CemNet Training - Course CKPC01

Module 1 Session 7

Cement Kiln
Process Chemistry
Module 1. Cement kiln energy efficiency and
productivity.
1.7 Alkali cycles.

Cement Kiln Chemistry

1.7 Alkali cycles

In the preceding sessions of the course we have been focusing on the

reactions of the major oxides, CaO, SiO2, Al2O3 and Fe2O3 to form
the clinker minerals C3S, C2S, C3A and C4AF.
We have seen that minor components such as MgO, K2O, Na2O,
SO3 and F- affect the heat of clinker formation, amount of flux
formed at different temperatures in the kiln, properties of that
flux and can inhibit or mineralise clinker formation.
In this module 1 we are concerned with the thermal energy
efficiency and productivity of the cement kiln..the reliability
of the kiln operation has a major role to play in determining this
thermal energy efficiency and productivity.

Cement Kiln Chemistry

1.7 Alkali cycles

In the preceding sessions of the course we have been focusing on the

reactions of the major oxides, CaO, SiO2, Al2O3 and Fe2O3 to form
the clinker minerals C3S, C2S, C3A and C4AF.
We have seen that minor components such as MgO, K2O, Na2O,
SO3 and F- affect the heat of clinker formation, amount of flux
formed at different temperatures in the kiln, properties of that
flux and can inhibit or mineralise clinker formation.
Every time the kiln stops the heat capacity must be re-established
to reach the temperatures required for C3S formation. .
.unplanned kiln stops can arise for many reasons,
mechanical or electrical equipment failures, mistakes in
operations. .these are not our concern in this course,
we are focusing on the process chemistry and its potential
effects on the reliability of kiln operations.

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 7

1.7 Alkali cycles

In the preceding sessions of the course we have been focusing on the

reactions of the major oxides, CaO, SiO2, Al2O3 and Fe2O3 to form
the clinker minerals C3S, C2S, C3A and C4AF.
We have seen that minor components such as MgO, K2O, Na2O,
SO3 and F- affect the heat of clinker formation, amount of flux
formed at different temperatures in the kiln, properties of that
flux and can inhibit or mineralise clinker formation.
Every time the kiln stops the heat capacity must be re-established
to reach the temperatures required for C3S formation. ..the
behaviour of the minor components in the kiln feed (and fuels)
have more affect on the reliability of kiln operations than do the
major oxides.
In particular the recirculation of volatile species which is
known as the alkali cycle.

Cement Kiln Chemistry

1.7 Alkali cycles

In the preceding sessions of the course we have been focusing on the

reactions of the major oxides, CaO, SiO2, Al2O3 and Fe2O3 to form
the clinker minerals C3S, C2S, C3A and C4AF.
We have seen that minor components such as MgO, K2O, Na2O,
SO3 and F- affect the heat of clinker formation, amount of flux
formed at different temperatures in the kiln, properties of that
flux and can inhibit or mineralise clinker formation.
The volatile species that participate in these alkali cycles are the
carbonates, sulphates and chlorides of the alkali metals, K+ and
Na+.
The alkali metals are introduced into the kiln with the clay
minerals where they occupy positions between the alumino-silicate
layers.

Cement Kiln Chemistry

1.7 Alkali cycles

In the preceding sessions of the course we have been focusing on the

reactions of the major oxides, CaO, SiO2, Al2O3 and Fe2O3 to form
the clinker minerals C3S, C2S, C3A and C4AF.
We have seen that minor components such as MgO, K2O, Na2O,
SO3 and F- affect the heat of clinker formation, amount of flux
formed at different temperatures in the kiln, properties of that
flux and can inhibit or mineralise clinker formation.
They may also be present as alkali carbonates, or carbonates may
be formed in the preheater.
.sulphates or sulphur can be
introduced in the raw materials or fuels
chlorides
may also be introduced in the raw materials or fuels, and can also
be introduced as salt, NaCl, in the process water introduced in
conditioning towers etc.

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 7

1.7 Alkali cycles

The mechanism of the alkali cycle will be well known to most

cement manufacturers:
Volatile species in the kiln feed
pass down the preheater and into
the rotary kiln.

Cement Kiln Chemistry

1.7 Alkali cycles

The mechanism of the alkali cycle will be well known to most

cement manufacturers:
Volatile species in the kiln feed
pass down the preheater and into
the rotary kiln.
Some of the volatiles pass out of
the kiln in the clinker.

Cement Kiln Chemistry

1.7 Alkali cycles

The mechanism of the alkali cycle will be well known to most

cement manufacturers:
Volatile species in the kiln feed
pass down the preheater and into
the rotary kiln.
Some of the volatiles pass out of
the kiln in the clinker.
Some evaporate in the burning
zone of the kiln and are carried
away with the combustion
product gases.

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 7

1.7 Alkali cycles

The mechanism of the alkali cycle will be well known to most

cement manufacturers:
Volatile species in the kiln feed
pass down the preheater and into
the rotary kiln.
Some of the volatiles pass out of
the kiln in the clinker.
This evaporation of volatiles in the
burning zone of the kiln absorbs
thermal energy which is carried away
with the combustion product gases.

Cement Kiln Chemistry

1.7 Alkali cycles

The mechanism of the alkali cycle will be well known to most

cement manufacturers:
Volatilised material from the
feed is joined by any volatile
material from the fuel.

Cement Kiln Chemistry

1.7 Alkali cycles

The mechanism of the alkali cycle will be well known to most

cement manufacturers:
Volatilised material from the
feed is joined by any volatile
material from the fuel.
The combined volatilised
material from the feed and fuel
are carried to the preheater in the
exhaust gases where they
condense on the incoming feed
and are carried back 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 1 Session 7

1.7 Alkali cycles

The mechanism of the alkali cycle will be well known to most

cement manufacturers:
Volatilised material from the
feed is joined by any volatile
material from the fuel.
Condensation of the volatiles on
the feed in the preheater releases
the thermal energy absorbed by
their evaporation in the burning
zone.
The alkali cycle transfers thermal energy from the burning
zone to the preheater, in a similar way to recarbonation
transferring thermal energy up the preheater, or
combustible materials in the feed.

Cement Kiln Chemistry

1.7 Alkali cycles

The mechanism of the alkali cycle will be well known to most

cement manufacturers:
Volatilised material from the
feed is joined by any volatile
material from the fuel.
Condensation of the volatiles on
the feed in the preheater releases
the thermal energy absorbed in
their evaporation in the burning
zone.
The thermal energy from the burning zone transferred
back to the preheater is not used efficiently and increases
preheater exhaust gas temperature and increases overall
thermal energy consumption.

Cement Kiln Chemistry

1.7 Alkali cycles

The mechanism of the alkali cycle will be well known to most

cement manufacturers:
The cycle of volatile material
builds up..
.until the amount of
material exiting in the clinker
equals the amount of material
entering in the feed & fuel.

Concentration of recirculating volatile material is significantly

higher than in either the feed, fuel or 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 1 Session 7

1.7 Alkali cycles

The mechanism of the alkali cycle will be well known to most

cement manufacturers:
Measurement of the input levels
in feed and fuel.
.output
levels in the clinker...
.and the
levels in the hot meal.
Allows the volatility of each species in the particular kiln to
be calculatated:
Volatility = 1 Volatile %Clinker / Volatile %Hot Meal
The concentration in hot meal, Volatile %Hot Meal, is on a
loss-free basis.

Cement Kiln Chemistry

1.7 Alkali cycles

The mechanism of the alkali cycle will be well known to most

cement manufacturers:
The concentration of the volatile
species in the hot meal at the
bottom of the preheater increases
the stickiness of the feed.
The hot meal can stick to the
walls of the preheater ducts
causing restrictions and in the
worst cases cause blockage of the
preheater.
This is one of potential causes of unplanned kiln stops that
..even without
can arise due to the alkali cycle..
blocking the preheater the restriction to venting the
exhaust gases is increased, reducing kiln output.

Cement Kiln Chemistry

1.7 Alkali cycles

The mechanism of the alkali cycle will be well known to most

cement manufacturers:
The concentration of the volatile
species in the hot meal at the
bottom of the preheater increases
the stickiness of the feed.
The hot meal can stick to the
walls of the preheater ducts
causing restrictions and in the
worst cases cause blockage of the
preheater.
The preheater blockage usually results from a piece of
coating falling from one of the ducts and bridging the bottom
of the cyclone outlets.

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 7

1.7 Alkali cycles

The mechanism of the alkali cycle will be well known to most

cement manufacturers:
The concentration of the volatile
species in the hot meal at the
bottom of the preheater increases
the stickiness of the feed.
Various strategies can be adopted
to reduce or eliminate these
problems:
1. Steps can be taken to reduce the intensity of the volatile
cycles. ..these strategies depend to a
great extent on the volatile species that are building up in
the alkali cycle... ..we will consider these factors
in the next two sessions of the course.

Cement Kiln Chemistry

1.7 Alkali cycles

The mechanism of the alkali cycle will be well known to most

cement manufacturers:
The concentration of the volatile
species in the hot meal at the
bottom of the preheater increases
the stickiness of the feed.
Distribution plate
Various strategies can be adopted
to reduce or eliminate these
problems:
2. Steps can be taken to prevent the material sticking to the
ducts in the preheater. ..meal distribution
plates in the preheater ensure that the feed is evenly
distributed through the rising gas stream in the
preheater... ..promoting condensation of volatiles
on the descending feed rather than the duct walls.

Cement Kiln Chemistry

1.7 Alkali cycles

The mechanism of the alkali cycle will be well known to most

cement manufacturers:
The concentration of the volatile
species in the hot meal at the
bottom of the preheater increases
the stickiness of the feed.
Distribution plate
Various strategies can be adopted
to reduce or eliminate these
problems:
2. Steps can be taken to prevent the material sticking to the
ducts in the preheater. ..meal distribution
plates in the preheater ensure that the feed is evenly
distributed through the rising gas stream in the
preheater... ..also cooling the rising gases and
preventing volatiles migrating higher up the preheater.

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 7

1.7 Alkali cycles

The mechanism of the alkali cycle will be well known to most

cement manufacturers:
Coating resistant refractory
The concentration of the volatile
species in the hot meal at the
bottom of the preheater increases
the stickiness of the feed.
Various strategies can be adopted
to reduce or eliminate these
problems:
2. Steps can be taken to prevent the material sticking to the
ducts in the preheater. ..the gas riser from the
kiln inlet and the ducts in the lower part of the preheater
can be lined with coating resistant refractories.

Cement Kiln Chemistry

1.7 Alkali cycles

The mechanism of the alkali cycle will be well known to most

cement manufacturers:
The concentration of the volatile
species in the hot meal at the
bottom of the preheater increases
the stickiness of the feed.
Various strategies can be adopted
to reduce or eliminate these
problems:
2. Steps can be taken to prevent the material sticking to the
ducts in the preheater. ..air cannons can be
fitted to prevent coating forming in known areas of
problems... ..local knowledge of the particular kiln
is critical to correctly siting the air cannons.

Cement Kiln Chemistry

1.7 Alkali cycles

The mechanism of the alkali cycle will be well known to most

cement manufacturers:
The concentration of the volatile
species in the hot meal at the
bottom of the preheater increases
the stickiness of the feed.
Various strategies can be adopted
to reduce or eliminate these
problems:
2. Steps can be taken to prevent the material sticking to the
ducts in the preheater. ..air cannons can be
fitted to prevent coating forming in known areas of
problems... .. air cannons must fire in the direction
of material flow, rather than opposing the material flow.

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 7

1.7 Alkali cycles

The mechanism of the alkali cycle will be well known to most

cement manufacturers:
The concentration of the volatile
species in the hot meal at the
bottom of the preheater increases
the stickiness of the feed.
Various strategies can be adopted
to reduce or eliminate these
problems:
2. Steps can be taken to prevent the material sticking to the
ducts in the preheater. ..air cannons can be
fitted to prevent coating forming in known areas of
problems... .. air cannons have limited range of no
more than 1.5m and therefore multiple cannons are likely
to be needed.

Cement Kiln Chemistry

1.7 Alkali cycles

The mechanism of the alkali cycle will be well known to most

cement manufacturers:
The concentration of the volatile
species in the hot meal at the
bottom of the preheater increases
the stickiness of the feed.
Various strategies can be adopted
to reduce or eliminate these
problems:
2. Steps can be taken to prevent the material sticking to the
ducts in the preheater. ..air cannons can be
fitted to prevent coating forming in known areas of
problems... ..acoustic horns are an alternative to air
cannons.

Cement Kiln Chemistry

1.7 Alkali cycles

The mechanism of the alkali cycle will be well known to most

cement manufacturers:
The concentration of the volatile
species in the hot meal at the
bottom of the preheater increases
the stickiness of the feed.
Various strategies can be adopted
to reduce or eliminate these
problems:
2. Steps can be taken to prevent the material sticking to the
ducts in the preheater. ..dead areas with low
gas velocity need to be avoided to prevent accumulation
of sticky dust.

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 7

1.7 Alkali cycles

The mechanism of the alkali cycle will be well known to most

cement manufacturers:
The concentration of the volatile
species in the hot meal at the
bottom of the preheater increases
the stickiness of the feed.
Various strategies can be adopted
to reduce or eliminate these
problems:
2. Steps can be taken to prevent the material sticking to the
ducts in the preheater. ..feed flaps need to be
fitted to cyclone exit chutes to prevent gas shortcircuiting up into the cyclones and preventing free flow
of the material out of the cyclones.

Cement Kiln Chemistry

1.7 Alkali cycles

The mechanism of the alkali cycle will be well known to most

cement manufacturers:
The concentration of the volatile
species in the hot meal at the
bottom of the preheater increases
the stickiness of the feed.
Various strategies can be adopted
to reduce or eliminate these
problems:
2. Steps can be taken to prevent the material sticking to the
ducts in the preheater. ..angle of incline of
cyclone exit chutes need to be at least 55 to ensure feed
falls rapidly through the chutes.

Cement Kiln Chemistry

1.7 Alkali cycles

The mechanism of the alkali cycle will be well known to most

cement manufacturers:
The concentration of the volatile
species in the hot meal at the
bottom of the preheater increases
the stickiness of the feed.
The hot meal can stick to the
walls of the preheater ducts
causing restrictions and in the
worst cases cause blockage of the
preheater.
The concentration of volatile species in the hot meal
entering the kiln also affects the properties of the flux and
the clinkering range of the hot meal 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 7

1.7 Alkali cycles

The mechanism of the alkali cycle will be well known to most

cement manufacturers:
The concentration of the volatile
species in the hot meal at the
bottom of the preheater increases
the stickiness of the feed.
The hot meal can stick to the
walls of the preheater ducts
causing restrictions and in the
worst cases cause blockage of the
preheater.
This can be the cause of ball and ring formation in the kiln,
which can again lead to unplanned stops of the kiln.
.again, more of this in succeeding sessions.

Cement Kiln Chemistry

1.7 Alkali cycles

The mechanism of the alkali cycle will be well known to most

cement manufacturers:
This cycle between the rotary kiln
and the preheater is the classical
internal alkali cycle.
There is also an external alkali
cycle, which must be considered.

Cement Kiln Chemistry

1.7 Alkali cycles

The volatilised fumes exit the rotary kiln to the preheater together
with the combustion product gases from the main burner..
..and encounter the
The volatilised fumes
feed descending the
condense and are
preheater.
collected in the
cyclone where the
temperature is below
the melting point of
the volatile species..
..chlorides will
condense higher up
the preheater than
sulphates.

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 7

1.7 Alkali cycles

The volatilised fumes exit the rotary kiln to the preheater together
with the combustion product gases from the main burner..
..and encounter the
The volatilised fumes
feed descending the
condense and are
preheater.
collected in the
cyclone where the
Melting Point
temperature is below
K2SO4
1069C
the melting point of
Na2SO4
884C
the volatile species..
NaCl
801C
KCl
776C
..chlorides will
condense higher up
the preheater than
sulphates.

Cement Kiln Chemistry

1.7 Alkali cycles

The volatilised fumes exit the rotary kiln to the preheater together
with the combustion product gases from the main burner..
..and encounter the
feed descending the
We have already
preheater.
seen in session 1.3
that the preheater
cyclones do not have
100% collection
efficiency..
..the
lower cyclones may
only have 80~85%
collection efficiency.
Some of the volatile species are therefore carried up the
preheater with the uncollected feed.. ..and some exits
the top cyclone in the dust.

Cement Kiln Chemistry

1.7 Alkali cycles

The volatilised fumes exit the rotary kiln to the preheater together
with the combustion product gases from the main burner..
..and encounter the
feed descending the
preheater.
There is therefore an
external cycle
between the preheater
and the precipitator in
the dust.
Some of the volatile species are therefore carried up the
preheater with the uncollected feed.. ..and some exits
the top cyclone in the dust.

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 7

1.7 Alkali cycles

Some components, such as sulphides, in the kiln feed will oxidise

..and are lost as
in the upper stages of the preheater..
gases (SO2) in the
preheater exhaust gas.
Some will be absorbed
onto the raw mix in the
raw mill... ...and
is returned to the kiln in
the kiln feed.
Another external cycle
between the preheater
and the raw mill.

Cement Kiln Chemistry

1.7 Alkali cycles

Other highly volatile species, such as ammonium compounds, will

evaporate in the upper stages of the preheater and be partially
absorbed in the raw mill.
Yet another external
cycle between the
preheater and the raw
mill.
We are going to return
to these external cycles
in Module 3 when we
consider emissions
from cement kilns.

Cement Kiln Chemistry

1.7 Alkali cycles

The melting points of volatile species we introduced earlier are of

the discrete species..
Melting Point
In practice there will
K2SO4
1069C
be a mixture of these
Na2SO4
884C
volatile species salts in
NaCl
801C
the hot meal..
KCl
776C
..softening and
melting points may
be even lower due to
the formation of low
temperature eutectics
between the salts.
We will talk about the cycles of the individual species and
the mixtures in 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 7

Cement Kiln
Process Chemistry
Module 1. Cement kiln energy efficiency and
productivity.
1.7 Alkali cycles.

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