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Cl i nker : r eact i ons i n t he ki l n

This page reviews the reactions which take place as the feed passes through the
The blended, milled raw materials go to a silo and from there to the kiln.
The reactions which take place in the kiln can be considered under three broad
headings:

Decomposition of raw materials - reactions at temperatures up to about 13

Alite formation and other reactions at 1300 C-1450 C in the burning zone.
Cooling of the clinker.

Decomposition of raw
w m a t e r i a l s - r e a c t i o n ss a t t e m p e r a t u r e s u p t
about 1300 C
This includes:
i.
ii.
iii.
iv.

Water evaporation in the raw feed, if any.

Loss of carbon dioxide from the limestone (ie: calcining).
Decomposition of the siliceous and aluminosilicate fractions of the feed.
Formation of a sulfate melt phase.

The decomposition products react with lime to form intermediate compounds whi
turn form other compounds as clinkering proceeds.

Wa t e r e v a p o r a t i o n
In wet-process kilns, and their derivatives, water must first be driven off. In a
wet-process kiln, calcining takes place after the water has been driven off, about
third of the way down the kiln. In the more modern pre-calciner kilns, the feed is
calcined prior to entering the kiln.

Cal ci ni ng
In isolation, decarbonation of calcium carbonate at 1 atmosphere takes place at 8
This temperature is reduced to 500 C-600 C if the reaction takes place in contact
quartz or the decomposition products of clay minerals, which react with the calciu
oxide as it forms.

In a wet-process or preheater system without a pre-calciner, most of the calcinat

takes place in the rotary kiln within a moving mass of feed. This situation is not id
for calcination because heat transfer has to take place through a large mass of m
and CO2 has to escape outwards as heat moves inwards.

A pre-calciner calcines the raw material much more efficiently than a wet-process
Raw meal is dispersed in the hot gas and calcination takes place in seconds, rathe
than the half an hour or so inside a kiln at the same temperature.

F o r ma t i o n o f e a r l y a n
nd
d i n t e r me d i a t e c o mp o u n d s
During calcination, the lime produced starts to react with other components of th
feed. The initial silicate product is belite. Some calcium aluminate and ferrite pha
also start to form.

A number of phases are formed in the clinker feed before the burning zone prope
reached. These intermediate phases dissociate in the burning zone and are not
therefore found in clinker but assist in forming the final clinker minerals.

S u l f a t e me l t p h a s e
At intermediate temperatures, sulfates combined with calcium and alkalis form a
phase. This is separate from the aluminate and aluminoferrite-based liquid forme
the burning zone - the two liquids are immiscible.

As with the main liquid phase, the sulfate liquid phase contributes to ion mobility
promotes combination.

A l i t e f o r m a t i o n a n d o tth
he r r e a c t i o n s a t
1 3 0 0 C - 1 4 5 0 C i n t h ee b u r n i n g z o n e

In the burning zone, above about 1300 C, reactions take place quickly. The clinke
the burning zone for perhaps 10-20 minutes but in this time a lot happens:
i.
ii.
iii.
iv.

The proportion of clinker liquid increases and nodules form.

Intermediate phases dissociate to form liquid and belite.
Belite reacts with free lime to form alite.
Some volatile phases evaporate.

Cl i nker l i qui d and nod

du
ul e f or mat i on
Above about 1300 C the proportion of liquid starts to increase - by 1450 C, perha
20-30% of the mix is liquid. The liquid forms from melting ferrite and aluminate p
and some belite. The liquid content is more than the sum of the aluminate and fe
phases in the cooled clinker because of the dissolved lime and silica.

The additional liquid causes coalescence of clinker particles, leading to the format
nodules.
Di ssoci at i on of i nt er m
meedi at e phases
The intermediate phases dissociate to form mainly aluminate phase, which then
becomes part of the liquid, and belite.

A l i t e f o r ma t i o n
Alite forms by the transition of some of the belite to alite and also directly from f
lime and silica to alite. These reactions occur rapidly once the clinker temperature
above about 1400 C.

Evaporat i on of vol at i llees

Volatile phases in the cement kiln are principally alkali sulfates, with a much sma
proportion of alkali chlorides. As the part-burned feed approaches the burning zo
these volatile phases are in liquid form and a proportion volatilizes, the remainde
passing out of the kiln in the clinker as inclusions within the pores.

The volatilized material passes back down the kiln, where it condenses on the rel
cool incoming feed. It again becomes part of the sulfate melt phase, promoting
reactions, and is once again carried within the clinker towards the burning zone.

This recirculating load of alkali and sulfate can occasionally become excessively h
Large quantities of condensing volatiles can then cause blockages in the kiln or in
preheater as the condensed liquid sticks feed particles together, forming accretio

Cooling of the clinker

As the clinker cools, the main liquid phase crystallizes to form aluminate phase, f
and a little belite.
Fast cooling of clinker is advantageous - it makes for more hydraulically-reactive
silicates and lots of small, intergrown, aluminate and ferrite crystals.

Slow cooling gives less hydraulically-reactive silicates and produces coarse crysta
aluminate and ferrite - over-large aluminate crystals can lead to erratic cement s
characteristics. Very slow cooling allows alite to decompose to belite and free lim

You are in Cl i nker : r eact i ons i n t he ki l n

The following pages have more details on clinker composition, reactions in the kil
cement milling:
Cement notation / Clinker compositional parameters / Bogue calculation /
Combinability / Cement milling

Check the Ar t i cl e Di r ect ory for more more articles on this or related

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