TECHNICAL FORUM

The final
frontier?
by
Michael
Clark, Whitehopleman
Technical
Forum has received a number of questions about the
TheDrCement
The cement technical forum has received a number of questions about the
addition of calcium fluoride to cement raw mix. The possibility that small
amounts of calcium fluoride can reduce the energy consumption of the kiln
is fairly widely known, but why is this? How much energy can be saved?
Are there other effects on kiln operation? Or on the quality of the clinker
or final cement? Dr Clark looks at the options.
he presence of fluoride in the raw
mix reduces the energy consumption of the kiln because the
fluoride
enters
into
solid
solution in the C3S, or alite, altering the
mineral and reducing the threshold temperature for formation of the mineral.
Formation of C3S is promoted at a lower
temperature, and less energy needs to be
supplied to bring the kiln up to this lower
threshold temperature. This process is
known as mineralisation.
As kiln fuel is one of the major costs
faced by cement companies, it might therefore be expected that all would add calcium
fluoride to their raw mix and reduce fuel consumption and costs. However, the high cost
of the calcium fluoride industrial mineral,
coupled with the other uncertainties highlighted above, generally prevents cement
companies from pursuing this strategy.

34

Some cement factories are fortunate

enough to have some calcium fluoride
naturally occurring in their raw materials.
Some other factories have conducted
trials with calcium fluoride additions
and adopted the long-term addition of the
mineral. From the experiences of these
factories some guidance on the answers
to important questions can be gained. The
following is based on some of these
experiences:
Between 20 and 50kJ/kg clinker can be
saved by the addition of each 0.1 per cent
of calcium fluoride to the raw mix. These
savings rise linearly up to 0.5 per cent
addition, beyond which the author is
unaware of further industrial experience.
The variation in the effectiveness is related
to the other components of the raw mix,
with the fluoride being most effective in
high silica modulus, low alkali mixes. Even
at the lower energy saving
it should be possible to
recover the cost of the
calcium fluoride in lower
fuel costs.
Cement companies worry
that alkali cycles and preheater
blockages
will
become more problematic,
or that there will be emissions of fluorine. Again
from the experience of the
same factories there is not
evidence of alkali cycle
problems. The temperature

INTERNATIONAL CEMENT REVIEW / MAY 2001

Improving the raw mix

in the burning zone is reduced and this

leads to lessening of the circulation of
alkalis. The calcium fluoride itself has a
low volatility and does not conspicuously
enter into a cycle in the kiln. All the fluoride is thus retained in the clinker and
there are no emissions of fluorine.
Again based on the experience, there is
a definite lengthening of the setting time
of mineralised cement containing fluoride.
The underlying reason for this is said to lie
in the changed C3S mineral structure and
hydraulic behaviour and also a change in
the amount of alumina entering into solid
solution in the silicate minerals. The formation of C11A7 CaF2 is not said to be the
cause of the long setting. In high earlystrength mineralised cements, gypsum is
also added to the raw mix to offset this
lengthening of the setting time.
Calcium fluoride additions to raw mix
should therefore be of great interest to
cement companies. Most other process
engineering means to reduce kiln fuel consumption have been exhausted. Extra
stages on the preheater have pulled down
exhaust gas losses to the economic minimum. The precalciner process has shortened kilns to minimise radiation losses.
The efficiency of direct aerated coolers is
also close to the limits of economic capability. The only major element of the modern kiln heat balance that might be
reduced is the 1250kJ/kg of clinker consumed by the chemical reactions of clinker
formation. Calcium fluoride seems to be
the best means to achieve this at the
current stage.
This can be seen as the next or the
final frontier in the evolution of cement
kiln technology. There is always a need for
more information from industrial experience. Perhaps some readers can share some
of their own experiences with fluoride in the
raw mix via the Cement Technical Forum?
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