute
positive value.coefficients
angular Despite the ofnature of the curves,
the dependences the in
∆G(T) ΔG values
this case remain negative. by
can be explained ∆
Thea change values
in the
for these reactions are positive, although their orders of magnitude are lower
heat capacity of the participants in the chemical transformation, which is described by the last term than those for other
of
reactions. Therefore, positive
the Temkin–Schwartzman equation. angular coefficients of the dependences ΔG(T) in this case can be
explained by a change
Temperature in the heat
dependences capacity
of Gibbs of theare
energies participants in the
characterized by chemical
relativelytransformation, which
large negative angular
is described by the last term of the Temkin–Schwartzman equation.
coefficients for all other reactions considered above which involved NaF addition. This feature is
Temperature
explained by the factdependences of Gibbs
that these reactions areenergies
accompanied are characterized by relatively
by a large increase in entropylarge
caused negative
by the
angular coefficients for all other reactions considered above which involved
formation of gaseous HF. If we take into account that the removal of gaseous HF from the reaction NaF addition. This
feature is explained by the fact that these reactions are accompanied by a large
zone displaces its equilibrium to the right according to the Le Chatelier principle, then it should be increase in entropy
caused
concludedby the
thatformation
the rutile of
cangaseous HF. If we
be completely take into Further,
dissolved. account itthat the removal
should be notedofthat
gaseous HF from
reactions (26),
the reaction zone displaces its equilibrium to the right according to the Le Chatelier principle, then it
should be concluded that the rutile can be completely dissolved. Further, it should be noted that
reactions (26), (28), (30) and (32) make it possible to reduce the molar ratio of NaF/TiO2 from 2 to 1.
However, the complete conversion of TiO2 will require the use of an excess of fluorides in the reaction
mixture because of possible losses of hydrogen fluoride during the leaching process.
It can be concluded from the above analysis of the scheme of chemical transformations that the
Processes 2020, 8, 640 12 of 15

(28), (30) and (32) make it possible to reduce the molar ratio of NaF/TiO2 from 2 to 1. However, the
complete conversion of TiO2 will require the use of an excess of fluorides in the reaction mixture
because of possible losses of hydrogen fluoride during the leaching process.
It can be concluded from the above analysis of the scheme of chemical transformations that the
fluorides which participate in reactions (25)–(32) can be regenerated in HF form. Therefore, fluorides
can be considered as a homogeneous–heterogeneous (so-called bifunctional) catalyst, which increases
the sulfate-fluoride decomposition of rutile. The simultaneous homogeneity and heterogeneity of such
a catalyst is due to the fact that the fluorine ions do not form an independent phase in a sulfuric acid
solution, but exhibit their effect only at the phase boundary of both reagents, i.e., on the surface of
titanium dioxide.

4. Conclusions
The rutile can spontaneously dissolve in H2 SO4 solutions with the formation of salts Ti(SO4 )2 and
TiOSO4 , as shown by thermodynamic analysis of leaching of titanium in the TiO2 –SO3 –H2 O system.
At the same time, the experimentally proven inhibition effect of such reactions forces technologists
to consider rutile as an inert (ballast) component of titanium-bearing raw materials. In our opinion,
the kinetic difficulties in the reactions of sulfuric acid dissolution of rutile should be explained by
the features of Ti(IV) cation properties and the rutile crystal structure. The low degree of lability of
Ti(IV) cations increases the activation energy of substitution reactions in its coordination sphere and
reduces the rate of exchange of oxygen ions to sulfate ions. It should be noted that the concentration of
sulfate ions in the concentrated H2 SO4 solutions is rather small and further reduces the rate of the
substitution reaction. Further, it should be borne in mind that the size of sulfate ions is more than two
times larger than oxygen ions. Therefore, the exchange of oxygen ions to sulfate ions in the rutile lattice
should be inhibited by local expansion of the rutile crystal lattice. The breaking of Ti–O–Ti bonds
without additional strains in the crystal lattice is suggested to be more beneficial using smaller anions,
specifically fluoride ions.
The thermodynamic analysis of sulfate-fluoride leaching of titanium confirmed an additional
decrease in the Gibbs energy of the dissolution reaction of rutile in sulfuric acid in the presence of
fluoride ions.
The sodium fluoride additive increases the reaction between sulfuric acid and rutile by reducing
the activation energy to 45 kJ/mol, as shown by the kinetic studies. A reaction mechanism was
proposed for the interaction of rutile with sulfuric acid, which includes the breaking of Ti–O–Ti
bonds on the surface of rutile due to the replacement of oxygen ions by fluoride ions and the
sulfuric acid decomposition of titanium dioxide on the sites of surface “defects” in the rutile lattice.
It was proposed to consider the decomposition of rutile by the sulfuric acid in the presence of NaF
additives as a homogeneous–heterogeneous catalytic process, where fluoride ions play the role of a
bifunctional catalyst.

Author Contributions: Conceptualization, A.V.D. and M.V.N.; methodology, M.V.N.; software, A.V.D.; validation,
M.V.N.; investigation, A.V.D. and M.V.N.; resources, M.V.N.; writing—original draft preparation, A.V.D. and
M.V.N.; writing—review and editing, E.V.A., A.K. and B.L.; visualization, A.V.D.; supervision, B.L.; project
administration, A.K.; funding acquisition, B.L. All authors have read and agreed to the published version of
the manuscript.
Funding: The work was supported by R&D project 24/170290 of the Ukrainian State University of
Chemical Technology.
Conflicts of Interest: The authors declare no conflicts of interest.
Processes 2020, 8, 640 13 of 15

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