Front. Chem. Eng.
China 2009, 3(2): 155–160
DOI 10.1007/s11705-009-0005-z
RESEARCH ARTICLE
Sulfate digestion process for high purity TiO2 from titania slag
T. A. LASHEEN (✉)
Researches Sector, Nuclear Materials Authority, P. O. Box 530 El Maadi, Cairo, Egypt
© Higher Education Press and Springer-Verlag 2009
Abstract A titania slag product of Rosetta ilmenite
assaying 72% TiO2 is treated by the sulfate process option
of the pigmentary TiO2 manufacture. The relevant factors
of acid concentration, particle size, slag/acid ratio besides
the reaction temperature, and time have been studied. After
dissolving the cured mass in dilute acid and clarification,
the obtained solution was subjected to hydrolysis of its
titanium content. The final product was bleached under
reducing conditions to redissolve the residual coloring
impurities before being dewatered and calcinated. The
obtained results indicated that a leaching efficiency of
about 92% was realized due to the presence of some
refractory components in the working slag material,
namely, rutile and magnesium iron titanate. The obtained
white pigment assay attained up to 99.85% TiO2, while the
analyzed impurities involve 77 ppm Mn and only 14 and
7 ppm of total iron and V, respectively.
Keywords titania, slag, sulfate process, pigment
1 Introduction
Titanium dioxide is a widely known material that is mostly
used as pigment in paints, plastics, rubber, and paper
industries. Pigmentary grade TiO2 is commercially produced
by either the sulfate or the chloride route. The process of
chloride route is generally limited to high-grade feedstocks
because of impurities interference in the chloride route that
would render it economically not feasible. They include
mainly rutile mineral concentrate and high-grade titania
slag. However, due to the increasing lack of rich rutile
mineral deposits, interest in the relatively lower grade
ilmenite has greatly increased due to its huge reserves
distributed in several parts of the world. To enrich the TiO2
content of the relatively low grade ilmenite mineral
concentrates, several processes have been suggested and
Received October 31, 2008; accepted January 12, 2009
E-mail: lasheen_ta@yahoo.com
industrially applied, namely, conversion to synthetic rutile
or else to titania slag.
According to Harben [1], the need for higher grade
titanium feedstocks has encouraged ilmenite upgrading by
removing iron oxide and other impurities from the grain
lattice, thus enriching the TiO2 content. For this purpose,
several processes have been studied, and some of which
were commercially applied. Common commercial pro-
cesses include smelting to produce a high-titania slag plus
low manganese iron product (South Africa, Canada,
Norway), roasting to a synthetic rutile via the Becher [2]
process (Australia) or roasting and acid leaching to
synthetic rutile such as in the Benelite[3] process (USA,
India, and Malaysia).
For conversion to titania slag, ilmenite is mixed with
coal and subjected to a reduction smelting at 1500°C–
1700°C in an electric furnace [4]. In this process, a titania
slag float is produced, and its assay can vary from 75%–
80% TiO2 (sulfatable) to 85%–86% TiO2 (chlorinatable),
while pig iron sinks as a byproduct that can be used in
several industries (ductile iron castings, gray iron, allotted
cast iron, carbon steels, and alloy steels).
FeO:TiO2 þ CaO þ C ! TiO2 slag þ Fe þ Ca slag þ CO2
On the other hand, the main chemical upgrade is by the
Becher [2] process, which involves roasting higher TiO2
(57%–63%) ilmenite to synthetic rutile (91%–95% TiO2)
and the Benelite [3] acid leach process with roasting and
HCl leaching in which a wide range of ilmenites (50%–63%
TiO2) is transformed to synthetic rutile (915%–95%TiO2).
In these processes, the ilmenite concentrate is mixed with
subbituminous coal and subjected to reduction at 1200°C.
FeO:TiO2 þ C !ðFe þ TiO2 Þ þ CO2
Fe þ TiO2 þ O2 ! FeO þ TiO2
In spite of high consumption, smelting of ilmenite or
other titanium-bearing ores has several advantages over the
synthetic rutile route by chemical process according to
Sahu et al. [5]. It converts iron oxide as part of the
156 Front. Chem. Eng. China 2009, 3(2): 155–160

concentrate to value-added iron metal and slag containing
enriched titanium. Smelting technology can indeed use
low-grade ilmenite with zero waste generation, and several
R and D organizations are involved in improving this
technology to bring down the power consumption besides
enriching the slag quality and its leachability. As cited by
Mackey [6] in 1994, titania slag is now the major source of
raw material supply to the pigment companies,; providing
about 39% of the feedstocks in comparison with 33% from
natural ilmenite [5]. It replaces the natural rutile in the
same manner as synthetic rutile. Accordingly, the pigment
and metal industries worldwide no longer fully depend on
natural minerals. The major advantages of the slag
technology actually involve high titanium content, low
waste generation, and its suitability for both the sulfate and
chloride processes besides a low chemical cost.
Several processes have been studied for the treatment of
titania slag, which are primarily concerned with the
destruction of its refractory nature. These could involve
chlorination of the impurities [7–10], salt roasting [11,12],
fluxing of the impurities, oxidation-reduction roasting
VanDyke [13], Borowiec et al. [14], sulphidization [15],
and sulfatizing of the impurities [16]. In the latter, the slag
was first mixed with an alkaline salt such as Na2CO3, reacted
with either SO3 or mixtures of SO2 and O2 at 700°C to
1100°C, and followed by leaching the formed sulfates in
water or HCl acid. Currently, the two process options for
the manufacture of titanium dioxide pigment, namely, the
sulfate and the chloride processes can also be directly
applied to the titanium slag. Both process options yield
final products falling in the category of titanium dioxide
pigment rutile grade (TDPRG) and titanium dioxide
pigment anatase grade (TDPAG).
In the present work, a sample of the titania slag product
of Rosetta ilmenite assaying 72% TiO2 was kindly
provided by the Nuclear Materials Authority (NMA)
Titanium project. Due to the relatively low TiO2 content, it
was decided to apply the sulfate option for studying the
relevant factors required for the manufacturing of titanium
dioxide pigment thereof. These factors involved the acid
concentration, particle size, and slag/acid ratio besides the
reaction temperature and time.
2 Experimental
2.1 Material
A titania slag sample prepared from Rosetta ilmenite by its
carbothermal reduction in an electric arc furnace was
kindly provided from NMA titanium project. The obtained
titania slag blocks were crushed, ground, and sized using
ordinary laboratory equipment. A representative sample of
about 50 kg thereof was obtained after proper mixing and
quartering. A proper portion of the representative sample
was then subjected to XRD analysis for the definition of its
constituents. For this purpose, a Philip X-ray unit (Pw
3020) fitted with a Cu target (Pw 2233), and a Ni filter and
was operated at 40 kV and 30 mA. Thus, it has been
possible to identify pseudobrookite Fe2TiO5, rutile TiO2
besides metallic iron and quartz components, Fig. 1.
Fig. 1 X-ray diffraction pattern of sample slag
M-magnesium iron titanate, P- pseudobrookite, R-rutile, I-metallic iron,
Q-quartz
2.2 Analytical procedures
A sample portion ground to – 325 mesh particle size was
then subjected to wet chemical and atomic absorption
spectroscopic analysis to define its chemical composition.
All chemical and reagents used in this study are of
analytical grade.
The representative portion of the slag material was first
opened by fusion with potassium pyrosulfate. Titanium
and total iron analyses in the titania slag feed, products,
and the different stream solutions were performed using
the colorimetric and titrimetric methods, respectively.
Thus, for titanium, tiron was used as the complexing
agent, and the absorbance was measured at 430 nm using
the Unicam UV2–100 model spectrophotometer. Total iron
was determined by titrimetry against EDTA using
sulfosalicylic acid. Both calcium and magnesium were
also titrimetrically determined against EDTA using
murexide and Eriochrome Black T indicators. The
molybdate reagent in the presence of tartaric acid has
been used to determine the silica content. Trace elements
analysis (Cr, V, and Mn) was performed by means of an
atomic absorption spectrometer (Unicam 969 Model) at
357.9, 318.4 and 279.5 nm, respectively. The obtained
analytical results are given in Table 1.
2.3 Leaching procedure
In each leaching experiment, a 100 g sample portion of the
working powdered titania slag was introduced into a
 T. A. LASHEEN. Sulfate digestion process for high purity TiO2 from titania slag
Table 1 Chemical analysis of the working titania slag
constituent wt-% constituent
TiO2 72.00 MnO
Fe2O3 a)
12.65 Cr2O3
Al2O3 1.80 V 2 O5
MgO 0.60 P2O5
CaO 0.78 SiO2
a) total iron
digestor vessel containing a defined amount of concen-
trated sulfuric acid. The reaction was then initiated by
adding a small amount of water, which was also required to
maintain the fluidity of the reaction mixture. Unless cited
otherwise, the concentration of sulfuric was adjusted to
about 17 mol/L, while the slag/acid ratio (w/V) was fixed at
1∶ 2.5, and the reaction temperature was maintained at
170°C. Accordingly, the reactant mixture was found to boil
releasing vast quantities of steam and vapor; a matter that
resulted in solidification of the reaction mass. This was
followed by allowing the digestion cake to cure for an extra
1 h so as to have a maximum effect on titanium recovery
upon later dissolution. After proper curing, the solid
product was dissolved in diluted sulfuric acid to form the
corresponding soluble metal sulfates in solution, which
was then separated from un-dissolved residue by filtration.
Finally, the obtained filtrate was subjected to proper
hydrolysis (four times dilution at 90°C) to yield the
hydrated titanium oxide. The obtained hydrolysis product
was separated from the mother liquor and repulped with
diluted hot sulfuric acid in the presence of zinc metal to re-
dissolve the hydrolyzed impurities. After filtration of the
hydrolyzed bleached titanium, it was filtered, washed
dewatered, and calcinated to a high-grade titanium dioxide
product.
3 Results and discussion
3.1 Effect of acid concentration
A series of slag digestion experiments were performed
using different molarities of sulfuric acid varying between
12 and 18.4 mol/L, whereas the other conditions were fixed
at a slag/acid ratio of 1 ∶2.5 using a powdered slag ground
to – 200 mesh size. The digestion temperature was fixed at
170°C, and agitation was allowed until the solidification of
the reacting slurry. As previously mentioned, the reacting
slurry or the solidified mass at the end of experiment was
left for one more hour before its dissolution in the diluted
sulfuric acid and filtration. This extra time was found
necessary for the completion of the reaction. This was due
to the fact that good dispersion of the ore material in the
acid is essential for higher recovery of titanium.
From the data presented in Fig. 2, it shows that at
17 mol/L acid, the dissolution efficiency of titanium and
157
iron attained 69.8% and 86.0%, respectively. However, at
wt-% an acid concentration ranging from 12 to 15 mol/L, the
1.63 dissolution efficiency of TiO2 increased from 39.7% to
0.32 54% respectively, while that of iron increased from 63.0%
0.55
to 71.0%, respectively. Depending on initial acid concen-
tration as well as the working temperature, solidification of
0.06
the reaction slurry might occur quite early. Consequently,
9.00 the optimum acid concentration for maximum dissolution
under these working conditions was 17 mol/L. However,
better efficiency conditions particularly the temperature
and the ore size will be later shown.
Fig. 2 Effect of acid concentration on the dissolution efficiency
of the working slag
3.2 Effect of particle size
To study the effect of the particle size of the working titania
slag, a portion ground to varying particle sizes ranging
from – 140 to – 325 mesh size was prepared. In these
experiments, the other digestion conditions were fixed at
17 mol/L sulfuric acid concentration at 170°C and using a
slag/acid ratio of 1∶2.5. As was expected, the results ep.
cited in Fig. 3 clearly indicate that the dissolution
efficiencies of titanium and iron are markedly dependent
upon the input particle size. Thus, at – 140 mesh size, the
dissolution efficiencies of titanium and iron were only
50.6% and 56.5%, respectively. and by decreasing the
particle size, a progressive increase to 88.7% and 92.0%,
respectively, has been realized at – 325 particle size. Given
the refractory nature of the working slag material,
increasing its surface area by fine grinding is essential to
realize better liberation of the slag component on one hand
and in turn, better contact with the acid.
3.3 Slag/acid ratio (w/V)
This factor was studied through a series of digestion
experiments carried at a slag/acid ratio varying from 1∶1 to
1∶2.75. Other digestion conditions were fixed at 17 mol/L
sulfuric acid concentration, 170°C, and a slag sample
portion ground to – 325 mesh size was used. The obtained
results shown in Fig. 4 proved that the slag/acid ratio seems
158 Front. Chem. Eng. China 2009, 3(2): 155–160
Fig. 3 Effect of particle mesh size on the dissolution efficiency of
the working slag
Fig. 4 Effect of slag/acid ratio on the dissolution efficiency of
the working slag
to have a significant effect. where at the ratio of 1∶2.25, the
dissolution efficiency attained 87.9% and 91.0% for
titanium and iron, respectively. With a further decrease in
the slag/acid ratio thereafter with consequent increase of the
acid amount, only a slight increase in the yield was shown.
On the contrary, increasing the slag/acid ratio to 1∶1.5, the
titania and iron dissolution was found to gradually decrease,
and at 1∶1 ratio, only 55% and 58% dissolution efficiency of
titanium and iron was realized; it is most probably due to a
decrease in the input acid amount. Accordingly, it is
important that the proportion of the input acid should be at
least sufficient to react with all the slag constituents in a
manner to ensure to be converted to soluble sulfates. At same
time, it has to be indicated that decreasing the slag/acid ratio
would increase the fluidity acid; consequently, the reaction
rate would be reduced further.
3.4 Effect of temperature
The effect of temperature for conducting the digestion
reaction was investigated in the range of 120°C up to 200°C.
The other digestion conditions were fixed at 17 mol/L acid
concentration, – 325 mesh size, and 1∶ 2.25 slag/acid ratio.
Results given in Fig. 5 clearly show that increasing the
digestion slag temperature strongly accelerates the reaction
yield up to 160°C. At this temperature, the obtained
dissolution efficiencies of titanium and iron attained 92%
and 93, respectively. Beyond this temperature, the
dissolved titanium spices started to progressively hydro-
lyze in association with a relatively lower iron amount. It is
important to indicate that when the reaction temperature
reached 200°C, some agglomerates have been formed in
the product and were not amenable to the leaching process.
This might be due to the polymerization effects of the
hydrolyzed titanium product. The agglomeration of
particles was reported previously by Liang et al. [17] and
Han et al. [18]. They reported that the insoluble hard grains
formed in the digestion reaction at high temperatures were
un-reacted ore enclosed by product layer composed of an
insoluble surface layer of titanium and iron sulfates, which
prevents further dissolution of the enclosed ore. On the
contrary, working at low temperatures should be avoided
since the rate of the digestion reaction is seriously affected.
Accordingly, the preferred operating temperature for
conducting a successful slag digestion would be in the
range of (160
2)°C.
Fig. 5 Effect of temperature on the dissolution efficiency of the
working slag
3.5 Effect of time
The required contact time between the slag and the
dissolving acid has been found to be greatly dependent on
the operating experimental conditions. Thus, when the acid
concentration and/or the temperature increases, the reac-
tion rate would greatly increase, resulting in excessive of
water evaporation and consequently early solidification of
the reacting slurry. In turn, the completion of the reaction
might be affected. Therefore, the titanium dissolution
efficiency would be reduced. This effect is clearly evident
from the data of the experimental results shown in Table 2.
3.6 Optimum digestion factors of Rosetta slag
From the foregoing studies of the digestion factors of
Rosetta slag, the relevant factors have been defined and
 T. A. LASHEEN. Sulfate digestion process for high purity TiO2 from titania slag
Table 2 Effect of temperature on the solidification time of the reacting
slag/acid slurry
temperature/°C 155 160 170 180 190
solidification time/ min 57.0 50.0 33.0 10.0 3.5
titanium dissolution efficiency/% 87.5 91.9 85.3 72.5 66.4
optimized. It includes fine grinding of the input slag to
– 325 mesh size, sulfuric acid concentration of 17 mol/L at
(160
2)°C, and using a slag slag/acid ratio of 1∶ 2.25.
Under these conditions, the titanium and iron dissolution
efficiencies attained about 92% and 93%, respectively. The
undissolved fraction of titanium and iron was most
probably due to their presence in some highly refractory
components of the working slag. To confirm this
conclusion, a part of the slag residue left after digesting
the Rosetta slag under the determined conditions, was
subjected to an XRD analysis. From the obtained diffraction
data shown in Fig. 6, it has been revealed that besides quartz,
the unreacted residue is composed essentially of rutile and
magnesium iron titanate. It is well known that rutile is
insoluble in sulfuric acid, and the solubility of the titanate
components is greatly variable depending on their composi-
tions. It can thus be mentioned that the defined magnesium
iron titanate must be of a refractory composition that is not
amenable to digestion under the working conditions and
would therefore be responsible for the undissolved titanium
percent of about 8%.
Fig. 6 X-ray diffraction pattern of unreacted slag sample
M-magnesium iron titanate, R-rutile, Q-quartz
The existence of a considerable amount of TiO2 as rutile
in the unreacted solid product is explained by different
authors. Sahu et al. [5] concluded that the leachability of
titanium in the slag in acid medium is mainly dependent
upon the phases present, grain size, and the oxidation states
of the corresponding oxides. They stated that the leaching
efficiency will decrease if the slag is rich in TiO2, Ti
159
carbide/nitride, or carbonitride, because these are partially
insoluble even in hot H2SO4 acid. To get higher leaching
200 efficiency, the contents of these phases have to be
3.00 minimized by controlling the electrosmelting process,
63.5
which will facilitate the formation of leachable oxides of
lower oxidation states such as TiO or Ti2O3. According to
Sinha [19], it was suggested that to achieve the required
high degree of solubility, the Ti originally present in the
feed material has to be converted to the anosovite phase,
which is a solid solution structure based on Ti3O5. In
addition, Mackey [6] has stated that the further reduction
of the slag having a pseudobrookite phase may yield the
anosovite phase, which is suitable for Ti recovery.
Finally, it has to be indicated that the obtained titania
hydrolyzate was found to be pale colored most probably due
to the presence of some iron and other trace impurities such
as Cr, Mn, and V. These species impart a honey color to the
produced titanium dioxide, whereas by extensive washing
were not removed. A bleaching operation consisting of
reslurry of the hydrolyzate product in 30% sulfuric acid in
the presence of zinc metal was found necessary. This would
redissolve most of these impurities after their proper
reduction. The titanium hydrolyzate left behind was then
filtered from the solution, extensively washed, dried, and
ignited at 600°C and 900°C for 1 h to obtain both anatase
and rutile, respectively, Johnsson et al. [20].
The two ignited products were then subjected to an XRD
analysis and the data obtained, shown in Fig. 7, confirmed
the production of anatase (TDPAG) and rutile (TDPRG),
respectively. The ignited rutile grade was chemically
analyzed, and the obtained results are given in Table 3 in
comparison with a finally ignited sample before and after
bleaching. From these data, it is clearly evident that
chromium was completely removed and that the purity of
the obtained product attains 99.85%, while the associated
impurities of manganese, iron, and vanadium assay were
77, 14, and 7 as ppm.
4 Conclusion
A high-quality pigment grade titanium dioxide of either
anatase or rutile structure has been prepared from a
titanium slag product of Rosetta ilmenite by application of
the sulfate process. The digestion reaction was accom-
plished as a batch reaction in one stage. Factors affecting
the digestion process was studied and optimized. These
were found to include a 17 mol/L sulfuric acid concentra-
tion; a slag ground to – 325 mesh size in a slag/acid ratio
(w/V) of 1∶ 2.25 at (160
2)°C. The obtained porous mass
was then allowed to cure for 1 h and then leached with
diluted acid to form a metal sulfates solution. The liquor
was then subjected to proper hydrolysis, where titanyl
sulfate hydrolyzed. Re-slurrying of the hydrolysable
product in the diluted sulfuric acid in presence of Zn as a
reducing agent followed by filtration and thorough
160 Front. Chem. Eng. China 2009, 3(2): 155–160

washing steps were found essential to get rid of most of the

associated coloring impurities. The obtained product was
found to assay up to higher than 99.85% TiO2 with less
than a total of 100 ppm impurities.

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