S.Afr.J.
Chem, 1997,50(3) NON-RESEARCH ARTICLES
High temperature chemistry in a cement
clinker kiln
J.H. Potgieter
Applied Chemistry Research Group, Pretoria Portland Cement
Technical Services, P.O. Box 40073, Cleveland, 2022,
Johannesburg
A cement kiln is a high temperature reactor and due to its
design, contains zones of varying temperature. The
production of various types of clinker from different raw
materials as well as a variety of refractories used in various
parts of the kiln, all lead to a multitude of reactions that can
occur in different parts of the kiln. This paper will give an
overview of the different types of clinker that are produced in
kilns and the associated chemical reactions that occur during
their production. In addition it will also focus on the types of
refractories used in cement kilns and their chemistry. Finally,
some of the interactions that can occur between the raw
materials and the lining materials will be examined.
For a chemist used to observing chemical reactions in con-
tainers in a laboratory, it is quite a paradigm shift to be con-
fronted with the types of chemical reactions that can occur in
a cement kiln. Not only do these reactions occur at very high
temperatures, they also occur in a very large reactor; typically
85 to 140 m long, with a diameter from 3.5 to 5 m.1 1 Further-
more, the reactor is not uniform with respect to either its con-
stitution or the temperature inside it. Different types of
refractories are used to line different parts of the cement kiln
and various temperature zones are encountered along the
length of the kiln during operation. If one takes into account
that a variety of raw materials are used in the production of
different types of cement or even one particular type of
cement, ail of these factors combine to produce a dazzling
array of possible chemical reactions and transformations that
can take place in a cement kiln.
There is a large amount of literature available on cement
production and refractories, and the purpose of this paper is to
examine only some of these reactions and interactions super-
ficially. In order to facilitate the discussion, the convention
used in the cement industry to abbreviate certain compounds
with certain letters, will be adopted. The preference to express
all elements as their respective oxides of interest will also be
followed. The nomenclature used is as follows:
Ca -CaO -C
Mg -MgO -M
Fe - Fe 2 0, - F
A1 - A120·, - A
Si - Si0 2 -S
S -SOt -s
Water - H 2 0 -H
The reaction vessel 1 - 1
The cement kilns in which the reactions occur can differ quite
significantly in design, size and type. These characteristics
influence the temperatures and types of refractories encoun-
tered in various parts of the kiln, and therefore the chemical
reactions occurring. For simplicity, we shall consider a long,
dry kiln as illustrated in Figure l. 1 Depending on the kiln con-
figuration, up to six different temperature zones can be distin-
111
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Figure 1 Long, dry cement kiln with different temperature zones
prevailing during operation.
guished along the length of the kiln. Each zone is normally
lined with a different type of refractory to cater for the spe-
cific temperature and type of reaction that can take place.
A short description of each of the zones and the type of
refractory used therein is given below: 1
Zone I: Preheating zone
The area where free moisture is lost from the raw materi-
als. Usually fairly short and normally lined with highly
specialised insulating bricks.
Zone 2: Calcining zone
Where removal of carbon dioxide from carbonates
(CaC01 & MgCO,) and decomposition of the clay miner-
als occurs. Generally lined with refractory bricks contain-
ing 40-70% alumina.
Zone 3: Intermediate zone
Sometimes referred to as the safety zone. Liquid forming
reactions can start to take place. High alumina (50-80%)
type bricks are used in this area.
Zone 4: Transition zone
Where liquid forming reactions occur and a coating can
build up on the refractory bricks. Magnesia-chrome or
magnesia-spinel bricks are preferred in this area.
Zone 5: Burning zone
Where the clinkering reactions take place and coating
forms easily on the refractories. Magnesia or
magnesia-chrome, dolomite and dolomite modified with
zirconium oxide bricks are normally used in this part of
the kiln.
Zone 6 . Outlet zone
The cooling and discharge zone which has a transitional
area just after the burning zone. High abrasion and wear
area in which high alumina bricks perform satisfactorily.
Magnesia-spinel bricks also perform well in this area.
Another important feature that should be borne in mind
about the reaction vessel, is that it is subject to significant
thermal and mechanical stresses. These two influences have a
dramatic effect on the types of refractory bricks used in dif-
ferent parts of the kiln and thus also the subsequent chemical
reactions that could take place. Figure 2 1 shows graphically
the real configuration in an operating kiln compared to the
ideal situation.
Manufacturing Ordinary Portland Cement Clinker
(OPC) '- 1
The raw mix for Portland cement clinker is generally obtained
by blending a calcareous material, typically limestone, with a
smaller amount of an argillaceous material, usually clay or
shale. It may be necessary to include minor proportions of
one or more corrective constituents, such as iron ore. bauxite
112 NON-RESEARCH ARTICLES S.-Afr.Tyd.skr.Clictti., IW7, 50(3)

UNDEFORMED DEFORMED 2(FeO.OH) Fe 2 0, + H 2 0

(Ideal) (Real) (iii) The formation of belite, aluminate and ferrite
2Ca0 + Si0 2 p-C 2 S (belite)
3CaO + ALO, C,A (aluminate)
4CaO + A1 2 0, + Fe2(), C4AF (ferrite)
(b) Those at 1300-I450°C, when a melt is formed from
the ferrite and aluminate and much of the belite reacts
with nearly all the lime to give alite
C2S + CaO -> C,S (alite)
The material nodulizes and forms clinker.
(c) The cooling phase when the liquid crystallizes into
aluminate and ferrite phases and polymorphic transitions
of alite and belite occur. Figure 3 2 shows a photomicro-
graph displaying the microstructural appearance of OPC
clinker with the various phases, while Figure 4 1 represents
graphically the changes for a typical OPC clinker as a
function of temperature .

Figure 2 Real vs. ideal configuration of a cement kiln during

operation.

or sand, to increase the proportions of FejO^, A1 2 0, or S i 0 2 ,

respectively. The contribution of the fuel ash (coal ash) to the
clinker composition must also be taken into account.
The principal reactions taking place can be divided conven-
iently into three groups, namely:
(a) Those below 1300°C, of which the most important are "IRON OXIDES
(i) The decomposition of calcite
CaCO CaO + C 0 2 800 1200 COOLING
0 400 TEMPFRATURF (°CI
(ii) The decomposition of clay minerals
AS„H A1 2 0, + 4Si0 2 + H 2 0
Figure 4 Schematic diagram showing the variations in typical
AS,H 2 -> ALO, + 2Si0 2 + 2H 2 0 contents of phases during the formation of Portland Cement ( OPC )
clinker.

Manufacturing High Alumina Cement Clinker (HAC)1

Figure 3 Photomicrograph of OPC clinker microstructure.
Angular crystals represent G,S (alite), while rounded crystals are
C2S (belite). The interstitual phase represents the liquid formed in
the manufacturing process and contains a variety of compounds,
mostly calcium aluminate types.
High alumina cement is normally produced by the complete
fusion of limestone and bauxite at 1450-I600°C. In order to
produce a cement with the desired rapid-hardening properties,
both raw materials must be low in Si0 2 . The molten clinkcr is
tapped off continuously from the kiln, solidifies and is
crushed and ground to the required fineness. The main
compound of interest in all HAC is monocalcium aluminate,
CA, because it is mainly responsible for the hydraulic activity
and consequently the strength development. It normally
makes up 40-50% of the compounds present in the HAC. The
composition of these cements varies more widely than
Portland cements and is very sensitive to the operating
conditions and the presence and concentration of other
elements, for example, Ti0 2 , Fe 3 0„ etc., in the starting
materials.
The principal reactions that can take placc are the
following:
S.Afr.J.Chem, 1997, 50(3) NON-RESEARCH ARTICLES
CaO + ΑΙ,Οτ CA (monocalcium aluminate)
3CaO + A1 2 0, C^A (tricalcium aluminate)
4CaO + A1 2 0, +Fe 2 0, QAF (ferrite)
2CaO + Si0 2 P-C2S (belite)
12CaO + 7A1 2 0, C, 2 A 7
CaO + 2AljO, CA 2
CaO + 6A1 2 0, CAFT
2CaO + A! 2 0, + Si0 2
C 2 AS (gehlenite)
As a general rule, ferrite is always present, belite is often
present and gehlenite cannot coexist stably with C I2 A 7 in high
alumina cements.
Manufacturing expansive cement clinker
Clinkers of expansive cements can be produced at about
1200°C, that is, at temperatures 200-250°C lower than for
OPC clinker. Furthermore, the fired clinker is relatively soft
and friable and is easy to grind. Consequently the manufac-
turing process consumes less energy. Another attractive fea-
ture of expansive cements is that large-scale utilisation of
industrial process wastes and by-products can be made in the
production of these materials. Typically low-grade limestone,
bauxite fines, phosphogypsum, flyash and blast furnace slag
in various proportions, can be utilised to manufacture expan-
sive cements. Expansive cements earn their classification
from the formation of ettringite, C,A.3Cs.32H(3CaO.Al2Ov
3CaS0 4 .32H 2 0) during hydration; an expansive compound
which counters the shrinkage of concrete or mortar on hard-
ening. The main components of expansive cements are belite
(which normally comprises about half of the amount of com-
pounds present) and calciumsulphoaluminate, C4A.,s. How-
ever, a large number of other potential compounds can also be
encountered in this type of cement, depending on the type and
quantities of raw materials used in its production. It is also not
uncommon to find combinations of OPC and expansive
cements interground and applied together in the construction
industry.
The main reactions normally occurring during the manu-
facture of expansive cements are:
2CaO + Si0 2 ^ f}-C2S _ (belite)
3CaO + 3A1 2 0, + CaS0 4 -> C 4 A,s
(calciumsulphoaluminate)
4CaO + A1 2 0, + Fe 2 0, -> C 4 AF_ (ferrite)
4CaO + 2Si0 2 + CaS0 4 C s S 2 s (calciumsulphosilicate)
A large number of calcium aluminate and calcium ferrite
phases can also form, but are normally only present in minor
amounts. Very often calcium sulphate anhydrite is one of the
various compounds present in expansive cements.
The Refractory Lining
Before considering the possible reactions between the raw
material in the kiln and the lining, it is necessary to make a
few remarks about the refractory lining and the types of
refractory bricks that could be encountered in the cement kiln.
The primary purpose of the refractory lining is to protect the
steel shell of the kiln. A secondary function is to reduce heat
losses by radiation and convection from the rotary kiln shell.
From the application point of view, refractories can be
divided into two groups,1 namely formed refractory products
(bricks) and unshaped refractory products (castable). How-
ever, lining with bricks is the predominant practice, with
refractory concrete only being used in specific areas where
maintaining a brick lining is difficult. As far as their chemical
compositions are concerned, refractory bricks mainly consist
of A1 2 0 3 , Si0 2 , MgO, CaO, and Cr 2 0,, either alone or in vari-
ous combinations together. According to ISO recommenda-
tions,1 refractory products are divided into the following
types:
(a) acidic
(b) basic
(c) special,
cach with a defined percentage of component oxides.
Acidic refractory products: This class consists mainly of
A1 2 0, and/or Si0 2 as the predominant component in the
brick.
Basic refractory products: This class comprises the magnesia,
magnesia-chrome, chrome-magnesia, dolomite and dolomite
modified with zirconium oxide types of hricks.
Special refractory products: This class contains compounds
such as zirconium silicate, graphite, carbon, silicon carbide,
spinels(except chromite) and products based on pure oxides.
Spinel is added so that the bricks are able to cope with
mechanical stresses exerted during kiln operation. Stress fac-
tors prevailing in cement kilns demand high elasticity from
bricks, a characteristic that pure oxide components cannot
offer. Fracture toughness of refractories can be significantly
enhanced by the addition of spinel to the brick. The composi-
tions of some typical refractory bricks are given in Table 1.
Chemical reactivity of the refractory lining
Refractories can take part in a large number of high tempera-
ture chemical reactions inside a cement kiln, some of which
will now be considered in more detail. The type of reaction
that can occur, can be classified as either:
(a) corrosion (loss of bonding between compounds)
(b) infiltration
(c) condensation
and is due to the interaction of the refractory lining with:
(i) the clinker melt
(ii) the volatile components of the raw materials
(iii) the oxidising or reducing atmosphere in the kiln,
or combinations of these.
Reactions with the clinker melt
It should be borne in mind that one of the aims during kiln
operation is to build up a stable coating on the refractory
bricks in the burning zone in order to increase the working
life of the bricks. A stable coating reduces the wear of the
bricks and results in better insulation that decreases the ther-
mal load on the kiln shell. However, when the liquid phase of
cement raw meal infiltrates into the bricks, the bonding struc-
ture can be destroyed, thus causing spalling of the refractory
brick. Some of the reactions that can occur, are as follows:
CaO (in brick) + P-C2S C,S
7Α1 2 Ο λ (brick) + 12CaO C I 2 A 7 (mayenite)
MgO. CaO (brick) + Si0 2 -> CMS (monticellite)
3(MgO.CaO) (brick) + 2Si0 2 C,MS2(merwinite) + 2MgO
2Mg0.Si02 (brick) +2CaO -> C2S(belite) + 2MgO
 14 NON-RESEARCH ARTICLES S.-Afr.Tydskr.Chcm., 1997, 50(3}

Table 1 Chemical composition of some refractory bricks used in cement kilns

Sindoform Sindoform Radex
BrickName K11103 K i t 105 Permag HZ96 Ankral RI7 AS90S VR60KL
Z r 0 2 modified Z r 0 2 modified Magnesia Magnesia Magnesia Alumina-
Type of brick Dolomite dolomite magnesia spinel spinel chrome 1 silica
Chemical com-
position (%)
Si02 10 1.0 0.5 0.2 0.2 2.3 44.0
A1 2 0, 0.5 0.5 0.2 12.0 6.5 5 1.0
Fe 2 0, O.S 0.8 0.5 0.5 0.4 4.0 2.0
CaO 59 2 58.0 1.0 0.7 0.8 0.7 0.8
MgO 38.5 37.0 96.0 86.0 92 72.0 0.0
ZrO, 2.7 1.8
Cr20, I2.0

Reactions with the volatile components (alkalies, chlo-
rides and sulphates)
Volatile compounds not only corrode certain types of refrac-
tory bricks, they can also infiltrate the brick and densify its
structure. Infiltration decreases the refractoriness of the brick.
Alkali penetration into the refractory and subsequent conden-
sation or reaction with the matrix leads to the formation of
compounds that can cause expansion and ultimately structural
deterioration. Some of the reactions that can occur are:
2Cr 2 0 3 + 9 0 2 + 4K 2 0 4K2O.CrOf,
Na 2 0 + 3AI20_1.2Si02
Na 2 O.Al 2 0 3 .2Si0 2 (Na 2 0.AS 2 >+-2Al 2 0,
3Na 2 0 + 2(3AI 2 0 1 .2Si0 2 ) [2A,S2] ->•
3Na 2 0.2Al 2 0 1 .4Si0 2 (3Na 2 0.A 2 S 4 )44Al 2 0,
K 2 0 + 3AI 2 0 v 2Si0 2 (mullite)
K 2 0.Al 2 0. v 2Si0 2 (K 2 0.AS 2 )+2Al 2 0,
CaO + SOt CaSQ
CaO + 2MgO.Si02 Ca0.Mg0.Si0 2 + MgO
2CaO + 3SO·, + K 2 0 K 2 S0 4 .2CaS0 4
Reactions in the oxidising or reducing atmosphere of
the kiln
Reactions of this kind lead to structural destruction and spel-
ling of the refractory bricks. Typical examples are:
2Mg0.Fe 2 0, + CO 2(Mg, Fe)0 + C0 2 + 0 2
(Mg, Fe)0 + CO MgO + Fe + C0 2
Mn 2 0 3 +CO 2MnO + C0 2
It should be borne in mind that refractory brick life is not only
limited by chemical reactions, but also by mechanical and
thermal stresses. Stable kiln and operating conditions are
essential to extend refractory life. A summary of the various
parameters influencing refractory lifetime is shown in
Figure 5.
Conclusions
The discussion above indicates that a wide variety of chemi-
cal reactions can occur at high temperatures in a cement kiln.
The temperature, the nature of the raw materials and the com-
position of the different types of refractories are important
parameters influencing the chemical reactions that can take
place. The large number of complex compounds that are
formed in the various chemical reactions present an impres-
sive picture of real life chemistry.

Acknowledgements
Brick
This paper is published with permission of PPC.

References
A complete list of references is available from the author of this
<? ^
paper, and therefore only the main ones are given below:
/ compressive flexural tensile
/and shcar-forces SQueeung aclion abrasive wear dueto kiln feed \
(clinker notiulei) \
1 H.F.W. Taylor, Cement Chemistry, Academic Press Ltd.,
/ due lo kiln shell defbrma lion London, 1990, 1,316,335.
2 D.G. Mantel, The Manufacture, Properties and Applications of
Portland Cements, Cement Additives and Blended Cements,
Figure 5 Schematic diagram summarising the various different
types of parameters influencing refractory lifetime. Penrose Press, 1991, 4.
3 Μ. Kearns, PPC Cement Technology Course, 1994.