CemNet Training - Course CKPC01

Module 1 Session 6

Cement Kiln
Process Chemistry
Module 1. Cement kiln energy efficiency and
productivity.
1.6 Mineralisation.

Cement Kiln Chemistry

1.6 Mineralisation

In the preceding session we discussed the equilibrium of the

combination reaction between C2S and CaO to form C3S.
No C3S will be formed until the temperature rises above
1250C as the equilibrium of the reaction:
C2S + CaO

C3S

..is predominantly to the left.

Above 1250C the equilibrium shifts to the right to favour the
formation of C3S.
C2S + CaO

C3S

..with the formation of a liquid phase significantly

increasing the rate of reaction to form C3S
how can that be explained?

Cement Kiln Chemistry

1.6 Mineralisation

In the preceding session we discussed the equilibrium of the

combination reaction between C2S and CaO to form C3S.
No C3S will be formed until the temperature rises above
1250C as the equilibrium of the reaction:
C2S + CaO

C3S

..is predominantly to the left.

Above 1250C the equilibrium shifts to the right to favour the
formation of C3S.
C2S + CaO

C3S

The explanation relies on consideration of free energies and

chemical potentials of the reactants and products at different
temperatures.

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 6

1.6 Mineralisation

In the preceding session we discussed the equilibrium of the

combination reaction between C2S and CaO to form C3S.
Below 1250C the Gibbs Gibbs
Free Energy
free energy (chemical
potential) of C3S is higher
than free CaO or C2S and
therefore C3S will not be
formed from an intimate
mixture of CaO and C2S
because it is unstable.
CaO and C2S are stable...
...and C3S unstable.
C2S + CaO

CaO

C3S

C2S

Increasing SiO2 content

C3S

The equilibrium lies to the left.

Cement Kiln Chemistry

1.6 Mineralisation

In the preceding session we discussed the equilibrium of the

combination reaction between C2S and CaO to form C3S.
Above 1250C the Gibbs Gibbs
Free Energy
free energy (chemical
potential) of C3S is lower
than free CaO or C2S and
therefore C3S is the most
stable compound and will be
formed.
CaO

C3S

C2S

Increasing SiO2 content

Cement Kiln Chemistry

1.6 Mineralisation

In the preceding session we discussed the equilibrium of the

combination reaction between C2S and CaO to form C3S.
Above 1250C the Gibbs Gibbs
Free Energy
free energy (chemical
potential) of C3S is lower
than free CaO or C2S and
therefore C3S is the most
stable compound and will be
formed.
Dependent on the SiO2
CaO
content either CaO and C3S
are stable... ...or C3S and
C2S are stable.
C2S + CaO C3S
The equilibrium lies to the right.

C3S

C2S

Increasing SiO2 content

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 6

1.6 Mineralisation

In the preceding session we discussed the equilibrium of the

combination reaction between C2S and CaO to form C3S.
Above 1250C the Gibbs Gibbs
Free Energy
free energy (chemical
potential) of C3S is lower
than free CaO or C2S and
therefore C3S is the most
stable compound and will be
formed.
Dependent on the SiO2
CaO
CS
content either CaO and C3S
are stable... ...or C3S and
Increasing SiO content
C2S are stable.
C2S + CaO C3S
C3S will be formed because it is the most stable.
3

C2S

Cement Kiln Chemistry

1.6 Mineralisation

In the preceding session we discussed the equilibrium of the

combination reaction between C2S and CaO to form C3S.
Returning to the chemical Gibbs
Free Energy
potentials below 1250C
. .the free energy of any
compound can be reduced by
incorporation of minor
substitutions or impurities.
Most common impurities,
Na2O, K2O, SO3, Al2O3,
are incorporated in the
belite, C2S..
..free
energy of the C2S is
reduced.

CaO

Cement Kiln Chemistry

C3S

C2S

Increasing SiO2 content

1.6 Mineralisation

In the preceding session we discussed the equilibrium of the

combination reaction between C2S and CaO to form C3S.
Returning to the chemical Gibbs
Free Energy
potentials below 1250C
. .the free energy of any
compound can be reduced by
incorporation of minor
substitutions or impurities.
Most common impurities,
Na2O, K2O, SO3, Al2O3,
CaO
CS
are incorporated in the
belite, C2S..
..free
Increasing SiO content
energy of the C2S is
reduced.
.C2S is stabilised and formation of
C3S becomes more difficult.
3

C2S

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
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CemNet Training - Course CKPC01

Cement Kiln Chemistry

Module 1 Session 6

1.6 Mineralisation

In the preceding session we discussed the equilibrium of the

combination reaction between C2S and CaO to form C3S.
Returning to the chemical Gibbs
Free Energy
potentials below 1250C
. .the free energy of any
compound can be reduced by
incorporation of minor
substitutions or impurities.
Most common impurities,
Na2O, K2O, SO3, Al2O3,
CaO
CS
are incorporated in the
belite, C2S..
..free
Increasing SiO content
energy of the C2S is
reduced.
.Na2O, K2O, SO3 and Al2O3 inhibit
the formation of C3S.
3

C2S

Cement Kiln Chemistry

1.6 Mineralisation

In the preceding session we discussed the equilibrium of the

combination reaction between C2S and CaO to form C3S.
Returning to the chemical Gibbs
Free Energy
potentials below 1250C
. .the free energy of any
compound can be reduced by
incorporation of minor
substitutions or impurities.
Fluorides are an important
exception to the rule that
CaO
CS
impurities are
preferentially incorporated
Increasing SiO content
in C2S, belite fluorides are preferentially
incorporated in the alite, C3S, reducing its free energy.
3

C2S

Cement Kiln Chemistry

1.6 Mineralisation

In the preceding session we discussed the equilibrium of the

combination reaction between C2S and CaO to form C3S.
Returning to the chemical Gibbs
Free Energy
potentials below 1250C
. .the free energy of any
compound can be reduced by
incorporation of minor
substitutions or impurities.
Fluorides are preferentially
incorporated in the alite,
CaO
CS
C3S, reducing its free
energy.
Increasing SiO content
the temperature at which C3S becomes the
most stable compound is reduced..
..fluorides
mineralise the formation of C3S.
3

C2S

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 6

1.6 Mineralisation

In the preceding session we discussed the equilibrium of the

combination reaction between C2S and CaO to form C3S.
Mineralisation is sometimesGibbs
Free Energy
thought to be synonymous
with the production of
mineralised clinker, as
practiced at Aalborg in
Denmark, and promoted by
FL Smidth.
This does involve the
CaO
CS
CS
addition of fluoride to the
kiln feed
Increasing SiO content
but also in combination with sulphate, SO3, an
inhibitor.
.the principle aims relate to
clinker and cement quality.
3

Cement Kiln Chemistry

1.6 Mineralisation

In the preceding session we discussed the equilibrium of the

combination reaction between C2S and CaO to form C3S.
Mineralisation is sometimesGibbs
Free Energy
thought to be synonymous
with the production of
mineralised clinker, as
practiced at Aalborg in
Denmark, and promoted by
FL Smidth.
We will return to the subject
CaO
CS
of the quality related benefits
of mineralised clinker in
Increasing SiO content
module 2 of the course
in module 1 we are
focusing on the impact on kiln energy efficiency and
productivity.
3

C2S

Cement Kiln Chemistry

1.6 Mineralisation

In the preceding session we discussed the equilibrium of the

combination reaction between C2S and CaO to form C3S.
Mineralisation is sometimesGibbs
Free Energy
thought to be synonymous
with the production of
mineralised clinker, as
practiced at Aalborg in
Denmark, and promoted by
FL Smidth.
SO3 is an inhibitor, but it is
CaO
CS
CS
also a fluxing agent ..SO3
forms low temperature melts
Increasing SiO content
from ~1100Cclinker mineral formation takes place
through the medium of this SO3 melt..
.the SO3 also reduces
the viscosity of the C4AF and C3A melt when it forms.
3

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 6

1.6 Mineralisation

In the preceding session we discussed the equilibrium of the

combination reaction between C2S and CaO to form C3S.
Mineralisation is sometimesGibbs
Free Energy
thought to be synonymous
with the production of
mineralised clinker, as
practiced at Aalborg in
Denmark, and promoted by
FL Smidth.
SO3 is an inhibitor, but it is
CaO
CS
CS
also a fluxing agent ..SO3
forms low temperature melts
Increasing SiO content
from ~1100Chowever, this low temperature flux is
not useful in the absence of fluoride
.C3S is not stable at
those temperatures in the absence of fluoride.
3

Cement Kiln Chemistry

1.6 Mineralisation

In the preceding session we discussed the equilibrium of the

combination reaction between C2S and CaO to form C3S.
Mineralisation is sometimesGibbs
Free Energy
thought to be synonymous
with the production of
mineralised clinker, as
practiced at Aalborg in
Denmark, and promoted by
FL Smidth.
SO3 is an inhibitor, but it is
CaO
CS
CS
also a fluxing agent ..SO3
forms low temperature melts
Increasing SiO content
from ~1100Cin the presence of fluoride the combined
mineralisation effect of fluoride, and fluxing effect of
SO3 more than overcome the inhibiting effect of SO3.
3

Cement Kiln Chemistry

1.6 Mineralisation

Mineralisation of the raw mix fed to a cement kiln is not entirely

straight-forward.
Aalborgs technology and patent derive from a patent first taken
out by Blue Circle in the 1970s.
In part Blue Circles discoveries
arose for experience at their Hope
Works in the UK where fluoride, as
CaF2 in limestone, and sulphur, as
pyrites, FeS2, in shale, were present
in the raw materials.
Trials with mineralised kiln feed
were carried out on long wet, Lepol
and suspension preheater kilns..
..with severe
blockages of the preheater of the suspension preheater 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 6

1.6 Mineralisation

Mineralisation of the raw mix fed to a cement kiln is not entirely

straight-forward.
Aalborgs technology and patent derive from a patent first taken
out by Blue Circle in the 1970s.
In part Blue Circles discoveries
arose for experience at their Hope
Works in the UK where fluoride, as
CaF2 in limestone, and sulphur, as
pyrites, FeS2, in shale, were present
in the raw maerials.
Trials with mineralised kiln feed
were carried out on long wet. Lepol
and suspension preheater kilns..
..this increased
stickiness of the hot feed in the preheater is often
reported when mineralisation is introduced.

Cement Kiln Chemistry

1.6 Mineralisation

Mineralisation of the raw mix fed to a cement kiln is not entirely

straight-forward.
Mineralisation with fluoride will stabilise C3S and promote its
formation from CaO and C2S at 1170C.
in practice
~1350C is required to overcome the inhomogeneities in the kiln
feed we have already discussed.
Never-the-less this represents a reduction in the combination
temperature of 125~150C.
The kiln burning zone temperature must be reduced in response
to this lower combination temperature requirement.. .if
not the additional thermal energy input, over-and-above
that required for clinker combination, will be absorbed to
volatilise alkalis and sulphates from the kiln charge and a
heavy alkali cycle will develop.. ..leading to the hot
meal stickiness and preheater blockages.

Cement Kiln Chemistry

1.6 Mineralisation

Mineralisation of the raw mix fed to a cement kiln is not entirely

straight-forward.
Mineralisation with fluoride will stabilise C3S and promote its
formation from CaO and C2S at 1170C.
in practice
~1350C is required to overcome the inhomogeneities in the kiln
feed we have already discussed.
Never-the-less this represents a reduction in the combination
temperature of 125~150C.
The kiln burning zone temperature must be reduced in response
to this lower combination temperature requirement..
.kiln operators will need support and coaching to make
the necessary reductions in burning zone 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 6

1.6 Mineralisation

Mineralisation of the raw mix fed to a cement kiln is not entirely

straight-forward.
Mineralisation with fluoride will stabilise C3S and promote its
formation from CaO and C2S at 1170C.
in practice
~1350C is required to overcome the inhomogeneities in the kiln
feed we have already discussed.
Never-the-less this represents a reduction in the combination
temperature of 125~150C.
Provided the kiln burning zone temperature is lowered by this
amount the thermal energy requirement is significantly reduced..
.and therefore the amount of fuel which must be burnt
per tonne of clinker produced. ..kiln exhaust gas
volume is reduced and exhaust fan capacity released to
allow kiln output to be increased.

Cement Kiln Chemistry

1.6 Mineralisation

Mineralisation of the raw mix fed to a cement kiln is not entirely

straight-forward.
Mineralisation with fluoride will stabilise C3S and promote its
formation from CaO and C2S at 1170C.
in practice
~1350C is required to overcome the inhomogeneities in the kiln
feed we have already discussed.
Never-the-less this represents a reduction in the combination
temperature of 125~150C.
Thermal load on the burning zone refractories is also
significantly reduced .. .longer kiln campaigns between
..or less
refractory replacement should follow..
expensive refractories will be required to the desired
length of kiln campaign.

Cement Kiln Chemistry

1.6 Mineralisation

Mineralisation of the raw mix fed to a cement kiln is not entirely

straight-forward.
Mineralisation with fluoride will stabilise C3S and promote its
formation from CaO and C2S at 1170C.
in practice
~1350C is required to overcome the inhomogeneities in the kiln
feed we have already discussed.
Never-the-less this represents a reduction in the combination
temperature of 125~150C.
The lower temperature in the burning zone can cut NOx levels at
the kiln inlet to 40% of those prior to mineralisation..
.we are going to spend a couple of sessions talking about
NOx generation and emissions mitigation in Module 3...
..kiln feed mineralisation is one means to achieve
this... ...along with better quality clinker,
lower fuel consumption and more output.

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 6

1.6 Mineralisation

Mineralisation of the raw mix fed to a cement kiln is not entirely

straight-forward.
Mineralisation with fluoride will stabilise C3S and promote its
formation from CaO and C2S at 1170C.
in practice
~1350C is required to overcome the inhomogeneities in the kiln
feed we have already discussed.
Never-the-less this represents a reduction in the combination
temperature of 125~150C.
The lower temperature in the burning zone can cut NOx levels at
the kiln inlet to 40% of those prior to mineralisation..
.we are going to spend a couple of sessions talking about
NOx generation and emissions mitigation in Module 3...
..kiln feed mineralisation is one means to achieve
this... ...CO2 emissions will also be reduced as
a consequence of the lower fuel consumption.

Cement Kiln Chemistry

1.6 Mineralisation

Mineralisation of the raw mix fed to a cement kiln is not entirely

straight-forward.
Mineralisation with fluoride will stabilise C3S and promote its
formation from CaO and C2S at 1170C.
in practice
~1350C is required to overcome the inhomogeneities in the kiln
feed we have already discussed.
Never-the-less this represents a reduction in the combination
temperature of 125~150C.
The lower temperature in the burning zone can cut NOx levels at
the kiln inlet to 40% of those prior to mineralisation..
.we are going to spend a couple of sessions talking about
NOx generation and emissions mitigation in Module 3...
..kiln feed mineralisation is one means to achieve
this... ...one of the few win-win-win-win
options provided by cement kiln chemistry!

Cement Kiln Chemistry

1.6 Mineralisation

Mineralisation of the raw mix fed to a cement kiln is not entirely

straight-forward.
F.L. Smidth promote the production of mineralised clinker and
have developed methodologies to overcome the difficulties
which can arise.
The first requirement is to install the equipment to dose the
fluoride and sulphate needed for the production of mineralised
clinker.
This might simply be additional feed bins and weigh feeders to
dose the fluoride mineral and gypsum into the raw mill.

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 6

1.6 Mineralisation

Mineralisation of the raw mix fed to a cement kiln is not entirely

straight-forward.
F.L. Smidth promote the production of mineralised clinker and
have developed methodologies to overcome the difficulties
which can arise.
The first requirement is to install the equipment to dose the
fluoride and sulphate needed for the production of mineralised
clinker.
If the additional sulphur is to be provided by a high sulphur fuel,
such as petroleum coke, then there are modifications to solid fuel
grinding circuits, precalciners and main burners that may be
required.. ..that is a technology in itself and not
specifically related to mineralisation.

Cement Kiln Chemistry

1.6 Mineralisation

Mineralisation of the raw mix fed to a cement kiln is not entirely

straight-forward.
F.L. Smidth promote the production of mineralised clinker and
have developed methodologies to overcome the difficulties
which can arise.
As discussed a couple of sessions ago mineralisation might the
solution if the kiln feed is particularly hard to burn
..allowing rotational speed to be increased and kiln output to
be boosted..or if a two support, short rotary kiln
does not provide sufficient residence time for the sintering
reactions to be completed.

Cement Kiln Chemistry

1.6 Mineralisation

Mineralisation of the raw mix fed to a cement kiln is not entirely

straight-forward.
F.L. Smidth promote the production of mineralised clinker and
have developed methodologies to overcome the difficulties
which can arise.
As previously stated the burning zone temperature must be
reduced to prevent the volatilisation of alkalis
..sulphate volatilisation is particularly to be avoided with the
Aalborg technology as sulphur loads in the kiln are boosed as
part of the technology. .the main burner of the
kiln may require modification to avoid these problems.
These issues of volatile cycles in the kiln will be the topic of
the next sessions of the course.

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

Module 1 Session 6

Cement Kiln
Process Chemistry
Module 1. Cement kiln energy efficiency and
productivity.
1.6 Mineralisation.

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