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CemNet Training - Course CKPC01

Module 2.9

Cement Kiln
Process Chemistry
Module 2. Cement clinker quality and composition.
2.9 Soluble alkalis.

Cement Kiln Chemistry

2.9 Soluble Alkalis

We have already discussed the importance of the alkali and sulphate


minor components in the clinker in previous sessions.
In sessions 1.5 and 1.6 we saw that alkalis and sulphates
increase the volume of flux in the kiln and in that way promote
the formation of the clinker minerals.. ..but that
they are also preferentially taken into solid solution in the C2S,
and as a result inhibit the formation of C3S.

Cement Kiln Chemistry

2.9 Soluble Alkalis

We have already discussed the importance of the alkali and sulphate


minor components in the clinker in previous sessions.
In session 1.9 we talked about the importance of the alkali to
sulphate ratio in the hot meal.. ..an excess of
sulphate over alkalis can bring many kiln operational problems
in the shape of hard build-ups in the preheater, ring formations
in the kiln inlet, possible clinker balling, finer granulometry of
the clinker.. ..at worst leading to heavy dust
recirculation from cooler to kiln.. ..possible
decomposition of C3S to C2S and attendant high free CaO
clinker.
These problems arise from the formation of CaSO4 in the
clinker.. ..in terms of clinker quality and composition any
CaO combined as CaSO4 will effectively reduce the LSF
and C3S content of 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 2.9

2.9 Soluble Alkalis

We have already discussed the importance of the alkali and sulphate


minor components in the clinker in previous sessions.
In session 2.6 we saw that if K2O is present in significant excess
of sulphate then there is the possibility of the formation of
KC23S12.. ..if this occurs then the KC23S12 is not
available for conversion to C3S.
..the lime saturation
of the remainder of the material is raised and high free CaO
clinker can result.
These problems can be avoided by balancing the molar ratio of
..in addition
the alkalis and sulphate in the clinker.
to the hot meal.
However, balancing the alkalis and sulphates has its own
significant effect on the clinker quality and the hydraulic
performance of the clinker minerals.

Cement Kiln Chemistry

2.9 Soluble Alkalis

We have already discussed the importance of the alkali and sulphate


minor components in the clinker in previous sessions.
Alkali sulphates in the clinker dissolve very quickly when
cement is mixed with water. ..this changes the solution
equilibrium with sulphate, SO42-, ions displacing hydroxide,
OH, from solution.
Calcium hydroxide, Ca(OH)2, is one of the products of
hydration of C3S.
C3S + H2O C-S-H + Ca(OH)2
Displacement of hydroxide from the cement mixing water
solution means that the equilibrium of this reaction is shifted
towards the products.. ..leading to more rapid hydration.

Cement Kiln Chemistry

2.9 Soluble Alkalis

We have already discussed the importance of the alkali and sulphate


minor components in the clinker in previous sessions.
This more rapid hydration leads to accelerated setting and early
strength development...however, later strengths at 28
days can be depressed.
The magnitude of these effects depends on the total amount of
alkali sulphate present in the clinker.
Total alkalis as sodium equivalent, Na2Oeq, is limited to less
than 0.6% in low alkali cement in order to avoid durability
problems in concrete due to the alkali-silica reaction.
Na2Oeq, = %Na2O + %K2O x 62/94
Where 62 and 94 are the molecular weight of
Na2O and K2O respectively.

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 2.9

2.9 Soluble Alkalis

We have already discussed the importance of the alkali and sulphate


minor components in the clinker in previous sessions.
This more rapid hydration leads to accelerated setting and early
strength development...however, later strengths at 28
days can be depressed.
The magnitude of these effects depends on the total amount of
alkali sulphate present in the clinker.
Total alkalis as sodium equivalent, Na2Oeq, is limited to less
than 0.6% in low alkali cement in order to avoid durability
problems in concrete due to the alkali-silica reaction.
There should be no problems controlling the setting or
workability of low alkali cement.

Cement Kiln Chemistry

2.9 Soluble Alkalis

We have already discussed the importance of the alkali and sulphate


minor components in the clinker in previous sessions.
This more rapid hydration leads to accelerated setting and early
strength development...however, later strengths at 28
days can be depressed.
The magnitude of these effects depends on the total amount of
alkali sulphate present in the clinker.
However, with higher alkali cements setting can become
increasingly rapid... ..potentially leading to workability
problems.
1.8% K2SO4 (0.97% K2O) in clinker is suggested as a
maximum to avoid these problems ..as K2O
content increases, the degree of sulphatisation is
reduced to achieve this.

Cement Kiln Chemistry

2.9 Soluble Alkalis

We have already discussed the importance of the alkali and sulphate


minor components in the clinker in previous sessions.
This more rapid hydration leads to accelerated setting and early
strength development...however, later strengths at 28
days can be depressed.
The magnitude of these effects depends on the total amount of
alkali sulphate present in the clinker.
This increased clinker reactivity is useful when blended
cements are being produced... ..the pozzolanic reaction is
activated by the hydration of the clinker minerals..
..helping to offset the low early reactivity and strength
development of blended cements.
Some cement companies add sodium sulphate,
Na2SO4, to blended cement to achieve this effect.

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 2.9

2.9 Soluble Alkalis

We have already discussed the importance of the alkali and sulphate


minor components in the clinker in previous sessions.
This more rapid hydration leads to accelerated setting and early
strength development...however, later strengths at 28
days can be depressed.
The soluble alkali sulphate content of cement has the strongest
correlation with the early strength development.. .early
strength can be boosted by up to 10%..........
.but at
the expense of a 10~15% reduction in 28 day strength.

Cement Kiln Chemistry

2.9 Soluble Alkalis

We have already discussed the importance of the alkali and sulphate


minor components in the clinker in previous sessions.
In Session 1.6 we saw that the Aalborg technology of
mineralised cement manufacture involves the addition of
..this
sulphate and fluoride to the kiln feed.
certainly involves high levels of soluble alkali sulphates being
present in the clinker.
We will return to the topic of mineralised clinker and its
quality characteristics in the next and final session of this
module 2 of the course.

Cement Kiln
Process Chemistry
Module 2. Cement clinker quality and composition.
2.9 Soluble alkalis.

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