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Environmental problems of finely dispersed titanium dioxide production

Article  in  Russian Journal of General Chemistry · December 2013

DOI: 10.1134/S1070363213130100

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ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 82, No. 13, pp. ????–????. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © A.P. Voznyakovskii, V.P. Ponimatkin, V.V. Timkin, 2012, published in Ekologicheskaya Khimiya, 2012, Vol. 21, No. 4, pp. 205–218.

Environmental Problems of Finely Dispersed

Titanium Dioxide Production
A. P. Voznyakovskiia,b, V. P. Ponimatkina, and V. V. Timkina
a
Faktoriya LS Ltd., ul. Latyshskikh strelkov 25, St. Petersburg, 195213 Russia
b
Lebedev Research Institute of Synthetic Rubber, ul. Gapsal’skaya 1, St. Petersburg, 198035 Russia
e-mail: [email protected]

Received November 20, 2012

Abstract—Finely dispersed titanium dioxide is widely used in modern technologies. Proved reserves of
titanium ores in Russia are expected to meet industrial needs. However, the available facilities for the
manufacture of titanium dioxide from ores are clearly insufficient, which naturally requires new plants to be put
into operation. The technologies used for the production of titanium dioxide were developed as early as 1940s,
when ecological aspects of the production process were almost not taken into account. The present survey
analyzes environmental problems related to the titanium dioxide production according to the sulfate and
chloride technologies in comparison with the fluoride process proposed for industrial implementation. The
fluoride process has been examined as applied to ilmenite from the Turan deposit in Tomsk oblast, and some
actions directed toward improvement of ecological parameters of this process have been proposed.

Keywords: titanium dioxide, production technology, sulfate process, chloride process, hydrothermal process,
fluoride process.
DOI: 10.1134/S107036321313????

INTRODUCTION However, only ilmenite deposits are developed in

the Russian Federation. From the chemical viewpoint,
Titanium dioxide is among most important ilmenite is a mixture of oxides, mainly of titanium and
inorganic compounds used in modern industry [1–10]. iron oxides. The present article is focused on ecolo-
Unique properties of titanium dioxide determine the gical aspects of titanium dioxide production just from
level of technological progress in various fields of ilmenite.
World economics. Only 5% of the total produced
titanium ore is consumed for the manufacture of METHODS OF TITANIUM DIOXIDE
titanium metal, whereas the major part of annually PRODUCTION
produced titanium minerals is used to obtain titanium
dioxide. Finely dispersed titanium dioxide is the most Titanium dioxide occurs in nature as two minerals,
needed product in the World market. Its global anatase and rutile, and its production from either of
production is estimated at 4.5 million tonnes. these minerals is based on two technological schemes,
sulfate and chloride processes.
The main application of titanium dioxide is its use
as pigment in paint-and-lacquer industry. It is also used Sulfate process [11–39]. The sulfate technology for
in the manufacture of synthetic rubber, paper, refrac- the manufacture of titanium dioxide is based on the
tory glasses, and construction materials. Titanium treatment of ilmenite with sulfuric acid. The sulfate
dioxide is obtained from titanium-containing ores, method was put into operation in 1931 for the
such as rutile, anatase, and ilmenite (Fig. 1). Rutile and manufacture of titanium dioxide from anatase, and
anatase are most appropriate for the manufacture of later (in 1941), from rutile.
titanium dioxide whose concentration in these minerals Ilmenite is subjected to grinding and drying and
reaches 92–98 and 90–95%, respectively. then treated with concentrated sulfuric acid. The

????
2 VOZNYAKOVSKII et al.

Ilmenite (mixture
Rutile Anatase of minerals, FeTiO3) Titanium dioxide

Fig. 1. Appearance and structure of titanium ores and titanium dioxide.

resulting molten titanyl sulfate is cooled and dissolved High sulfuric acid concentration ensures rapid tem-
in water to a definite concentration. Iron(III) present in perature rise to 190–220°C without additional energy
the titanyl sulfate solution is reduced to iron(II). The expenditures (via addition of water or recycled waste
solution is allowed to settle down and subjected to acid solution). As a result, high rate of the process and
rough filtration. The filtrate is cooled, and crystalline high concentrate conversion (96–97%) are achieved. In
iron(II) sulfate is separated from the mother liquor by the continuous process, titanyl sulfate obtained from
centrifugation. The solution of titanyl sulfate thus ilmenite is hydrolyzed directly in the reaction mixture
obtained is concentrated to a required level and according to the equation:
transferred to the hydrolysis step.
TiOSO4 + 2H2O = H2TiO3 + H2SO4.
In the hydrolysis step, titanium dioxide hydrate
separates from the solution in the form of amorphous This reaction produces a large amount of dilute
flakes. The titanium dioxide hydrate pulp is subjected (20–22%) sulfuric acid containing titanium and other
to filtration in two steps, in which it is washed from metal sulfates. This acid is a waste material. Its
chromophoric impurities and bleached. After addition possible utilization implies evaporation to a concentra-
of necessary ingredients, the titanium dioxide hydrate tion of 55% and subsequent use in the manufacture of
paste is calcined in a calcining furnace to remove superphosphate. After hydrolysis, up to 95–96% of
hydration water and endow the product with pigment titanium precipitates from the solution, and metatitanic
properties. acid (H2TiO3) thus formed adsorbs a considerable
amount of SO3. Metatitanic acid is washed, dried, and
After calcination, the product is ground in two steps
calcined, so that it initially loses water (at 200–300°C)
and subjected to surface treatment with some chemicals;
and then SO3 (at 500–800°C); at 850–900°C neutral
as a result, pigmentary titanium dioxide acquires re-
(pH = 7) titanium dioxide is obtained. Iron(II) sulfate
quired application properties. The treated pigmentary
heptahydrate formed as by-product is calcined to
titanium dioxide is dried and subjected to fine
obtain monohydrate FeSO4 · H2O, and the latter is
grinding. The finished product is packed and stocked.
ground. The sulfate method requires 4.0–4.5 t of sulfuric
The TiO2 content of ilmenite does not exceed 43–53%;
acid per metric ton of ilmenite concentrate (TiO2
therefore, its preliminary enrichment is required.
content 42%). Figure 2 shows the process scheme for
The production of titanium dioxide from ilmenite the manufacture of titanium dioxide implemented at
can be organized as batch or continuous process. The the Krymskii titan works. The sulfate technology for
batch technology utilizes concentrated sulfuric acid. the titanium dioxide production from ilmenite and

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 13 2013

 ENVIRONMENTAL PROBLEMS OF FINELY DISPERSED TITANIUM DIOXIDE PRODUCTION 3

Sulfuric
acid Reducing agent

Drying and Decomposition Clarification

Ilmenite/slag Reduction
grinding
Slag
Cold circulating water

Vacuum
1st fine Crystallization and Rough
Hydrolysis Vacuum
filtration centrifugation filtration
Evaporation

Slag
Dilute sulfuric Cold circulating water Condensate
acid Iron(II)
slfate
Repulping Calcination
2nd fine Salt treatment
Bleaching
filtration
Inorganic salts,
organic agents

Wet Dry
Micronization Drying Surface grinding
treatment grinding

Packing

Fig. 2. Technological scheme of the sulfate process for titanium dioxide production (Krymskii titan).

titanium slags has a number of essential drawbacks, in and other metal chlorides as by-products which are
particular complex multistep process and high subsequently removed. After fine purification, TiCl4 is
consumption of sulfuric acid a considerable amount of oxidized at high temperature to form intermediate
which is unproductively wasted with iron(II) sulfate titanium dioxide which is characterized by high
(more than 3 t of FeSO4 · H2O per metric ton of TiO2) brightness. The oxidation step assumes the possibility
and dilute (20–22%) impure sulfuric acid (after to rigorously control particle size distribution, as well
hydrolysis). Therefore, the sulfate technology cannot as their crystalline structure, so that titanium dioxide
be regarded as admissible from the viewpoint of up-to- with excellent covering and bleaching capacities.
date stringent requirements for environmental safety. 2FeTiO3 + 7CI2 + 3C → 2TiCI4 + 2FeCI3 + 3CO2
Chloride process [40]. The chloride method is TiCl4 + O2 → TiO2 + 2CI2.
more economic and less environmentally harmful. In The most important step in the production of finely
addition, it is free from the iron(II) sulfate utilization dispersed titanium dioxide by the chloride method is
problem, but additional requirements to the quality of oxidation (combustion) of titanium(IV) chloride. This
titanium concentrates should be met. The chloride process is carried out at 900–1000°C using specially
process was developed and put into operation in 1948 designed burners which ensure the reaction tempera-
by DuPont, thus initiating the production of rutile ture to be maintained within the required limits and a
titanium dioxide (Fig. 3). definite dwell time of the combustion products. The
oxidation of titanium(IV) chloride with oxygen follows
The process is based on two high-temperature
the reaction equation
water-free gas-phase reactions. Titanium ore is treated
with gaseous chlorine to obtain titanium(IV) chloride TiCl4 + O2 → TiO2 + 2Cl2.

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 13 2013

4 VOZNYAKOVSKII et al.

Chloride process

Titanium ore Chlorine Carbon Oxygen

Titanium dioxide
Chlorination Purification Oxidation pigment base

Metal chlorides
(except for
titanium
tetrachloride)
Final step

Surface Filtration,
Pigment base washing, drying Grinding Packing
treatment

Additives

Suspension Suspension Transport

preparation stabilization

Fig. 3. Technological scheme of the chloride process for titanium dioxide production.

Liberated chlorine can be recycled to the and the use of chlorine and high-temperature condi-
manufacture of titanium(IV) chloride; therefore, the tions require corrosion-resistant equipment.
combustion process is already used on an industrial
Hydrothermal process [41, 42]. Nanopowders are
scale.
commonly obtained by high-temperature hydrolysis of
Titanium dioxide obtained by oxidation of titanium various compounds directly in a high-pressure reactor
(IV) chloride contains up to 0.6% of adsorbed chlorine, or by hydrothermal treatment of reaction products.
and its aqueous suspension is characterized by a pH Hydrothermal conditions strongly accelerate
value higher than 7. The chlorine content of TiO2 can crystallization of many amorphous phases. In the first
be reduced to 0.1% by calcination at 300–900°C. The case, a high-pressure reactor is charged with an
resulting product has a pH value of aqueous extract of aqueous solution of salt precursors, and in the second,
5–6.8 and is suitable for industrial applications. with a suspension of reaction products obtained under
conventional conditions. As a rule, there is no need of
Some manufacturers, e.g., DuPont, make use of
special equipment and temperature gradient.
direct chlorination of ilmenite concentrates. A problem
related to this technology is increased discharge of Advantages of the hydrothermal method include the
sodium hydroxide (1,1 t of NaOH per metric ton of possibility for obtaining crystals unstable near the
chlorine). The problem of sodium hydroxide utilization melting point, as well as large high-quality crystals.
may be solved in part by cooperation with aluminum Among disadvantages, high cost of the equipment and
manufacturers. impossibility of visual control over crystal growth.
The chloride process is more environmentally However, the development of hydrothermal
friendly and perfect than the sulfate method due to the methods for the manufacture of titanium dioxide still
possibility for its implementation in the continuous remains at the pilot plant level. Their general drawback
mode and hence for making it completely automated. is unsatisfactorily solved problem of utilization of
However, this process is sensitive to the raw materials, hydrogen chloride or aqueous HCl formed as a result

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 ENVIRONMENTAL PROBLEMS OF FINELY DISPERSED TITANIUM DIOXIDE PRODUCTION 5

of hydrolysis, which could not be recycled. Hydrolysis vative technologies with sharply improved economic
of titanium(IV) chloride with water vapor at 25–75°C and ecological parameters. An example of such
on exposure to air gives a viscous liquid which technologies is a recently developed process which
solidified to form a white material on prolonged may be referred to as fluoride process. Scientific
storage. Gas phase hydrolysis at 1000–1200°C ensures principles of this process are based on a new line in the
preparation of finely dispersed titanium dioxide. chemistry of inorganic fluorides, namely on the use of
Nevertheless, the problem of hydrogen chloride fluorine-containing oxidants in the chemistry, analysis,
utilization still restrains large-scale implementation of and technology of noble metals. The fluoride process
the hydrothermal technology. was designed for processing of ilmenite concentrate
from the Tugansk deposit in Tomsk oblast. While
Ecology or economy? Analysis of modern industrial
choosing raw material suppliers, the following factors
technologies for the production of titanium dioxide
were taken into account:
allowed us to draw the following conclusions.
(1) Conformance of products (raw materials) to the
The classical sulfate and chloride processes are
technological requirements (concentration of main
energy consuming, which increases the cost of the
components, persistence of composition, etc.);
final product. Although the energy intensity of the
sulfate process is considerably higher as compared to (2) Cost of finished product (raw materials);
the chloride process, both these are characterized by
(3) Location;
approximately equal costs of production of commercial
titanium dioxide. (4) Industrial potential (production facilities,
deposit reserve, etc.).
The sulfate method does not allow sulfuric acid to
be recycled; therefore, large-scale production of Table 1 shows the mineral and chemical composi-
sulfuric acid is necessary. The chloride process is operative tions of the concentrate from the Tugansk deposit in
only with rutile as raw material, so that this method is Tomsk oblast.
inapplicable in Russia, where natural rutile reserves are The technological process for the manufacture of
insignificant. titanium dioxide and iron oxide from the ilmenite
In addition, analysis of the sulfate and chloride concentrate includes the following steps:
technologies showed that their impacts on the environ- (1) Treatment of ilmenite concentrate with ammo-
ment are comparable. Ecological problems associated nium hydrogen difluoride at 150°C to produce ammo-
with utilization of hydrogen chloride in the chloride nium hexafluorotitanate and ammonium pentafluoro-
process, large amount of solid wastes from processing ferrate(II);
of ores with low titanium content, pollution of
wastewater, and the necessity of wastewater treatment (2) Decomposition of ammonium titanium fluoride
constitute an important factor retarding the develop- and ammonium iron fluoride complexes at 350°C;
ment of titanium dioxide market. (3) Separation of titanium fluoride by sublimation
It should be noted that titanium dioxide was at 550°C;
initially produced according to the sulfate method. (4) Desublimation of titanium fluoride by cooling
Since the development of the chloride process, the the process gas, its dissolution, and treatment with
contribution of the sulfate method to the total titanium aqueous ammonia to obtain titanium dioxide hydrate
dioxide production started to decrease. However, over (TDH); isolation of anatase TiO2 powder from the
a period of 1998 to 2009 the fraction of titanium di- TDH pulp;
oxide manufactured by the chloride method decreased
(5) Transformation of anatase TiO2 into rutile TiO2
from 60 to 57%. This reduction resulted from im-
at 800°C;
plementation of new facilities for the manufacture of
titanium dioxide by the sulfate method in China. Thus (6) Transformation of FeF2 into Fe2O3 via
we have one more example demonstrating that envi- pyrohydrolysis;
ronmental safety is sacrificed to gain economic profit. (7) Absorption of ammonia from the gas phase;
Fluoride process [43–48]. Exploitation of new (8) Evaporation of the ammonia mother liquors and
titanium dioxide deposits should be based on inno- crystallization of ammonia dihydrofluoride;

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 13 2013

6 VOZNYAKOVSKII et al.

Table 1. Mineral and chemical compositions of the ilmenite concentrate from the Tugansk deposit in Tomsk oblast
Chemical composition of
Mineral Concentration in ore, wt % Concentration of oxide in ore, wt %
mineral
Ilmenite 95.5 TiO2 63
FeO 25.1
Limonite 3 ZrO2 1.04
Zircon 1 SiO2 4
Chromite 0.5 Al2O3 0.36
Pyrite Scattered grains CaO 0.66
Anatase MgO 0.58
Leucoxene SO3 0.1
Rutile K2O 0.05
Sphene P2O5 0.1
Pyroxene Na2O 0.11
Kyanite Cr2O3 1.5
Sillimanite MnO 1.4

(9) Treatment with special reagents at the The process gas is purified from dust and is
calcination step to endow titanium dioxide with pigment transmitted to desublimation.
properties. NH3 + HF = NH4F.
The chemical processes occurring in the course of Titanium and iron fluorides are separated by sublima-
preparation of titanium dioxide according to the above tion in a furnace at 550°C. Titanium fluoride vaporizes,
operation sequence can be represented by the follow- and the process gas also contains ammonia and hydrogen
ing equations. fluoride. Separation of dust should be avoided (dust
Ilmenite concentrate is subjected to hydrofluorina- containing foreign metal fluorides may contaminate
tion in molten ammonium fluoride at 150°C in a final titanium dioxide). The process gas is subjected to
rotary-drum furnace. As a result, ammonium hexa- desublimation. The solid phase consists of iron(II) fluoride
fluorotitanate and ammonium pentafluoroferrate(II) are which is treated with water vapor and atmospheric
formed together with gaseous ammonia and water. oxygen at 200°C. This reaction yields iron(III) oxide and
gaseous hydrogen fluoride which is used to convert
FeTiO3 + 5.5NH4F·HF = (NH4)2TiF6 + (NH4)3FeF5
+ 0.5NH3 + 3H2O.
ammonium fluoride into ammonium hydrogen difluoride.
2FeF2 + 0.5O2 + 2H2O = Fe2O3 + 4HF,
To complete the reaction and ensure maximum
NH4F + HF = NH4F·HF.
extraction from ilmenite, the reactants should be
efficiently stirred. The process gas is purified from Solid iron(III) oxide is cooled and packed.
dust and is supplied to the “Ammonia station.” Desublimed titanium fluoride is dissolved in water and
treated with aqueous ammonia to precipitate titanium
NH3 + H2O = NH4OH.
hydroxide.
The ammonium metal fluoride complexes are
TiF4 + NH4OH = Ti(OH)4 + NH4F.
subjected to thermal decomposition in a furnace at
350°C, where gaseous ammonia, hydrogen fluoride, Titanium hydroxide is separated from ammonium
unreacted ammonium fluoride, and ammonium fluoride fluoride solution by filtration, and the precipitate is
silicon compound are removed. subjected to repulping with aqueous ammonia (25%) to
pH = 12. This procedure removes residual ammonium
(NH4)2TiF6 = NH4TiF5 + NH3 + HF,
fluoride, and subsequent filtration yields high-purity
(NH4)3FeF5 = FeF2 + NH3 + HF. titanium hydroxide.

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 ENVIRONMENTAL PROBLEMS OF FINELY DISPERSED TITANIUM DIOXIDE PRODUCTION 7

The mother liquors obtained after the first and Table 2. Main toxic chemicals involved in the technological
second filtrations are evaporated at 100°C to recover process
ammonium fluoride and are then used for the treatment Maximum allowable
of the next batch of ilmenite concentrate. If necessary, Class of
Toxic chemical concentration
hazard
ammonium fluoride is converted into ammonium in workplace air, mg/m3
hydrogen difluoride on heating at 170°C. Ammonium fluoride 1.0/0.2 2
2NH4F = NH4F·HF + NH3. NH4F
Ammonia NH3 20 4
Depending on the required structure of final
titanium dioxide pigment, titanium hydroxide paste is Hydrogen fluoride 0.5 2
(aqueous solution)
heated at 600°C to obtain rutile or at 800°C to obtain
anatase.
Ti(OH)4 =TiO2 + 2H2O.
The process gas is pipelined to desublimation
The process scheme is illustrated by Fig. 4. apparatus A117 (if A117 is remote from the sub-
Ilmenite concentrate and ammonium hydrogen difluo- limation furnace, the pipeline should be maintained at
ride are loaded into feeder bins A101 and A102 and are 300°C) where solid titanium fluoride and ammonium
supplied at a certain rate to screw mixer with the aid of fluoride separate from the gas phase.
dosing augers A103 and A104. The screw mixer
Iron fluoride from furnace A116 is transferred
should be cooled since the heat transferred from the
(through feeding bin A118 and dosing auger A119) to
furnace could initiate chemical reaction, which could
pyrohydrolysis furnace A120 heated to 200°C. Direct
lead in turn to sticking of the auger shaft with viscous
steam from steam generator A136 and preliminarily
intermediate products. The blend obtained in A105 is
heated atmospheric air are also supplied to A120. The
supplied at a required rate to rotary drum furnace A106
oxidative hydrolysis yields solid iron(III) oxide and
charged with grinding balls or rods and heated to 150°C.
gaseous hydrogen fluoride, and the latter is used to
The gas fraction containing ammonia and water is
prepare ammonium hydrogen difluoride via saturation
transferred through a pipeline to separator A107 (if the
of NH4F in A135. Iron(III) oxide is cooled in cooling
next apparatus is considerably distant from the
auger A137 and packed. Titanium fluoride and
leaching furnace, the pipeline should be heated to
ammonium fluoride obtained in A117 are dissolved in
240°C) where dust is separated, and solid particles are
water in agitator A121, and the solution is transferred
returned to the leaching furnace. The purified process
to A122 for precipitation with aqueous ammonia. As a
gas passes to aqueous ammonia setup A108. Inter-
result, hydrated titanium dioxide pulp containing
mediate product containing ammonium fluoride
dissolved ammonium fluoride is formed. The pulp is
titanium and iron complexes goes from furnace A106
subjected to first filtration in drum vacuum filter A123,
to bin A109 and is then transferred with the aid of
followed by washing and final filtration. The solid
dosing auger A110 to rotary drum furnace A111 heated
cake is dried in A126 where it is fed through feeder bin
to 350°C, where the complexes decompose with
A124 with dosing auger A125.
liberation of gaseous ammonia and hydrogen fluoride.
Titanium hydroxide is dried at 130°C, and the
The process gas is pipelined to dust separator A112,
removed water is transferred to the preparation of
and solid particles are returned to furnace A111. The
aqueous ammonia. The filtrate containing ammonium
purified process gas is transmitted to desublimation
fluoride is evaporated in screw crystallizer A132 at
apparatus A113 where ammonium hydrogen difluoride
105°C (or 70°C in a vacuum crystallizer). The water
is separated.
released from A132 is partly consumed for the dis-
The solid phase containing titanium and iron solution of the next titanium fluoride batch in A121,
fluorides is loaded into bin A114 and is supplied partly for pyrohydrolysis step in A120, and partly for
therefrom with the aid of dosing auger A115 into the preparation of aqueous ammonia. If necessary,
sublimation furnace A116 heated to 550°C. Titanium ammonium fluoride is converted into ammonium
fluoride sublimes, the gas phase also contains ammo- hydrogen difluoride in A132 at 170°C, and the
nia and hydrogen fluoride, and iron fluoride remains in liberated ammonia is used for the preparation of aqueous
the solid phase. ammonia.

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 13 2013

 8

FeTiO4 NHF–NF
NH4TiF5
Water out Aqueous
Condensate ammonia
A101 A102 A107 A114
TiF4

A117
A109
A121 A122

A115
Ti(OH)4

A103 A104
A106 A116 TiF4 A124
A123
A105
A126
A125 Exhaust
FeF2 vent

vent
Anatase TiO2

Exhaust
FeF2 Vacuum
A127
A129 A130
A109 A118 A128
A138 A131 A132
A136

A113
A112 NH4F
VOZNYAKOVSKII et al.

Steam generator
A133
A110 Water
A120
A119 A135 Water out
A134 in
A111 A132 Water
out NH4F
Water Water
in out
Water
NH4TiF in
NH4F–HF

Fig. 4. Process scheme for the production of titanium dioxide and iron oxide from ilmenite concentrate (for comments, see text).

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 13 2013

 ENVIRONMENTAL PROBLEMS OF FINELY DISPERSED TITANIUM DIOXIDE PRODUCTION 9

Table 3. Characteristics of different technologies for the production of pigmentary titanium dioxide
Technology Sulfate Chloride Fluoride
Feedstock material Ilmenite and titanium slag (with addi- Rutile (natural or synthetic) Ilmenite, rutile
tion of rutile), ??*??sphene, ??*?? and titanium slag containing (SiO2 <5%, Al2O3 and CaO
perovskite 55 to 60% of TiO2 are not limited)
(with addition of rutile, sphene, perovskite)

Pre-treatment (leaching) 85–92% H2SO4, 40 atm, 200–220°C; Desilication, reductive melting Decomposition in melt at
passing of pressurized air after melt- at 900–1200°C, magnetic sepa- 150–200°C, sublimation of
ing; maturing for 2–3 h ration, treatment with a solu- titanium tetrafluoride at 500°
tion of iron(III) chloride, C
chlorination of rutile

Hydrolysis of intermediate prod- Supersaturation of the solution, seed- Combustion of a mixture of Precipitation of hydrated tita-
uct ing, double filtration, bleaching puri- titanium tetrachloride and nium dioxide with aqueous
fication aluminum trichloride at 1000– ammonia (regeneration of
1200°C ammonium fluoride after
filtration)
Surface treatment Treatment with inorganic and organic Not required Not required
salts
Thermal treatment Rutilizing agents, 900–1000°C Dry air pulsation under high 700–800°C
pressure

Reagent regeneration directly in No Chlorine (95%), by combus- Ammonium fluoride, 97%;

the production process tion of titanium tetrachloride in aqueous ammonia, 95%
oxygen
Wastes (by-products) per metric Iron(II) sulfate, 3–5 t; 10% aqueous HCl, 0.35 t; Iron oxide pigment, 1 t
ton of titanium dioxide dilute sulfuric acid, ≤10 t; calcium hypochlorite solution,
polluted wastewater, ≤60 t 0.31 t

Environmental impact High Moderate Low

Class of hazard Moderate High Low

Pigment quality Medium High High

Net cost (kg) at a production $1.8–2.0 $1.6–1.8 $1.2–1.3

level of 2000 t annually (strongly depends on the sulfuric acid (excluding enrichment of tita- (excluding commercialization
price) nium slag or synthetic rutile of iron oxide pigment)
manufacture)

Anatase titanium dioxide from A126 is loaded into of hazardous chemicals into occupational air and
A127 and is fed with A128 to calcining furnace A129 prevent their impact on the operating personnel, we
where it is converted into rutile TiO2 at 800°C. Rutile propose the following technical measures:
TiO2 is cooled in A138 and packed.
(1) Organization of a continuous technological
Fluoride process risks. The fluoride technology process;
for the production of titanium dioxide involves some
adverse and harmful physical and chemical factors. (2) Automatic monitoring of the main process flow
Harmful chemical factors originate from circulation in parameters and deviation alarm;
the technological process of hazardous chemicals of (3) Remote control;
2nd to 4th class of hazard according to GOST (State
Standard) 12.1.005–88. In order to minimize discharge (4) Rational process area and equipment layout;

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10 VOZNYAKOVSKII et al.

(5) Full-time local and general ventilation of the (Table 3). It is seen that the latter offers considerable
process areas. Taking into account the possibility for advantages from the environmental and economic
accidental ammonia discharge, the process areas viewpoints. Moreover, the fluoride technology still has
should be equipped with gas analyzers with automatic not exhausted its possibilities for further improvement
warning of excess concentration of toxic chemicals; of ecological and process parameters. This work is
now in progress in Faktoriya LS.
(6) Pressurization of all equipment, pipelines, and
fittings, and isolation of all loading/unloading opera- For example, it was found that the use of excess
tions with loose materials; ammonium fluoride (5–15 wt %) ensures most com-
plete leaching of ilmenite. The subsequent separation
(7) The use of equipment and service lines made of of the titanium-containing component by sublimation
corrosion-resistant materials and fitting them with is accompanied by evaporation of excess fluorinating
built-in or covering local exhausts; agent and decomposition of ammonium metal fluoride
(8) Purging of equipment with an inert gas (nitro- complexes. The proposed solution makes it possible to
gen) before repair works; reduce by half the amount of mixture subjected to
precipitation. Correspondingly, a smaller amount of
(9) Mechanization of assembly, disassembly, and ammonia is required, and the energy consumption in
transport of equipment; the entire production process is reduced by 15–20%.
(10) Maintenance of safe working environment The developed technological scheme is now under
during repair works; laboratory testing.

(11) Monitoring of operation of the gas-cleaning Implementation of the fluoride technology in

units and discharge of hazardous chemicals into Russia is expected to afford efficient utilization of
atmosphere; natural resources in our country and increase of the
number of jobs without impairment of the environ-
(12) Provision of personal protective equipment; ment, in particular in the Tomsk region. Unfortunately,
the existing titanium dioxide production facilities
(13) The use of pressure suits for repair works.
designed for the sulfate technology will operate for a
Harmful physical factors include electric current, long time. Undoubtedly, studies aimed at improving
elevated temperature of materials and outer surface of both chemical and technological aspects of the titanium
equipment, moving parts of equipment. dioxide production process should be continued.

To protect personnel from harmful physical factors, REFERENCES

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