DIAH AYU SAFITRI

2713100053

Manufacturing TiO2 Particles by Chloride Process

TiO2 pigment is a white powder with high opacity, brilliant whiteness, excellent
covering power and resistance to colour change. These properties have made it a valuable
pigment and opacifier for a broad range of applications in paints, plastics, inks and paper. The
TiO2 pigment is made by two commercial processes sulphate and chloride. The chloride
process has become more dominant process because it produces superior pigment with
significantly fewer waste products. The flow charts in below illustrate, in simplified form, the
chloride processing routesfor TiO2 pigment production.

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The chloride process can be summarized as follows:

TiO2-containing ore, coke, O2, and Cl2 gas are fed into a fluidized bed reactor (chlorinator)
where they react to form TiCl4, additional metal chlorides, and other byproducts.
The crude TiCl4 is condensed and distilled to remove impurities. It is then stored as a liquid.
Off gas is sent to a scrubbing system. (HCl in this off gas is what we will purify and
concentrate.)
Purified TiCl4 is vaporized and fed into the oxidizer (labeled burner in Fig. 1) along with O2,
gaseous AlCl3, a combustible fuel, and other additives. While the target reaction is the
production of fine TiO2 particles from TiCl4 and O2, byproducts make up a significant
portion of the product stream.
The oxidizer product stream is rapidly cooled and TiO2 particles are filtered and collected.
The gas separated from the TiO2 particles during filtration, largely composed of Cl2, is
recycled to the chlorinator.
Following filtration, several finishing steps (e.g. milling, surface treatments, etc.) may be
necessary before the TiO2 particles are packaged and ready for shipment.

The design project 1 pose aims to capitalize on HCl produced during this process. Off gas
sent to the scrubber contains significant amounts of HCl which is of potential economic
value. The challenge is to purify and concentrate the HCl from around 17% to a percentage
that is sellable. Students should design an HCl purification and concentration system which
can produce either 33-38% HCl or 100% HCl based on sound chemical engineering
principles and economic analyses.
For the chloride process with a recycle loop, students should consider the following:
Assume an annual TiO2 production of 100,000 tons for an average manufacturing site.
HCl produced in the chloride process may contain dissolved solids at nearly 0.3% TiO2
and/or 0.3% SiO2.
Typical moisture content in the ore is approximately 0.2%, for the coke its approximately
0.6%, and hydrogen content in the coke is approximately 0.2%.
The amount of ore needed will be dependent on the TiO2 content in the ore selected.
Chlorination occurs at temperatures of around 1000 C, burning approximately 350-375 kg of
coke in the chlorinator per ton of TiO2 produced.
TiCl4 and AlCl3 may be preheated to around 500-1000 C and O2 may be preheated to
around 1000 C before injection into the oxidation reactor.
A typical oxidizer operates at around 1400-1600 C, burning a combustible fuel to supply
roughly 120-170 kW of power per ton of TiO2 produced.
Oxygen is supplied to the oxidizer in 5-20% stoichiometric excess to ensure that all TiCl4
reacts.
AlCl3 is supplied such that the TiO2 particles contain 0.5-1.5% Al2O3.
The oxidizer product must be rapidly cooled to below 600 C in order to prevent further
aggregation and/or agglomeration of particles. The temperature rating of the particle filter
need also be considered.
The recycled chlorine stream from the oxidizer to the chlorinator may contain additional
byproducts from reactions in the oxidizer.
Note that not all specifications listed above need be considered for the design of a
standalone HCl purification and concentration system. However if such a system is to be
integrated into the chloride process for continuous plant operation, then the above process
specifications (e.g. as necessary for material and energy balance) will be of particular
importance.