CemNet Training - Course CKPC01

Module 1 Session 4

Cement Kiln
Process Chemistry
Module 1. Cement kiln energy efficiency and
productivity.
1.4 Preheating and calcination.

Cement Kiln Chemistry

1.4 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?

Cement Kiln Chemistry

1.4 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.
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.

This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd
http://Training.CemNet.com

CemNet Training - Course CKPC01

Cement Kiln Chemistry

Module 1 Session 4

1.4 Calcination

All the raw minerals in the cement kiln feed raw mix will dissociate
below 1000C.
In a pure CO2 atmosphere CaCO3 starts to
dissociate at 900C.. ..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.
FL Smidth Separate-line (SLC) precalciner

Cement Kiln Chemistry

1.4 Calcination

All the raw minerals in the cement kiln feed raw mix will dissociate
below 1000C.
In a pure CO2 atmosphere CaCO3 starts to
dissociate at 900C.. ..at lower CO2
partial pressure the dissociation of CO2 starts at a
lower temperature.
Therefore the calcination in a separate line
calciner would be expected to commence at a
lower temperature than an in-line calciner.
A separate line calciner is swept with pure
tertiary air containing virtually no CO2.

FL Smidth Separate-line (SLC) precalciner

Cement Kiln Chemistry

1.4 Calcination

All the raw minerals in the cement kiln feed raw mix will dissociate
below 1000C.
In a pure CO2 atmosphere CaCO3 starts to
dissociate at 900C.. ..at lower CO2
partial pressure the dissociation of CO2 starts at a
lower temperature.
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.

This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd
http://Training.CemNet.com

CemNet Training - Course CKPC01

Cement Kiln Chemistry

Module 1 Session 4

1.4 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.
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.

Cement Kiln Chemistry

1.4 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.
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 ~500C+, 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.

Cement Kiln Chemistry

1.4 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.
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 ~500C+, producing highly
reactive, finely divided SiO2 and Al2O3.
No CaO is produced until the temperature exceeds 850C, 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.

This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd
http://Training.CemNet.com

CemNet Training - Course CKPC01

Cement Kiln Chemistry

Module 1 Session 4

1.4 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.
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,
and the reactivity of the
Al2O3, Fe2O3)
acidic minerals.
Quartz is more crystalline and breaks
down more slowly to produce silicic
acid which then reacts with the CaCO3
to produce low lime silicates.

Cement Kiln Chemistry

1.4 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.
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.
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.

Cement Kiln Chemistry

1.4 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.
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.
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.

This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd
http://Training.CemNet.com

CemNet Training - Course CKPC01

Cement Kiln Chemistry

Module 1 Session 4

1.4 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.
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,
and the reactivity of the
Al2O3, Fe2O3)
acidic minerals.
Some siliceous minerals have
intermediate reactivity between the clay
minerals and quartz sand, i.e.
chalcedony, opal, mica, feldspars and
glasses.

Cement Kiln Chemistry

1.4 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.
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.
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.

Cement Kiln Chemistry

1.4 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.
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.
The hydroxides, bauxite and laterite,
dissociate below 500C, which is too low
a temperature to react with CaCO3.
The Al2O3 and Fe2O3 produced, therefore
recrystallise and stabilise before reacting
with CaCO3.

This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd
http://Training.CemNet.com

CemNet Training - Course CKPC01

Cement Kiln Chemistry

Module 1 Session 4

1.4 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.
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
calcine.

CO2
CO2

CO2

CO2

CO2

The partial pressure of CO2 in the outer layers

of the particle is then raised inhibiting
calcination of the centre.

CO2

Cement Kiln Chemistry

1.4 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.
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.
CO
Finer grinding helps to allevatiate these
CO
potential problems.
CO
On long kilns this can be the reason for
CO
slower kiln speed assisting in the
combination of the clinker.
CO
However, with preheater, and particularly precalciner
kilns, slowing the kiln speed is generally detrimental
to energy efficiency and productivity.
2

CO2

Cement Kiln Chemistry

1.4 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.
Once the CaCO3 has been calcined very rapid heating from the
calcination temperature of 850~900C 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 document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd
http://Training.CemNet.com

CemNet Training - Course CKPC01

Cement Kiln Chemistry

Module 1 Session 4

1.4 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.
Once the CaCO3 has been calcined very rapid heating from the
calcination temperature of 850~900C is beneficial.
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.

Cement Kiln Chemistry

1.4 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.
Once the CaCO3 has been calcined very rapid heating from the
calcination temperature of 850~900C is beneficial.
This is also the explanation for the
benefits of high kiln rotational
speed of 3.5 rpm+, particularly
with precalciner kilns.

Cement Kiln Chemistry

1.4 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.
Once the CaCO3 has been calcined very rapid heating from the
calcination temperature of 850~900C is beneficial.
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 mineralisation
a little later in this module.

This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd
http://Training.CemNet.com

CemNet Training - Course CKPC01

Cement Kiln Chemistry

Module 1 Session 4

1.4 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.
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.

Cement Kiln Chemistry

1.4 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.
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.
CaCO3 dissociation takes place from ~550C 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.

Cement Kiln Chemistry

1.4 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.
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.

This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd
http://Training.CemNet.com

CemNet Training - Course CKPC01

Cement Kiln Chemistry

Module 1 Session 4

1.4 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.
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.

Feed

Cement Kiln Chemistry

1.4 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.
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

Cement Kiln Chemistry

1.4 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.
The CaO in the calcined material
in the lower stage cyclones can
recarbonate in the higher stages
of the preheater.
CaO + CO2 CaCO3

Feed

This liberates exothermic energy in the higher stages of the

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

This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd
http://Training.CemNet.com

CemNet Training - Course CKPC01

Cement Kiln Chemistry

Module 1 Session 4

1.4 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.
The CaO in the calcined material
in the lower stage cyclones can
recarbonate in the higher stages
of the preheater.
CaO + CO2 CaCO3

Feed

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.

Cement Kiln Chemistry

1.4 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.
The CaO in the calcined material
in the lower stage cyclones can
recarbonate in the higher stages
of the preheater.
CaO + CO2 CaCO3

Feed

However, recarbonation can significantly reduce the thermal

energy efficiency and productivity of a cement kiln..
.preheater exhaust gas temperatures rise and with them
energy losses and the thermal energy consumption of the kiln.

Cement Kiln Chemistry

1.4 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.
The CaO in the calcined material
in the lower stage cyclones can
recarbonate in the higher stages
of the preheater.
CaO + CO2 CaCO3

Feed

F.L. Smidths 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 ~1C rise
in preheater exhaust gas temperature.

This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd
http://Training.CemNet.com

CemNet Training - Course CKPC01

Cement Kiln Chemistry

Module 1 Session 4

1.4 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.
The CaO in the calcined material
in the lower stage cyclones can
recarbonate in the higher stages
of the preheater.
CaO + CO2 CaCO3

Feed

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.

Cement Kiln Chemistry

1.4 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.
The CaO in the calcined material
in the lower stage cyclones can
recarbonate in the higher stages
of the preheater.
CaO + CO2 CaCO3

Feed

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.

Cement Kiln
Process Chemistry
Module 1. Cement kiln energy efficiency and
productivity.
1.4 Preheating and calcination.

This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd
http://Training.CemNet.com