Role of alkali, chloride and sulphates in the kiln

1. The alkali/sulphur ratio is used in two ways in kiln operation. The first is to measure if there is
a molar balance between the total inputs of alkalis and sulphur contributed by all of the raw
materials, fuels and AFR streams entering the kiln... the second is to measure the instantaneous
molar alkali/sulphur balance in the kiln/preheater system (based on hot meal)
Both use the same equation;-

{ K2O/94) + (Na2O/62) - (Cl/71) }
A/S = --------------------------------------------
(SO3/80)

However, if there is little or no chloride in the raw material and fuel inputs to the kiln, the
chloride component is often ignored when calculating the A/S ratio of the total inputs.

For hot meal though, chloride is always subtracted from the alkali molar total because alkali
chlorides are far more volatile than alkali sulphates and recirculate within the kiln. (Over 98% of
alkali chlorides (particularly KCl) are re-evaporated in the high temperature of the burning zone
and return to thekiln inlet with the kiln gases where they condense on the incoming hot meal and
continue to recycle.) Any K2O or Na2O tied up with the chlorides are therefore not considered
in the A/S ratio calculation for hot meal.
The purpose of the hot meal A/S ratio is to predict the likelihood of alkali or sulphur related
buildups in the kiln inlet. In particular, sudden decreases in this ratio can indicate lack of oxygen
in the back end of the kiln and impending sulphur buildups. A high value indicates an excess of
alkalis. The portion of the alkalis which do not combine with SO3 to form sulphates will also
recirculate in the kiln, increasing the potential for rings and preheater buildups.
When applied to the kiln material inputs, the alkali/sulphur ratio is used to manage raw material,
fuel and AFR inputs. New raw materials, fuels and AFRs should be chosen taking their effect on
the overall akali/sulphur ratio into consideration. Similarly, selective mining can "fine tune" the
chemistry of existing raw materials to optimise the raw mix alkali/sulphur ratio, if it is not
within the range 0.8 --> 1.2

2. If alkalis are very high and are not balanced by sulphur, it will be very difficult for them to
exit the kiln. They will therefore continue to recirculate within the kiln/preheater system and
increase the probabliity of kiln rings and preheater buildups. Clinker quality may suffer because
free alkalis can enter into solid solution within the clinker minerals affecting their reactivity.
3. If sulphur is very high and is not balanced by alkalis, it will also continue to recirculate within
the kiln/preheater system and increase the probabliity of kiln rings and preheater buildups.
Excess sulphur in the hot meal can also form sulphospurrite (2(CaO).SiO2.CaS04) in the middle
cyclones, which forms exceedingly hard and dense buildups which can take a long time to
remove. Clinker quality would also suffer because sulphur which is not combined with alkalis
forms a solid solution with the silicate minerals, particularly C2S (up to 2%). Sulphur
incorporated in this way stabilises C2S and inhibits its reaction with CaO to form C3S. As a
result, C2S content is increased and C3S content is decreased in the clinker, causing a reduction
in cement strengths.
4. If chloride is very high, it will first combine with all of the alkalis present forming alkali
chlorides which will recirculate in the kiln and increase the probability of buildups in the
preheater. Any remaining chloride will then combine with CaO to form CaCl2 which has a very
low melting point (770-780oC). This will make the hot meal extremely "sticky" at this
temperature and increase the chance of buildups higher up the preheater. Chlorides also form
eutectic mixtures with sulphates of potassium, sodium, calcium and magnesium. These eutectic
mixtures have melting points much lower than that of the pure compounds, further increasing the
likelyhood of rings and buildups. Above 0.015%, in the raw meal, chloride recirculation is so
bad that blockages in the preheater are eventually inevitable. If the chloride does manage to
escape the kiln(ie during kiln trips, stoppages etc), too much chloride in the clinker can
accelerate the corrosion of reinforcing steel in the concrete.