Cement Kiln Chemistry 1.

4 Preheating and Calcination

Cement Kiln Process Chemistry

Module 1. Cement kiln energy efficiency and productivity.
1.4 Preheating and Calcination

In the preceding session we saw that thermodynamics alone cannot explain the
differences in burnability of cement raw mixes and thermal energy efficiency of cement
kilns.

It is also important to consider the kinetics of the individual reactions

taking place in the different sections of the kiln. How quickly will the
reactions take place?…Will the reactions be completed in the appropriate
sections of the kiln?

In the preceding section we learned that CaCO3 calcination is the reaction

which consumes the most energy in the decomposition of the raw
minerals in the kiln feed. In this session we will further explore the
CaCO3 calcination reaction and its kinetics.

All the raw minerals in the cement kiln feed raw mix will dissociate
below 1000°C. In a pure CO2 atmosphere CaCO3 starts to dissociate at
900°C, at lower CO2 partial pressure the dissociation of CaCO3 starts at
a lower temperature. Therefore, the calcination in a separate line calciner
would be expected to commence at a lower temperature than in an in-
line calciner.

An in-line calciner is swept with vitiated gases from the kiln containing
the CO2 and H2O combustion products from the main burner, and
therefore the partial pressure of CO2 is higher.

A separate line calciner is swept with pure tertiary air containing

virtually no CO2.

FL Smidth Separate-line (SLC) precalciner

The calcination in kilns fired with natural gas might be at a

lower temperature than those fired with coal or oil as the
natural gas produces less CO2 in the combustion products
when burnt.

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Cement Kiln Chemistry 1.4 Preheating and Calcination

The fineness and crystal structure of the CaCO3 are also

important determinants of CaCO3 reaction temperature and
velocity.

A finer ground raw mix is likely to begin to calcine at a lower

temperature, and complete its calcination more quickly. A
highly crystalline marble or calcite is likely to calcine at a
higher temperature than a limestone or marl.

However, the most important determinant of the CaCO3 reaction temperature and
velocity are the reactions which take place with the decomposing acidic components of
the kiln feed (the SiO2, Al2O3, Fe2O3) and the reactivity of the acidic minerals.

Clay minerals start to decompose at ~500°C+, producing highly reactive, finely divided
SiO2 and Al2O3. These react with CaCO3 to produce calcium silicates, aluminates and
ferrites at well below the dissociation temperature of CaCO3. No CaO is produced until
the temperature exceeds 850°C, all the CaO from the dissociation of CaCO3 below this
temperature reacts with the acidic SiO2, Al2O3 and Fe2O3 to produce low lime silicates
and aluminates.

Quartz is more crystalline and breaks down more slowly to

produce silicic acid which then reacts with the CaCO3 to
produce low lime silicates. Particle size of the quartz is the
critical factor, explaining the importance of the granulometry
of the kiln feed. In natural clays any quartz grains can vary in
size affecting the reactivity of the clay.

If silica sand is added to boost the silica modulus, then this will
concentrate in the coarse fraction of the ground mix due to the
low grindability of quartz compared with limestone,
exacerbating the low reactivity of the quartz. Some siliceous
minerals have intermediate reactivity between the clay
minerals and quartz sand, i.e. chalcedony, opal, mica, feldspars
and glasses.

The origin of the Al2O3 and Fe2O3 also affects the reactivity of
the kiln feed. Al2O3 and Fe2O3 derived from the clay minerals
are more reactive than when derived from the hydroxides,
bauxite and laterite. The hydroxides, bauxite and laterite,
dissociate below 500°C, which is too low a temperature to
react with CaCO3. The Al2O3 and Fe2O3 produced, therefore
recrystallise and stabilise before reacting with CaCO3.

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Cement Kiln Chemistry 1.4 Preheating and Calcination

The effects of the rate of heating are complex, with the conduction of heat into the centre
of the particles sometimes being a deciding factor.

If the surface of the particles is at the CaCO3 dissociation

temperature, but not the centre then, the outer layers may CO2
calcine. The partial pressure of CO2 in the outer layers of the
CO2
particle is then raised inhibiting calcination of the centre. CO2

Finer grinding helps to allevatiate these potential problems.

CO2 CO2
On long kilns this can be the reason for slower kiln speed
assisting in the combination of the clinker. However, with
CO2
preheater, and particularly precalciner kilns, slowing the kiln
speed is generally detrimental to energy efficiency and
productivity.

Once the CaCO3 has been calcined very rapid heating from the calcination temperature of
850~900°C is beneficial. The newly liberated CaO does not then have time to
recrystallise before reacting with SiO2 to increase the lime content of the silicate
minerals. The CaO contains many lattice defects and voids and is highly reactive towards
the acidic minerals in the kiln.

This is one of the principal benefits put forward for short,

two-support rotary kilns. The CaO formed in the precalciner
is transported as quickly as possible to the burning zone due
to the short length of the kiln and therefore remains highly
reactive. This is also the explanation for the benefits of high
kiln rotational speed of 3.5 rpm+, particularly with
precalciner kilns.

However, with particularly hard to burn raw materials short

rotary kilns and high rotational speed may not allow
sufficient time for the sintering reactions. In that case finer grinding of the kiln feed, or
the use of mineralisers might be a solution, we will consider mineralization a little later.

Besides the clay minerals other potential raw mix components can accelerate the
dissociation velocity of CaCO3. Alkali salts precipitating on the surface of the CaCO3
will accelerate the dissociation - the reactions of the alkalis in the cement kiln will be the
major topic of the second part of this module. Sodium silicofluoride, basalt, lead and
copper slags, apatite and phosphorous slag will all reduce the activation energy of CaCO3
dissociation, leading to increased kiln output due to accelerated CaCO3 calcination.

All these effects on the calcination reaction kinetics. CO2 partial pressure, kiln feed
granulometry, CaCO3 crystallinity and acidic mineral reactivity affect the temperature at
which CaCO3 dissociation takes place and the operating temperature of a precalciner.

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Cement Kiln Chemistry 1.4 Preheating and Calcination

CaCO3 dissociation takes place from ~550°C by reaction of the liberated SiO2 and Al2O3
from the clay minerals. However, only at higher temperatures does the rate of
dissociation increase sufficiently for the temperature to stabilise as the endothermic
calcination reaction absorbs the heat energy in the precalciner.

After completion of the dissociation of the CaCO3 the sintering reactions are the next
stage of the formation of cement clinker, these will be the topic of the next session of the
course. However, we cannot leave the reactions taking place in the preheater without
discussing the phenomena of recarbonation.

The cyclones in a cement kiln preheater do not have

100% collection efficiency. Some of the feed
entering the cyclone is not collected and passes out
of the cyclone, up the preheater tower with the
exhaust gas.

The cyclones at the bottom of the preheater tower

may have collection efficiencies of 85% or lower,
meaning that there is a considerable recirculating
load of material in the preheater. Feed

The CaO in the calcined material in the lower stage

cyclones can recarbonate in the higher stages of the
preheater.

CaO + CO2 → CaCO3

This liberates exothermic energy in the higher stages of the preheater.

Thermodynamically this does not affect the overall heat of clinker formation- the same
amount of energy is liberated by the recarbonation as is consumed by the calcination.

However, recarbonation can significantly reduce the thermal energy efficiency and
productivity of a cement kiln. In a similar fashion to pyrites and organic carbon in the
kiln feed the effect is to increase the temperatures higher up the preheater. Preheater
exhaust gas temperatures rise and with them energy losses and the thermal energy
consumption of the kiln. F.L. Smidth’s models of cement kilns suggest that each 1%
increase in recarbonation in the preheater results in ~ 2 kJ/kg clinker increased thermal
energy consumption and a ~1°C rise in preheater exhaust gas temperature.

Low efficiency of the lower stage cyclones in the preheater is a common root cause for
higher fuel consumption and low productivity of cement kilns. In the next session of the
course we will cover the sintering reactions undergone by the CaO liberated from the
CaCO3 in the calcination reactions.

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