CemNet Training - Course CKPC01

Module 1 Session 8

Cement Kiln
Process Chemistry
Module 1. Cement kiln energy efficiency and
productivity.
1.8 Chloride cycles, bypasses and purges.

Cement Kiln Chemistry

1.8 Chloride cycles

In the preceding session we talked about the general principles of

the alkali cyclesin this session we will consider the
cycles of chlorides in the cement kiln.
Melting Point
Alkali chlorides melt at ~800C or less: NaCl
801C
KCl
776C
When mixed with sulphates, K2SO4, Na2SO4, CaSO4, low
temperature eutectic melting takes place below 700C.
As the condensed chlorides are carried into the rotary kiln
with the feed the vapour pressure increases with temperature
until the boiling point is reached:
Boiling Point
NaCl
KCl

Cement Kiln Chemistry

1440C
1411C

1.8 Chloride cycles

In the preceding session we talked about the general principles of

the alkali cyclesin this session we will consider the
cycles of chlorides in the cement kiln.
These boiling points of the alkali chlorides are lower than the
burning zone temperature of a cement kiln.
It is therefore very difficult for
any chloride to pass through the
kiln and exit in the clinker.

NaCl
KCl

Boiling Point
1440C
1411C

chloride volatility in a cement kiln is very high and the

concentration in the hot meal can be ~100x that in the feed and
fuel inputs to 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 8

1.8 Chloride cycles

In the preceding session we talked about the general principles of

the alkali cyclesin this session we will consider the
cycles of chlorides in the cement kiln.
These boiling points of the alkali chlorides are lower than the
burning zone temperature of a cement kiln.
It is therefore very difficult for
any chloride to pass through the
kiln and exit in the clinker.

NaCl
KCl

Boiling Point
1440C
1411C

Cl volatility = 1 Cl %Clinker/Cl %Hot Meal

99% = 100% 0.02%/2.00%
In a closed system the outputs in clinker must equal the
inputs in the feed and fuel.

Cement Kiln Chemistry

1.8 Chloride cycles

In the preceding session we talked about the general principles of

the alkali cyclesin this session we will consider the
cycles of chlorides in the cement kiln.
These boiling points of the alkali chlorides are lower than the
burning zone temperature of a cement kiln.
If the inputs exceed 0.02% per kg clinker then the concentration
in hot meal is likely to exceed 2% (loss free)preheater
blockage problems are likely at this Cl concentration in hot
meal.
Cl volatility = 1 Cl %Clinker/Cl %Hot Meal
0.99 = 1 0.02%/2.00%
If the chloride inputs exceed 0.02% then some way is
required to break the cycle of chlorides.

Cement Kiln Chemistry

1.8 Chloride cycles

One solution to this chloride cycle problem can be the installation

of an alkali bypass or bleed.
Part of the exhaust gases
exiting the rotary kiln to the
preheater are extracted
before entering the
preheater...
.and quench cooled to
precipitate the volatiles.
The effectiveness of alkali bleeds or bypasses is closely
connected with the cycle itself.

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 8

1.8 Chloride cycles

One solution to this chloride cycle problem can be the installation

of an alkali bypass or bleed.
A bypass relies on the concentration of
recirculating volatile material being
significantly higher than in either the
feed, fuel or clinker.
This means that bleeding out a
small proportion of the
recirculating material.
is sufficient to take out the equivalent amount
that is entering in the feed and fuel.

Cement Kiln Chemistry

1.8 Chloride cycles

One solution to this chloride cycle problem can be the installation

of an alkali bypass or bleed.
A bypass relies on the concentration of
recirculating volatile material being
significantly higher than in either the
feed, fuel or clinker.
The concentration in the
recirculating material reduces, and
with it the tendency for the
preheater to block.

Cement Kiln Chemistry

1.8 Chloride cycles

One solution to this chloride cycle problem can be the installation

of an alkali bypass or bleed.
The concentration factor of
recirculating volatile material is the
ratio of the quantity in the hot meal to
the quantities entering the kiln in the
feed and the fuel.
Concentration factor is directly related
to the volatility of the recirculating
species in the burning zone.
Alkali bypasses are effective for highly volatile materials which
have high concentration factors.

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 8

1.8 Chloride cycles

One solution to this chloride cycle problem can be the installation

of an alkali bypass or bleed.
Chlorides have a very high volatility
in the burning zone (>97%), and
therefore high concentration factors.
Alkali bypasses are very effective in
reducing the cycle of chlorides, and
alleviating chloride based clogging of
the preheater.
If the raw materials and/or fuel have chloride content in excess of
0.02% on clinker an alkali bypass will be required to allow the
kiln to operate without preheater clogging problems.

Cement Kiln Chemistry

1.8 Chloride cycles

One solution to this chloride cycle problem can be the installation

of an alkali bypass or bleed.
Chlorides have a very high volatility
in the burning zone (>97%), and
therefore high concentration factors.
Alkali bypasses are very effective in
reducing the cycle of chlorides, and
alleviating chloride based clogging of
the preheater.
When alternative fuels are burnt in a cement kiln, installation of
an alkali bypass can be necessary to alleviate chloride based
preheater clogging problems.

Cement Kiln Chemistry

1.8 Chloride cycles

One solution to this chloride cycle problem can be the installation

of an alkali bypass or bleed.
When a bypass is installed on a
cement kiln the volatility of the
potassium, K+, and sodium, Na+, in
the feed can be increased by the
addition of chloride to the feed as
calcium chloride, CaCl2.
Potassium and sodium will preferentially combine with chloride
in the hot meal of the kiln and their volatility will be boosted by
the volatility of the chloride.

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 8

1.8 Chloride cycles

One solution to this chloride cycle problem can be the installation

of an alkali bypass or bleed.
When a bypass is installed on a
cement kiln the volatility of the
potassium, K+, and sodium, Na+, in
the feed can be increased by the
addition of chloride to the feed as
calcium chloride, CaCl2.
This means that a bypass can be used to produce low alkali
clinker from high alkali raw materials if calcium chloride is added
to the kiln feed.

Cement Kiln Chemistry

1.8 Chloride cycles

One solution to this chloride cycle problem can be the installation

of an alkali bypass or bleed.
The precalciner kiln process
particularly lends itself to the
installation and operation of an alkali
bypass.
Less than 50% of the fuel is fired in the
main burner of the kiln... ...and the
feed is virtually fully calcined by the
time it enters the rotary section of the
kiln alkalis volatilised in the rotary kiln are
therefore concentrated in the lower volume of kiln exit
exhaust gases.
.therefore a lower percentage of the kiln
exit gases have to be bypassed to break the chloride
cycle.

Cement Kiln Chemistry

1.8 Chloride cycles

One solution to this chloride cycle problem can be the installation

of an alkali bypass or bleed.
The operation of an alkali bypass
needs to be optimised to minimise the
amount of dust drawn out of the kiln
exit with the bypassed gas.
1 gram of dust per kilogram of clinker
produced per percent of bypassed gas
should be possible by correct siting of
the bypass take-off.
Disposing of the bypassed dust can be a major problem,
therefore the less drawn out of the kiln the better.

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 8

1.8 Chloride cycles

One solution to this chloride cycle problem can be the installation

of an alkali bypass or bleed.
Drawing kiln exit gases out of the kiln
at 1000C+, and then quenching those
gases inevitably imposes a thermal
energy penalty on the process.
Each percent of bypass means ~20
kJ/kg clinker increased fuel
consumption on a preheater kiln
or 10 kJ/kg clinker per percent of bypass on a precalciner
kiln as the volume of hot kiln inlet exhaust gases is that much
less.

Cement Kiln Chemistry

1.8 Chloride cycles

However, if no bypass is installed then that solution is not available

to solve chloride cycle problems.
Because the melting
point of chlorides is so
low they condense
higher up the preheater
This means that the
amount of chloride
exiting the preheater in
Purging some of the
the dust to the external
dust and interrupting
cycle can be as high as
the external cycle can
the total inputs in the
then be sufficient to
feed and fuel.
avoid preheater
blockagesas much chloride can be purged in the dust
as is entering the kiln.

Cement Kiln Chemistry

1.8 Chloride cycles

However, if no bypass is installed then that solution is not available

to solve chloride cycle problems.
Because the melting
point of chlorides is so
low they condense
higher up the preheater
This means that the
amount of chloride
exiting the preheater in
Purging some of the
the dust to the external
dust and interrupting
cycle can be as high as
the external cycle can
the total inputs in the
then be sufficient to
feed and fuel.
avoid preheater
blockagesof course there is then the problem of
disposing of the purged 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 8

1.8 Chloride cycles

However, if no bypass is installed then that solution is not available

to solve chloride cycle problems.
Because the melting
point of chlorides is so
low they condense
higher up the preheater
This means that the
amount of chloride
exiting the preheater in
Purging some of the
the dust to the external
dust and interrupting
cycle can be as high as
the external cycle can
the total inputs in the
then be sufficient to
feed and fuel.
avoid preheater
blockagesThis solution is more applicable to grate
preheater and 1 or 2 stage preheater kilns.

Cement Kiln Chemistry

1.8 Chloride cycles

A further solution to chloride problems can be to modify the material

flow in the preheater creating meal curtain at the kiln inlet.

Some cool material

from the upper stages
of the preheater is
diverted to the kiln
inlet.

Cement Kiln Chemistry

The chlorides are

intercepted before they
reach the preheater and
therefore cannot cause
blockages of the
preheater.

The chloride in the gas

exiting the kiln
condenses on the cool
meal in the curtain.

1.8 Chloride cycles

Bypasses and dust purges are much less effective as solutions to

sulphate recirculation problems.

Sulphur inputs to
cement kilns are
significantly higher
than chloride inputs.

The volatility of
sulphates is not as high
as chlorides so the
concentration factor is
not high enough for a
bypass or dust purge to
be effective.

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 8

1.8 Chloride cycles

We will consider the chemistry of sulphates in the cement kiln in the

next session of the course.

Sulphur inputs to
cement kilns are
significantly higher
than chloride inputs.

The volatility of
sulphates is not as high
as chlorides so the
concentration factor is
usually not high enough
for a bypass or dust
purge to be effective.

Cement Kiln
Process Chemistry
Module 1. Cement kiln energy efficiency and
productivity.
1.8 Chloride cycles, bypasses and purges.

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