CemNet Training - Course CKPC01

Module 2.8

Cement Kiln
Process Chemistry
Module 2. Cement clinker quality and composition.
2.8 Combustion oxidation and reduction.

Cement Kiln Chemistry

2.8 Combustion

In session 1.10 of the course we talked about the stoichiometry of

combustion of the fuels in a cement kiln, the quantity of combustion
air that must be drawn into the kiln, and the combustion product
gases that must be exhausted from the kiln.
In the preceding session we talked about the need for a sharp
temperature profile to achieve rapid heating to the combination
temperature of the clinker.
Also that the main burner must be inserted the minimum
practical distance into the kiln to minimise the cooling zone in
the kiln after the clinker has passed under the flame.. ..the
clinker is then rapidly cooled by falling into the cooler while
still at a high temperature.

Cement Kiln Chemistry

2.8 Combustion

In session 1.10 of the course we talked about the stoichiometry of

combustion of the fuels in a cement kiln, the quantity of combustion
air that must be drawn into the kiln, and the combustion product
gases that must be exhausted from the kiln.
In the preceding session we talked about the need for a sharp
temperature profile to achieve rapid heating to the combination
temperature of the clinker.
In order to understand how to produce that sharp temperature
profile we have to understand the dynamics of cement kiln
burners and flames.. ..even though this is not strictly
chemistry.
The design and adjustment of the burner produces the flame that
can provide the sharp hot temperature profile required
..along with the amount of excess air and oxygen
drawn into 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 2.8

2.8 Combustion

In session 1.10 of the course we talked about the stoichiometry of

combustion of the fuels in a cement kiln, the quantity of combustion
air that must be drawn into the kiln, and the combustion product
gases that must be exhausted from the kiln.
The cement kiln flame is generated by the combustion of
hydrocarbon fuels. ..i.e. fuels that are composed
principally of hydrogen and carbon combined in various
hydrocarbon molecules.
Oxidation of this hydrogen and carbon liberates the exothermic
energy that produces the temperature for combination of the
feed into the clinker minerals.
C +
O2 CO2
2H + O2 H2O

Cement Kiln Chemistry

2.8 Combustion

These oxidation reactions can only take place when the

hydrocarbons in the fuel are brought into contact with the oxygen in
the combustion air by mixing of the combustion air and fuel.
C +
O2 CO2
2H + O2 H2O
Once the fuel and combustion air are mixed the combustion
continues through the following sequence of processes:
Mixing Ignition Oxidation Exhaust
Once mixing is completed ignition and oxidation take place
very rapidly. ..therefore mixing is the rate determining
process....provided that the combustion product gases are
adequately exhausted from the flame.

Cement Kiln Chemistry

2.8 Combustion

These oxidation reactions can only take place when the

hydrocarbons in the fuel are brought into contact with the oxygen in
the combustion air by mixing of the combustion air and fuel.
C +
O2 CO2
2H + O2 H2O
Once the fuel and combustion air are mixed the combustion
continues through the following sequence of processes:
Mixing Ignition Oxidation Exhaust
Once mixing is completed ignition and oxidation take place
very rapidly. ..therefore mixing is the rate determining
process....exhausting of the combustion product gases is
provided by the induced draft fan, which serves a dual purpose
by also drawing the combustion air into 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 2.8

2.8 Combustion

Mixing of the combustion air and fuel in a cement kiln flame relies
on jet entrainment of the secondary combustion air into the flame.
The burner blows a jet of primary air and fuel into the kiln.
Friction between the jet of
primary air and fuel and the
surrounding air accelerates
the surrounding secondary
air.
The accelerated secondary
air is then pulled into the
flame, expanding it.
The process is momentum controlled and continues until the velocity
of the jet is the same as the surrounding air.

Cement Kiln Chemistry

2.8 Combustion

Mixing of the combustion air and fuel in a cement kiln flame relies
on jet entrainment of the secondary combustion air into the flame.
The burner blows a jet of primary air and fuel into the kiln.
In a rotary kiln the
entrainment of secondary
air and expansion of the
flame is constrained by the
kiln shell and refractory
lining.
The availability of
secondary air also
constrains the entrainment
into the flame.
The excess momentum of the jet then pulls back exhaust gases from
further up the kiln and entrains them into the flame.

Cement Kiln Chemistry

2.8 Combustion

Mixing of the combustion air and fuel in a cement kiln flame relies
on jet entrainment of the secondary combustion air into the flame.
This phenomenon is known as external recirculation and is critical for
characteristics of the flame.
The primary air mixes with the fuel very quickly.The entrainment of the
secondary air is then
dependent on the ratio of
the primary air/fuel jet and
the momentum of the
secondary air.
The higher the flow rate
and velocity of the primary
air the quicker the mixing.
Recirculation is an indication that all the secondary air has been
entrained into the flame and fuel/air mixing is complete.

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 2.8

2.8 Combustion

Mixing of the combustion air and fuel in a cement kiln flame relies
on jet entrainment of the secondary combustion air into the flame.
This phenomenon is known as external recirculation and is critical for
characteristics of the flame.
A recirculating flame provides the short burning zone and sharp temperature
profile required for optimum clinker quality.. .and other non-quality
related benefits.
The recirculation prevents
the flame expanding to
impinge on the refractory.
The recirculating gases
provide a cushion of cooler
exhaust gas that protects the
refractory.
Recirculation is an indication that all the secondary air has been
entrained into the flame and fuel/air mixing is complete.

Cement Kiln Chemistry

2.8 Combustion

Mixing of the combustion air and fuel in a cement kiln flame relies
on jet entrainment of the secondary combustion air into the flame.
This phenomenon is known as external recirculation and is critical for
characteristics of the flame.
With a recirculating flame oxidising burning conditions can be guaranteed
with a small excess of air above that required for combustion. .as
little as 1~2% oxygen at the
kiln inlet.
Without recirculation the
mixing of secondary air and
fuel is inadequate and
reducing burning conditions
and CO can be present at
4~5% oxygen at the kiln
inlet..

Cement Kiln Chemistry

2.8 Combustion

Mixing of the combustion air and fuel in a cement kiln flame relies
on jet entrainment of the secondary combustion air into the flame.
Production of clinker in a reducing atmosphere in a cement kiln can seriously
degrade the quality of clinker and the cement produced from the clinker.
However, an industrial cement kiln is tolerant of reducing conditions without
these adverse effects manifesting themselves .provided that the clinker
falls into the cooler at a
temperature above 1250C
and is cooled in air.
Cooling in air from a
sufficiently high
temperature negates the
adverse affects of reductive
burning as the clinker
reoxidises during cooling.

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 2.8

2.8 Combustion

Mixing of the combustion air and fuel in a cement kiln flame relies
on jet entrainment of the secondary combustion air into the flame.
The conditions that must be avoided are the clinker cooling to below 1250C
in reducing conditions in the kiln. ..if that happens the liquid flux
crystallises under reducing conditions and this leads to the serious
degradation of clinker quality.
In those conditions a
sequence of detrimental
affects on clinker quality
arise, dependent on the
degree of reduction.

The clinker colour changes from grey to

brown as Fe2+ replaces Mg2+ in solid solution
in C4AF, which reverts to a brown colour.

Cement Kiln Chemistry

The reduction of Fe3+ to

Fe2+ and the solid solution
of Fe2+ in the clinker
minerals is the cause of
these detrimental affects.

2.8 Combustion

Mixing of the combustion air and fuel in a cement kiln flame relies
on jet entrainment of the secondary combustion air into the flame.
The conditions that must be avoided are the clinker cooling to below 1250C
in reducing conditions in the kiln. ..if that happens the liquid flux
crystallises under reducing conditions and this leads to the serious
degradation of clinker quality.
In those conditions a
sequence of detrimental
affects on clinker quality
arise dependent on the
degree of reduction.

The normal grey colour of clinker arises from

..the
solid solution of Mg2+ in C4AF..
Mg2+ distorts the electron cloud of Fe3+ in
C4AF resulting in the typical grey colour
of clinker and cement.

Cement Kiln Chemistry

The reduction of Fe3+ to

Fe2+ and the solid solution
of Fe2+ in the clinker
minerals is the cause of
these detrimental affects.

2.8 Combustion

Mixing of the combustion air and fuel in a cement kiln flame relies
on jet entrainment of the secondary combustion air into the flame.
The conditions that must be avoided are the clinker cooling to below 1250C
in reducing conditions in the kiln. ..if that happens the liquid flux
crystallises under reducing conditions and this leads to the serious
degradation of clinker quality.
In those conditions a
sequence of detrimental
affects on clinker quality
arise dependent on the
degree of reduction.

Under more intense reducing conditions the

C4AF content is depleted and C3A content
..less Fe3+ and therefore
increased..
Fe2O3 is available to form C4AF, meaning
that Al2O3 is released to form more C3A.

The reduction of Fe3+ to

Fe2+ and the solid solution
of Fe2+ in the clinker
minerals is the cause of
these detrimental affects.

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 2.8

2.8 Combustion

Mixing of the combustion air and fuel in a cement kiln flame relies
on jet entrainment of the secondary combustion air into the flame.
The conditions that must be avoided are the clinker cooling to below 1250C
in reducing conditions in the kiln. ..if that happens the liquid flux
crystallises under reducing conditions and this leads to the serious
degradation of clinker quality.
In those conditions a
sequence of detrimental
affects on clinker quality
arise dependent on the
degree of reduction.

Under more intense reducing conditions the

C4AF content is depleted and C3A content
..setting of cement
increased..
becomes increasingly rapid and
uncontrollable due to flash setting.

Cement Kiln Chemistry

The reduction of Fe3+ to

Fe2+ and the solid solution
of Fe2+ in the clinker
minerals is the cause of
these detrimental affects.

2.8 Combustion

Mixing of the combustion air and fuel in a cement kiln flame relies
on jet entrainment of the secondary combustion air into the flame.
The conditions that must be avoided are the clinker cooling to below 1250C
in reducing conditions in the kiln. ..if that happens the liquid flux
crystallises under reducing conditions and this leads to the serious
degradation of clinker quality.
In those conditions a
sequence of detrimental
affects on clinker quality
arise dependent on the
degree of reduction.

C3S is destabilised by solid solution of Fe2+ as

FeO and the decomposition to C2S and CaO
during cooling is accelerated.
..subsequent rapid cooling cannot
stabilise C3S.

Cement Kiln Chemistry

The reduction of Fe3+ to

Fe2+ and the solid solution
of Fe2+ in the clinker
minerals is the cause of
these detrimental affects.

2.8 Combustion

Mixing of the combustion air and fuel in a cement kiln flame relies
on jet entrainment of the secondary combustion air into the flame.
The conditions that must be avoided are the clinker cooling to below 1250C
in reducing conditions in the kiln. ..if that happens the liquid flux
crystallises under reducing conditions and this leads to the serious
degradation of clinker quality.
In those conditions a
sequence of detrimental
affects on clinker quality
arise dependent on the
degree of reduction.
The reduction of Fe3+ to
Fe2+ and the solid solution
The inversion of C2S to the hydraulically inactive of Fe2+ in the clinker
polymorph is promoted by the incorporation of minerals is the cause of
Fe2+ in C2S as FeO, with attendant dusting of the
these detrimental affects.
clinker.

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 2.8

2.8 Combustion

Mixing of the combustion air and fuel in a cement kiln flame relies
on jet entrainment of the secondary combustion air into the flame.
However, this catalogue of potentially serious quality problems.
..colour change from grey to brown, rapid setting due to more C3A and
low strength development due to less C3S and hydraulically inactive C2S...
..can all be avoided, provided that the clinker does not cool to below
1250C in a reducing atmosphere in the cement kiln..
.and the liquid
flux does not crystallise in a
reducing atmosphere.

Cement Kiln
Process Chemistry
Module 2. Cement clinker quality and composition.
2.8 Combustion oxidation and reduction.

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