CemNet Training - Course CKPC01 Module 1 Session 6

This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent fromTradeship Publications Ltd
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1.6 Mineralisation.
Cement Kiln
ProcessChemistry
Module 1. Cement kiln energy efficiency and
productivity.
Cement Kiln Chemistry
1.6 Mineralisation
In the preceding session we discussed the equilibriumof the
combination reaction between C
2
S and CaOto formC
3
S.
No C
3
S will be formed until the temperature rises above
1250C as the equilibriumof the reaction:
C
2
S + CaO C
3
S

..is predominantly to the left.

..with the formation of a liquid phase significantly
increasing the rate of reaction to formC
3
S
Above 1250C the equilibriumshifts to the right to favour the
formation of C
3
S.
C
2
S + CaO C
3
S

how can that be explained?

Cement Kiln Chemistry
In the preceding session we discussed the equilibriumof the
combination reaction between C
2
S and CaOto formC
3
S.
No C
3
S will be formed until the temperature rises above
1250C as the equilibriumof the reaction:
C
2
S + CaO C
3
S

..is predominantly to the left.

Above 1250C the equilibriumshifts to the right to favour the
formation of C
3
S.
C
2
S + CaO C
3
S

The explanation relies on consideration of free energies and

chemical potentials of the reactants and products at different
temperatures.
1.6 Mineralisation
CemNet Training - Course CKPC01 Module 1 Session 6
This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent fromTradeship Publications Ltd
http://Training.CemNet.com
...and C
3
S unstable.
Cement Kiln Chemistry
In the preceding session we discussed the equilibriumof the
combination reaction between C
2
S and CaOto formC
3
S.
CaOand C
2
S are stable...
1.6 Mineralisation
Below 1250C the Gibbs
free energy (chemical
potential) of C
3
S is higher
than free CaOor C
2
S and
therefore C
3
S will not be
formed froman intimate
mixture of CaOand C
2
S
because it is unstable.
CaO C
3
S C
2
S
IncreasingSiO
2
content
Gibbs
FreeEnergy
C
2
S + CaO C
3
S
The equilibriumlies to the left.

Cement Kiln Chemistry

In the preceding session we discussed the equilibriumof the
combination reaction between C
2
S and CaOto formC
3
S.
1.6 Mineralisation
Above 1250C the Gibbs
free energy (chemical
potential) of C3S is lower
than free CaOor C
2
S and
therefore C
3
S is the most
stable compound and will be
formed.
CaO C
3
S C
2
S
IncreasingSiO
2
content
Gibbs
FreeEnergy
Cement Kiln Chemistry
In the preceding session we discussed the equilibriumof the
combination reaction between C
2
S and CaOto formC
3
S.
Dependent on the SiO
2
content either CaOand C
3
S
are stable...
1.6 Mineralisation
Above 1250C the Gibbs
free energy (chemical
potential) of C3S is lower
than free CaOor C
2
S and
therefore C
3
S is the most
stable compound and will be
formed.
CaO C
3
S C
2
S
IncreasingSiO
2
content
Gibbs
FreeEnergy
...or C
3
S and
C
2
S are stable.
C
2
S + CaO C
3
S

The equilibriumlies to the right.

CemNet Training - Course CKPC01 Module 1 Session 6
This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent fromTradeship Publications Ltd
http://Training.CemNet.com
Cement Kiln Chemistry
In the preceding session we discussed the equilibriumof the
combination reaction between C
2
S and CaOto formC
3
S.
Dependent on the SiO
2
content either CaOand C
3
S
are stable...
1.6 Mineralisation
Above 1250C the Gibbs
free energy (chemical
potential) of C3S is lower
than free CaOor C
2
S and
therefore C
3
S is the most
stable compound and will be
formed.
CaO C
3
S C
2
S
IncreasingSiO
2
content
Gibbs
FreeEnergy
...or C
3
S and
C
2
S are stable.
C
2
S + CaO C
3
S

C3S will be formed because it is the most stable.

Cement Kiln Chemistry
In the preceding session we discussed the equilibriumof the
combination reaction between C
2
S and CaOto formC
3
S.
1.6 Mineralisation
Returning to the chemical
potentials below 1250C
.
CaO C
3
S C
2
S
IncreasingSiO
2
content
Gibbs
FreeEnergy
.the free energy of any
compound can be reduced by
incorporation of minor
substitutions or impurities.
Most commonimpurities,
Na
2
O, K
2
O, SO
3
, Al
2
O
3
,
are incorporated in the
belite, C
2
S.. ..free
energy of the C
2
S is
reduced.
Cement Kiln Chemistry
In the preceding session we discussed the equilibriumof the
combination reaction between C
2
S and CaOto formC
3
S.
1.6 Mineralisation
Returning to the chemical
potentials below 1250C
.
CaO C
3
S C
2
S
IncreasingSiO
2
content
Gibbs
FreeEnergy
.the free energy of any
compound can be reduced by
incorporation of minor
substitutions or impurities.
Most commonimpurities,
Na
2
O, K
2
O, SO
3
, Al
2
O
3
,
are incorporated in the
belite, C
2
S.. ..free
energy of the C
2
S is
reduced. .C
2
S is stabilisedand formation of
C
3
S becomes more difficult.
CemNet Training - Course CKPC01 Module 1 Session 6
This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent fromTradeship Publications Ltd
http://Training.CemNet.com
Cement Kiln Chemistry
In the preceding session we discussed the equilibriumof the
combination reaction between C
2
S and CaOto formC
3
S.
1.6 Mineralisation
Returning to the chemical
potentials below 1250C
.
CaO C
3
S C
2
S
IncreasingSiO
2
content
Gibbs
FreeEnergy
.the free energy of any
compound can be reduced by
incorporation of minor
substitutions or impurities.
Most commonimpurities,
Na
2
O, K
2
O, SO
3
, Al
2
O
3
,
are incorporated in the
belite, C
2
S.. ..free
energy of the C
2
S is
reduced. .Na
2
O, K
2
O, SO
3
and Al
2
O
3
inhibit
the formation of C
3
S.
Cement Kiln Chemistry
In the preceding session we discussed the equilibriumof the
combination reaction between C
2
S and CaOto formC
3
S.
1.6 Mineralisation
Returning to the chemical
potentials below 1250C
.
CaO C
3
S C
2
S
IncreasingSiO
2
content
Gibbs
FreeEnergy
.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
impurities are
preferentially incorporated
in C
2
S, belitefluorides are preferentially
incorporated in the alite, C
3
S, reducing its free energy.
..fluorides
mineralise the formation of C
3
S.
the temperature at which C
3
S becomes the
most stable compound is reduced..
Cement Kiln Chemistry
In the preceding session we discussed the equilibriumof the
combination reaction between C
2
S and CaOto formC
3
S.
1.6 Mineralisation
Returning to the chemical
potentials below 1250C
.
CaO C
3
S C
2
S
IncreasingSiO
2
content
Gibbs
FreeEnergy
.the free energy of any
compound can be reduced by
incorporation of minor
substitutions or impurities.
Fluorides are preferentially
incorporated in the alite,
C
3
S, reducing its free
energy.
CemNet Training - Course CKPC01 Module 1 Session 6
This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent fromTradeship Publications Ltd
http://Training.CemNet.com
This does involve the
addition of fluoride to the
kiln feed
Cement Kiln Chemistry
In the preceding session we discussed the equilibriumof the
combination reaction between C
2
S and CaOto formC
3
S.
1.6 Mineralisation
CaO C
3
S C
2
S
IncreasingSiO
2
content
Gibbs
FreeEnergy
but also in combination with sulphate, SO
3
, an
inhibitor. .the principle aims relate to
clinker and cement quality.
Mineralisationis sometimes
thought to be synonymous
with the production of
mineralised clinker, as
practiced at Aalborgin
Denmark, and promoted by
FL Smidth.
We will return to the subject
of the quality related benefits
of mineralisedclinker in
module 2 of the course
Cement Kiln Chemistry
In the preceding session we discussed the equilibriumof the
combination reaction between C
2
S and CaOto formC
3
S.
1.6 Mineralisation
CaO C
3
S C
2
S
IncreasingSiO
2
content
Gibbs
FreeEnergy
in module 1 we are
focusing on the impact on kiln energy efficiency and
productivity.
Mineralisationis sometimes
thought to be synonymous
with the production of
mineralised clinker, as
practiced at Aalborgin
Denmark, and promoted by
FL Smidth.
.the SO
3
also reduces
the viscosity of the C
4
AF and C
3
A melt when it forms.
clinker mineral formation takes place
through the mediumof this SO
3
melt..
..SO
3
forms low temperature melts
from~1100C
SO
3
is an inhibitor, but it is
also a fluxing agent
Cement Kiln Chemistry
In the preceding session we discussed the equilibriumof the
combination reaction between C
2
S and CaOto formC
3
S.
1.6 Mineralisation
CaO C
3
S C
2
S
IncreasingSiO
2
content
Gibbs
FreeEnergy
Mineralisationis sometimes
thought to be synonymous
with the production of
mineralised clinker, as
practiced at Aalborgin
Denmark, and promoted by
FL Smidth.
CemNet Training - Course CKPC01 Module 1 Session 6
This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent fromTradeship Publications Ltd
http://Training.CemNet.com
.C
3
S is not stable at
those temperatures in the absence of fluoride.
however, this low temperature flux is
not useful in the absence of fluoride
..SO
3
forms low temperature melts
from~1100C
SO
3
is an inhibitor, but it is
also a fluxing agent
Cement Kiln Chemistry
In the preceding session we discussed the equilibriumof the
combination reaction between C
2
S and CaOto formC
3
S.
1.6 Mineralisation
CaO C
3
S C
2
S
IncreasingSiO
2
content
Gibbs
FreeEnergy
Mineralisationis sometimes
thought to be synonymous
with the production of
mineralised clinker, as
practiced at Aalborgin
Denmark, and promoted by
FL Smidth.
in the presence of fluoride the combined
mineralisationeffect of fluoride, and fluxing effect of
SO
3
more than overcome the inhibiting effect of SO
3
.
..SO
3
forms low temperature melts
from~1100C
SO
3
is an inhibitor, but it is
also a fluxing agent
Cement Kiln Chemistry
In the preceding session we discussed the equilibriumof the
combination reaction between C
2
S and CaOto formC
3
S.
1.6 Mineralisation
CaO C
3
S C
2
S
IncreasingSiO
2
content
Gibbs
FreeEnergy
Mineralisationis sometimes
thought to be synonymous
with the production of
mineralised clinker, as
practiced at Aalborgin
Denmark, and promoted by
FL Smidth.
..with severe
blockages of the preheater of the suspension preheater kiln.
and sulphur, as
pyrites, FeS
2
, in shale, were present
in the raw materials.
Cement Kiln Chemistry
Mineralisationof the raw mix fed to a cement kiln is not entirely
straight-forward.
1.6 Mineralisation
Aalborgstechnology and patent derive froma 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
CaF
2
in limestone,
Trials with mineralised kiln feed
were carried out on long wet, Lepol
and suspension preheater kilns..
CemNet Training - Course CKPC01 Module 1 Session 6
This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent fromTradeship Publications Ltd
http://Training.CemNet.com
and sulphur, as
pyrites, FeS
2
, in shale, were present
in the raw maerials.
Cement Kiln Chemistry
Mineralisationof the raw mix fed to a cement kiln is not entirely
straight-forward.
1.6 Mineralisation
Aalborgstechnology and patent derive froma 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
CaF
2
in limestone,
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 mineralisationis introduced.
..leading to the hot
meal stickiness and preheater blockages.
.if
not the additional thermal energy input, over-and-above
that required for clinker combination, will be absorbed to
volatilise alkalis and sulphates fromthe kiln charge and a
heavy alkali cycle will develop..
Never-the-less this represents a reduction in the combination
temperature of 125~150C.
Cement Kiln Chemistry
Mineralisationof the raw mix fed to a cement kiln is not entirely
straight-forward.
1.6 Mineralisation
Mineralisationwith fluoride will stabilise C
3
S and promote its
formation fromCaOand C
2
S at 1170C. in practice
~1350C is required to overcome the inhomogeneitiesin the kiln
feed we have already discussed.
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.
Never-the-less this represents a reduction in the combination
temperature of 125~150C.
Cement Kiln Chemistry
Mineralisationof the raw mix fed to a cement kiln is not entirely
straight-forward.
1.6 Mineralisation
Mineralisationwith fluoride will stabilise C
3
S and promote its
formation fromCaOand C
2
S at 1170C. in practice
~1350C is required to overcome the inhomogeneitiesin the kiln
feed we have already discussed.
The kiln burning zone temperature must be reduced in response
to this lower combination temperature requirement..
CemNet Training - Course CKPC01 Module 1 Session 6
This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent fromTradeship Publications Ltd
http://Training.CemNet.com
..kiln exhaust gas
volume is reduced and exhaust fan capacity released to
allow kiln output to be increased.
.and therefore the amount of fuel which must be burnt
per tonne of clinker produced.
Never-the-less this represents a reduction in the combination
temperature of 125~150C.
Cement Kiln Chemistry
Mineralisationof the raw mix fed to a cement kiln is not entirely
straight-forward.
1.6 Mineralisation
Mineralisationwith fluoride will stabilise C
3
S and promote its
formation fromCaOand C
2
S at 1170C. in practice
~1350C is required to overcome the inhomogeneitiesin the kiln
feed we have already discussed.
Provided the kiln burning zone temperature is lowered by this
amount the thermal energy requirement is significantly reduced..
..or less
expensive refractorieswill be required to the desired
length of kiln campaign.
.longer kiln campaigns between
refractory replacement should follow..
Never-the-less this represents a reduction in the combination
temperature of 125~150C.
Cement Kiln Chemistry
Mineralisationof the raw mix fed to a cement kiln is not entirely
straight-forward.
1.6 Mineralisation
Mineralisationwith fluoride will stabilise C
3
S and promote its
formation fromCaOand C
2
S at 1170C. in practice
~1350C is required to overcome the inhomogeneitiesin the kiln
feed we have already discussed.
Thermal load on the burning zone refractoriesis also
significantly reduced ..
..kiln feed mineralisationis one means to achieve
this...
.we are going to spend a couple of sessions talking about
NOxgeneration and emissions mitigation in Module 3...
Never-the-less this represents a reduction in the combination
temperature of 125~150C.
Cement Kiln Chemistry
Mineralisationof the raw mix fed to a cement kiln is not entirely
straight-forward.
1.6 Mineralisation
Mineralisationwith fluoride will stabilise C
3
S and promote its
formation fromCaOand C
2
S at 1170C. in practice
~1350C is required to overcome the inhomogeneitiesin the kiln
feed we have already discussed.
The lower temperature in the burning zone can cut NOx levels at
the kiln inlet to 40% of those prior to mineralisation..
...along with better quality clinker,
lower fuel consumption and more output.
CemNet Training - Course CKPC01 Module 1 Session 6
This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent fromTradeship Publications Ltd
http://Training.CemNet.com
..kiln feed mineralisationis one means to achieve
this...
.we are going to spend a couple of sessions talking about
NOxgeneration and emissions mitigation in Module 3...
Never-the-less this represents a reduction in the combination
temperature of 125~150C.
Cement Kiln Chemistry
Mineralisationof the raw mix fed to a cement kiln is not entirely
straight-forward.
1.6 Mineralisation
Mineralisationwith fluoride will stabilise C
3
S and promote its
formation fromCaOand C
2
S at 1170C. in practice
~1350C is required to overcome the inhomogeneitiesin the kiln
feed we have already discussed.
The lower temperature in the burning zone can cut NOx levels at
the kiln inlet to 40% of those prior to mineralisation..
...CO
2
emissions will also be reduced as
a consequence of the lower fuel consumption.
..kiln feed mineralisationis one means to achieve
this...
.we are going to spend a couple of sessions talking about
NOxgeneration and emissions mitigation in Module 3...
Never-the-less this represents a reduction in the combination
temperature of 125~150C.
Cement Kiln Chemistry
Mineralisationof the raw mix fed to a cement kiln is not entirely
straight-forward.
1.6 Mineralisation
Mineralisationwith fluoride will stabilise C
3
S and promote its
formation fromCaOand C
2
S at 1170C. in practice
~1350C is required to overcome the inhomogeneitiesin the kiln
feed we have already discussed.
The lower temperature in the burning zone can cut NOx levels at
the kiln inlet to 40% of those prior to mineralisation..
...one of the few win-win-win-win
options provided by cement kiln chemistry!
F.L. Smidthpromote the production of mineralised clinker and
have developed methodologies to overcome the difficulties
which can arise.
Cement Kiln Chemistry
Mineralisationof the raw mix fed to a cement kiln is not entirely
straight-forward.
1.6 Mineralisation
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 gypsuminto the raw mill.
CemNet Training - Course CKPC01 Module 1 Session 6
This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent fromTradeship Publications Ltd
http://Training.CemNet.com
F.L. Smidthpromote the production of mineralised clinker and
have developed methodologies to overcome the difficulties
which can arise.
Cement Kiln Chemistry
Mineralisationof the raw mix fed to a cement kiln is not entirely
straight-forward.
1.6 Mineralisation
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 petroleumcoke, then there are modifications to solid fuel
grinding circuits, precalcinersand main burners that may be
required.. ..that is a technology in itself and not
specifically related to mineralisation.
F.L. Smidthpromote the production of mineralised clinker and
have developed methodologies to overcome the difficulties
which can arise.
Cement Kiln Chemistry
Mineralisationof the raw mix fed to a cement kiln is not entirely
straight-forward.
1.6 Mineralisation
As discussed a couple of sessions ago mineralisationmight 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.
.the main burner of the
kiln may require modification to avoid these problems.
F.L. Smidthpromote the production of mineralised clinker and
have developed methodologies to overcome the difficulties
which can arise.
Cement Kiln Chemistry
Mineralisationof the raw mix fed to a cement kiln is not entirely
straight-forward.
1.6 Mineralisation
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
Aalborgtechnology as sulphur loads in the kiln are boosedas
part of the technology.
These issues of volatile cycles in the kiln will be the topic of
the next sessions of the course.
CemNet Training - Course CKPC01 Module 1 Session 6
This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent fromTradeship Publications Ltd
http://Training.CemNet.com
1.6 Mineralisation.
Cement Kiln
ProcessChemistry
Module 1. Cement kiln energy efficiency and
productivity.