Titanium dioxide

Titanium dioxide has remarkable optical properties, with a very high

refractive index close to that of diamond. It is also a very stable compound and
can be heated to over 2000 K before melting. It is these properties that underlie
its most important uses.

Uses of titanium dioxide

Titanium dioxide is the most used white pigment and provides whiteness and opacity
for paints and coatings (including glazes), plastics and paper.
It has many speciality uses. It is resistant to UV radiation and thus does not discolour
over a long period of time and ultra pure and fine crystal titanium dioxide grades are
being increasingly used for sun screens.
It is also being used in novel nanotechnology applications.

Figure 1 Uses of titanium dioxide

Data for 2013, Merchant Research and Consulting, 2015
Much smaller amounts of titanium dioxide are used as a semi-conductor and to catalyse
the photodecomposition of water into hydrogen and oxygen.
It also has a high dielectric constant and a high resistance and thus it is used to make
capacitors.
The strong bonding between titanium and oxygen gives great thermal stability, melting at
2100 K. It is thus used as a ceramic material. It is also used to increase the acid
resistance of vitreous enamels.
Annual production of titanium dioxide
World 5.7 million tonnes 1

China 2.7 million tonnes 1

US 1.3 million tonnes 2

Europ 1.3 million tonnes 1

e
1. Data for 2013, Merchant Research and Consulting, 2015
2. 2018 Elements of the Business of Chemistry, American Chemistry Council.

Manufacture of titanium dioxide

There are two main processes, the Sulfate Process and the Chloride Process (Table 1)
which use the two principal ores, ilmenite and rutile, respectively. Ilmenite contains 45-
60% TiO and rutile contains up to 99% TiO . The ores are mined worldwide but most
2 2

production is in Australia and South Africa.

Each large producer of titanium dioxide balances its production between the two
processes. Each produces the oxide in the rutile crystal form but the Sulfate
Process can also produce another form of the oxide, anatase, which is softer and
which is used for a small number of specialist applications.
The Sulfate Process is run as a batch process; the Chloride Process is run as
a continuous process.
It is estimated that about 65% of the world's production is based on the Chloride Process.
Sulfate Process Chloride Process
long established
and simple new technology
technology
uses lower grade, needs high grade
cheaper ores ore
batch process continuous process
small amounts of
large amounts of waste formed with
waste materials toxicity problems:
Cl and TiCl
2 4

recovery and
pollution control
recycling of
expensive
chlorine possible
produces anatase only produces rutile
and rutile pigments pigments

Table 1 Comparison of the two processes for the manufacture of titanium dioxide.
The Sulfate Process
The chemistry of the process involves three main stages:
a) dissolving the ore
b) formation of hydrated titanium dioxide
c) formation of anhydrous titanium dioxide
(a) Dissolving the ore
The ore is usually ilmenite, FeTiO . It is ground finely and dissolved in sulfuric acid to
3

form a mixture of sulfates:

Before the titanium dioxide is extracted, the iron ions must be removed from the solution
so that the colour of the final product is not spoiled. The solution is therefore reacted with
recycled iron sources to convert any iron(lll) ions that may be present to iron(ll) ions:

The solution is allowed to stand so that the unreacted solid settles, and the clear liquid is
poured off before being concentrated by evaporation. Cooling then allows light green
crystals of iron(ll) sulfate to form and to be filtered off. These are sold separately. The
remaining solution contains titanyl sulfate, TiOSO4.
(b) Formation of hydrated titanium dioxide
The next stage involves the hydrolysis of the titanyl sulfate in solution to give insoluble,
hydrated titanium dioxide:

This is a critical stage and the conditions must be controlled to ensure that the precipitate
is suitable for filtering and roasting.
(c) Formation of anhydrous titanium dioxide
The final stage of the process is the heating of the solid in a furnace, known as a calciner.
This is a rotating cylinder which is typically heated by gas flames. As the cylinder turns,
the titanium dioxide passes along it and its temperature rises from 313 K, as it enters, to
over 1000 K as it leaves:

Heating evaporates the water and decomposes any remaining sulfuric acid in the solid.
After cooling, the product is 'milled' to form crystals of the size needed. Crystals may
also be coated with another substance, such as aluminium oxide or silica, to make the
titanium dioxide mix more easily with liquids or to make the water-based paints made
from it last longer.
This coating is achieved by dispersing the dry product from the calciner in water
containing the dissolved coating chemicals which precipitate from solution onto the
TiO2 crystals. The coating is usually between 3 and 8% by weight in the final dried
pigment. This coating is achieved by changing the temperature and pH of the solution.
Each TiO2 crystal needs to be coated uniformly to maximize the effectiveness of the
coating. The coated TiO2 crystals are filtered from the water and dried before being
packed for dispatch to the final customer.
The Chloride Process
There are two main stages:
a) the conversion of rutile to titanium(IV) chloride
b) the oxidation of titanium(IV) chloride
(a) The conversion of rutile to titanium(IV) chloride
The rutile is fed into a heated bed together with a source of carbon, usually coke.
Chlorine is fed into the bed and the reaction takes place to form titanium(IV) chloride in
the vapour form which is removed from the bed. Iron and other metals in the ore are
chlorinated and also leave the bed in the vapour state. The oxygen in the ores is
combined with the carbon to form carbon monoxide and dioxide. The vapour stream is
cooled and the metal chlorides other than titanium(IV) chloride are condensed and
solidified. The titanium(IV) chloride vapour, which contains almost pure titanium(IV)
chloride and has a lower boiling point, is then condensed and stored as liquid. It is then
reboiled and distilled to give a purer product to feed to the next stage.
(b) The oxidation of titanium(IV) chloride
Liquid titanium(IV) chloride is vaporised and burnt in oxygen, together with a hydrocarbon
fuel source (for example, methane) to a high temperature to initiate the reaction and keep
the temperature high enough for the reaction to proceed:

The titanium dioxide is formed (by adding seed crystals) as a fine solid in the gas stream
and is filtered out of the waste gases using cyclones or filters. Once again control of
crystal growth is important to give particles of the correct size for pigments. This is done
by adding nucleating agents to the gas stream (e.g. water or aluminium chloride) and by
cooling the products. The chlorine in titanium(IV) chloride is released and recycled to the
chlorination stage of the process above.
The product contains small amounts of absorbed chlorine gas which are removed. The
product is washed and dried before milling and surface treatment in an identical manner
to that used in the Sulfate Process described.