Textbook: Package P3: Kiln - Operation and Optimisation Raw Material Characteristics

Package P3: Kiln – Operation and Optimisation
Module 4: Raw Material Characteristics
TEXTBOOK
Course name : Kiln operation and optimisation

Course number : P3
MODULE NUMBER : 4
Module title : Raw material characteristics
Module objectives : The participants will be able to:
Identify the influence of various raw mate-

rial characteristics on overall function and
operation of kiln system.
Explain how operation is supervised and
required corrective measures taken, given
the various raw mixture characteristics.
Duration : 0,5 day

Necessary facilities : Classroom.
Access to laboratory.
Necessary instruments : -
© F L Smidth
TABLE OF CONTENTS
RAW MATERIAL MIXTURES AND THEIR CHARACTERISTICS .......................... 4

4.1 INTRODUCTION ...................................................................................................... 4
4.2 BURNABILITY OF RAW MIX ................................................................................ 5
4.2.1 Coarse grains ....................................................................................................... 5
4.2.1.1 Coarse grains - determination ....................................................................... 7
4.2.2 Effects of chemical composition ......................................................................... 7
4.2.3 Alternative burnability determination ............................................................... 10
4.2.3.1 Burnability index. ....................................................................................... 10
4.2.3.2 The burnability factor ................................................................................. 10
4.3 CLINKER FORMATION ........................................................................................ 11
4.3.1 Effect of changes in chemistry .......................................................................... 13
4.3.1.1 Reduction in the alumina/iron ratio ............................................................ 13
4.3.1.2 Lowering of the silica modulus .................................................................. 14
4.3.1.3 Lowering the lime saturation factor............................................................ 14
4.4 THE BEHAVIOUR OF VOLATILE MATTER ..................................................... 15
4.4.1 Mechanism of circulation of volatile matter...................................................... 15
4.4.1.1 Evaporation in the kiln ............................................................................... 15
4.4.1.2 SO2 gas and volatile matter exiting the preheater ...................................... 16
4.4.1.3 Condensation in the preheater .................................................................... 16
4.4.2 Affinity between the volatile components ......................................................... 16
4.4.3 Volatility of the compounds of volatile components......................................... 17
4.4.3.1 Definition of volatility ................................................................................ 17
4.4.3.2 Average evaporation factors: ...................................................................... 18
4.4.3.3 Molecular ratio of sulphur and alkalis ........................................................ 19
4.4.3.4 Vapour pressure .......................................................................................... 20
4.4.4 A mathematical model ....................................................................................... 21
4.4.4.1 Definitions; evaporation factor and valves ................................................. 22
4.4.4.2 Rules of computations ................................................................................ 23
4.4.4.3 Average values for ε and valves ................................................................. 23
© F L Smidth Page 2
4.4.5 Three aspects of volatile matter ......................................................................... 24

4.4.5.1 Content of volatile matter in clinker ........................................................... 25
4.4.5.2 Emission to the environment ...................................................................... 26
4.4.5.3 Operational aspects ..................................................................................... 26
4.4.6 Solving problems with sulphur .......................................................................... 30
4.4.7 Solving problems with chloride......................................................................... 31
4.4.8 Solving problems with alkali ............................................................................. 32
4.4.9 Setting up a mass and volatile matter balance ................................................... 33
4.5 CONCLUSION ........................................................................................................ 37
RAW MATERIAL MIXTURES AND THEIR CHARACTERISTICS
4.1 INTRODUCTION
Designing a raw mix is a complex process involving many factors. Often it is possible
to obtain desired chemical properties of the clinker using a different blend of the avail-
able raw materials.
The behaviour of a new and untried raw mix in the kiln can to a large degree be pre-
dicted by the tools provided in the concept of Burnability. However, there are definitely
cases where more complex investigations are required to explain kiln behaviour and the
observed clinker properties. In this case microscopy examinations on the clinker is
widely used to provide further information.
While the goal is to produce clinker with uniform and predictable quality, it is necessary
that this is done with a minimum amount of energy that the kiln operation is smooth and
that expensive downtime of the kiln is avoided.
To achieve this goal it is necessary to know
• which parameters in the raw mix influence the kiln operation

• how and why they influence operation
• what can be done about it
In this module, three central concepts in the relation between raw meal characteristics
and kiln operation is treated, namely:
• the burnability of a raw mix,

• the clinker formation treated as a physical agglomeration process and
• the circulation phenomena of volatile matter in a kiln system.
Each of these concepts serve to explain how various characteristics of the raw mix in-
fluence the kiln operation and explain what appropriate action can be taken in kiln op-
eration.
4.2 BURNABILITY OF RAW MIX

Different types of raw mix are designed to give proper amounts of the clinker minerals:
alite (C3S), belite (C2S), aluminate (C3A) and ferrite (C4AF). The readiness with which
a raw mix is transformed into these minerals in the course of a high temperature treat-
ment is determined by their chemical, mineralogical and granular composition or a
combination of these elements. Such readiness of transformation into the clinker min-
erals is called the burnability. Burnability is the deciding factor for the temperature
necessary in the kiln burning zone in order to obtain a satisfactory clinker product.
The burnability is determined in the laboratory on a small representative sample of the

kiln feed. One procedure used in laboratories consists essentially of an isothermal
treatment of the calcined raw meal, one part at 1400 °C, another at 1450 °C, and a third
at 1500 °C, all for 30 minutes. After cooling, the content of free lime in the clinker is
determined, and the results, relative to those of a well-known standard sample similarly
treated, are taken as a measure of the burnability.
Different types of raw mix with the same chemical composition and equal fineness may
have greatly differing burnabilities. The reason for the differences in burnability can be
found in the differences in mineralogical composition of the raw mix types.
A formalised description of the various minerals in the raw mix according to their
chemical reaction rates during burning has been developed. The results gained from the
theoretical work together with the experience gained from practical implementation of
the description have revealed that poor burnability of a raw mix may be caused by
coarse grains from two mineral groups:
(1) Calcite and marl rich in CaCO3

(2) Quartz and flint rich in SiO2
4.2.1 Coarse grains

The clinker consists of Alite, Belite, solidified Liquid phase, Free lime, and Pores. The
effect of coarse grains in the raw mix can be illustrated by looking at the distribution of
the clinker minerals in the resulting clinker. This is done by making a polished section
of the clinker sample and examining the clinker by microscopy. The optimum distribu-
tion, as seen through microscopy, can be seen in Figure 4.1. However, if the chemical
reaction has not gone to completion the result may be as seen on Figure 4.2. The reason
for this is local inhomogeneity in the raw mix. This may stem from course grains of
calcite or coarse grains of quartz.
Figure 4.2 shows a clinker with a large belite cluster (small dark grains) surrounding
what was previously a quartz grain. The cluster has not reacted with CaO to form the
desired C3S during the clinkerisation, and therefore the unused CaO is present some-
where in the clinker as free lime.
Figure 4.1 Homogenous Clinker
Figure 4.2 Inhomogeneous clinker with large belite cluster from coarse quartz.
If the original coarse grain had been calcite, a cluster of C3S would have been formed
around a grain of free lime. In both cases the clinker will present a high free lime con-
tent. So both coarse quartz and coarse calcite may result in poor burnability, with corre-
sponding high free lime content and too little C3S in the clinker.
4.2.1.1 Coarse grains - determination

The question is how to determine what constitutes a coarse grain?
From calculations, experience, and many tests using standard sieves, the following par-
ticle sizes have been found to be critical for residual free lime after burning for 30 min-
utes:
quartz and silicates: +45 µm

calcite: +125 µm
It has been found that after burning for 30 minutes at 1400oC, an increase in the amount
of coarse particles results in the following increases in free lime:
+1% quartz + 45 µm leads to +0,93% free CaO

+1% calcite + 125 µm leads to +0,56% free CaO
(From the above can be deducted that coarse grains of Quartz is more serious than
coarse grains of Calcite).
If improved burnability of the raw mix is desired, a reduction of the coarse particles can
be achieved by finer grinding. However, this may only have a significant effect on the
amount of coarse calcite since this is the softer material. If a high content of the hard
quartz particles must be reduced, separate grinding may be necessary.
The content of the coarse particles in the raw mix is determined in the polarising mi-
croscope. The coarse quartz is determined in the acid insoluble residue + 45 µm and
coarse calcite is determined in the total sieving residue on 125µm.
4.2.2 Effects of chemical composition

In addition to the coarse grains, both the lime saturation factor and the amount of liquid
phase in the raw mix at the burning temperature influence the burnability. Knowing the
effect on burnability caused by the coarse grains, the effect attributable to chemical
composition can be determined.
Statistical treatment of the data from a large number of raw meals of different types has
shown that the chemical parameters of significance are the lime saturation factor LSF,
and the silica modulus MS (MS is inversely related to the content of the liquid phase).
The following formula may be used for estimating the free CaO after burning for 30
minutes at 1400°C:
CaO1400o C = 0,33 ⋅ (LSF − 95) +1,8 ⋅ (MS − 2)

+ 0,93 ⋅ SiO2 (+ 45µ ) + 0,56 ⋅ CaCO3 (+ 125µ )
As expected, an increase in LSF and MS will result in higher free lime.
Figure 4.3 shows the correlation between free lime calculated according to this equation
and the corresponding measured free lime after laboratory burnability tests. Each total
free lime consists of three contributions. It is clear that the various raw mixes are very
different from each other, with respect to which of the three factors (coarse quartz,
coarse calcite, or chemistry) contributes to the bulk of the potential free lime.
Figure 4.3 Correlation between measured and estimated free lime
Using this formula makes it possible to optimise the burnability of a raw mix consisting
of given raw materials, not only in laboratory experiments but also under plant condi-
tions. Assuming that the contributions from the calcite, the quartz and the chemical
composition are known, the free lime will be as shown in figure 4.4 on the following
page (represented by the bar on the left).
Figure 4.4 Effect of raw mix changes on resulting free lime
It is shown in figure 4.4 that grinding to a 12% residue on the 90 µm sieve instead of to
17%, improves the burnability from 7,8 to 6,5% free lime due to a reduction in the
amount of calcite grains coarser than 125 µm.
At the plant from which this example is taken, the clinker was burned to an average free
lime of 2,5%. After the feed fineness was increased, this free lime level could be
achieved at a lower burning temperature, or its equivalent - a shorter burning time. In
this case, a 10% reduction in burning time was realised. This corresponds, for practical
purposes, to a 10% increase of the kiln output.
The burnability may also be improved by changing the chemistry. Changing the lime
saturation factor from 98 to 94 improves the burnability from 6,5% to 5,2% free lime, as
shown in Figure 4.4. Decreasing MS will also improve the burnability.
An alternative way of reducing the temperature at which clinkerisation takes place is by

the addition of mineralisers and fluxors. In the pure four component system of CaO,
SiO2, Al2O3 and Fe2O3, C3S does not form below 1250°C. A mineraliser is a minor
component which encourages the formation of C3S by lowering this lower limit of
stability of C3S. An example of a mineraliser that is widely used is fluoride. A fluxor is
a minor components which reduces the temperature at which liquid phase is first
formed, and modifies the viscosity and the surface tension of the clinker liquid to pro-
mote the formation of the clinker minerals. Sulphate is often used as a fluxor and intro-
duced as gypsum.
4.2.3 Alternative burnability determination

Quantitative microscopy is a rather time consuming technique not available at most ce-
ment laboratories. It is therefore encouraging that an adequate description of burnability
may also be obtained by using the raw mix acid insoluble residue > 45 µm and the total
residue > 125 µm, instead of the microscopically determined parameters.
The burnability expression obtained with LSF, Ms, acid insoluble residue A45 > 45 µm,
and total residue T125 > 125 µm as parameters is slightly different:
CaO1400o C = 0,35⋅ (LSF − 96) +1,58⋅ (MS − 1,6)

+ 0,55⋅ A45 + 0,12 ⋅ T125
For an evaluation of burnability, other formulas have been developed by earlier authors
of which we will mention the burnability index and the burnability factor. Both formu-
las only consider the chemical influence on the burnability and disregards the influence
of the mineralogy. Hence the accuracy of the formulas is limited.
4.2.3.1 Burnability index.

An early formula for the estimation of raw meal burnability is Kuehl's burnability index
defined as:
C3 S
Burnabilit y index =
C 4 AF + C 3 A
The higher the content of C3S with corresponding lower contents in C4AF or C3A, the
harder the clinker is to burn. The index is indirectly dependent on the LSF and the MS
and roughly proportional to the earlier mentioned formula for CaO1400°C without regard-
ing the contribution of coarse grains.
4.2.3.2 The burnability factor

The factor is developed based on pure empirical notions and observations and hence
might be suspect in its fundamental reasoning. The coefficients x, y and z are best de-
termined by multiple regression analysis performed on laboratory tests.
Burnabilit y factor = x ⋅ LSF + y ⋅ MS + z ⋅ (MgO + alkalies )

In the originally published formula, the coefficients were stated as x = 100, y = 10 and z
= 3.
4.3 CLINKER FORMATION

The distribution of the cement clinker size is very important with respect to kiln opera-
tion and cement mill operation and therefore directly affects the production cost of the
cement.
Dusty, finely grained clinker seriously endangers satisfactory maintenance free opera-
tion of grate coolers, and generally strongly reduces the brick life in the burning zone of
the kiln. Dust returned from the clinker cooler often leads to the formation of a porous,
unstable and pumice-like coating on the brick lining, instead of the desired dense, stable
coating. Furthermore, the handling of very dusty clinker is problematic and the
grindability is often inferior to that of a coarser, dust free clinker.
Experience shows that energy consumption in the cement mills may increase 40% when
the clinker granulometry changes from clinker nodules to the dusty or pumice like type.
It is of interest to discuss whether, and if so, how this dusty type of clinker can be
avoided.
Reflections on clinker formation, especially regarding agglomeration, have led to a

model in which two processes compete.
1) One is the physical agglomeration and nodulisation of the material in the

burning zone due to the formation of the clinker liquid phase.
2) The other is the formation and growth of C3S particles, which counteract
the nodulisation process.
Nodulisation
Pelletisation or nodulisation in drums is well known in many industries. The particles
are held together by the capillary forces of the liquid. Theory and experiments have
shown that the rate of formation of nodules is a function of the amount of liquid, parti-
cle size, and speed of drum revolution. There is every reason to assume that the same
physical principles determine the agglomeration processes in a rotary kiln.
At the entrance to the burning zone a system of particulate material and a liquid is pre-
sent. Figure 4.5 demonstrates the amount of liquid as a function of temperature. The
liquid is formed in a narrow temperature interval at approximately 1330°C. After this,
the amount of liquid increases very little with increasing temperature, and may be re-
garded as constant; at this time, as long as the particles are not too coarse, nodulisation
may take place.
Figure 4.5 % Liquid versus temperature
The formulas for calculating the amount of liquid phase from the chemical composition
of the clinker is presented in module 1, section 1.2.8.1.
C3S is formed in the material in the rotary kiln during the burning process. Numerous
investigations of clinker samples have shown that dusty and pumice like clinker - an
un-nodulised product - is often made up of sintered C3S particles.
These particles consist of several individual crystals, which have grown together.
When two C3S crystals meet, they have a high probability of growing together to form
coarse C3S particles; increasing the particle size in a nodulising system will slow down
and eventually stop the nodulisation process.
Figure 4.6 schematically shows the combination of nodulisation caused by the liquid
phase and the counteraction due to the formation and sintering of C3S particles. The up-
permost curve demonstrates the mean size of the nodules versus time, and the lower
curves show the formation of C3S. The curves demonstrate the situations for different
mean temperatures of the burning zone: The higher the temperature, the higher the for-
mation rate of C3S.
Figure 4.6 Formation and size of nodules, and formation of c3s at various
temperatures, both as a function of time
The more C3S is formed, the higher the probability of getting large particles consisting
of several C3S crystals grown together. Above a certain quantity of C3S, the number of
C3S particles is so large that further formation of nodules is impossible.
It is inferred from the diagram that a high mean temperature of the burning zone will
result in a small average nodule size.
4.3.1 Effect of changes in chemistry

The most noticeable changes in clinker formation result from changes in the ratios of
alumina/iron, lowering of silica modulus and LSF.
4.3.1.1 Reduction in the alumina/iron ratio

This change causes formation of a greater amount of liquid phase at a lower tempera-
ture. The maximum effect is obtained by reducing the ratio from 2,0 to 1,6, which is the
optimum value. As this will not influence the formation of C3S, it means that we have a
longer time with enough liquid phase for nodulising at the entrance to the burning zone,
and thereby improved nodulisation. An increase of the alumina/iron ratio will cause the
opposite to happen.
4.3.1.2 Lowering of the silica modulus

When the silica modulus decrease, the amount of liquid phase increases. If the clinker is
dusty because of too little liquid, a decrease in the silica modulus will result in im-
proved nodulisation. The clinker will be easier to burn and require lower burning tem-
perature/shorter burning time.
4.3.1.3 Lowering the lime saturation factor

It is often seen that a decrease of the LSF (i.e. from 98% to 95%) has given better
clinker formation even if the change does not result in a corresponding change in the
amount of liquid phase in the clinker.
The decrease in LSF makes the clinker easier to burn and also decreases the total poten-
tial alite content; thus the extent of alite sintering is reduced. The necessary lower tem-
perature also implies a shrinkage of the maximum temperature zone in relation to the
liquid zone. This, together with the reduced amount of alite sintering, provides for im-
proved nodulisation.
Figure 4.7 Dependence of kiln temperature profile on mix burnability
When the raw mix is difficult to burn, the temperatures in the burning zone may be very
high and The Maximum Temperature Zone is too long, at the expense of The Heating
and Liquid Zones, as shown in figure 4.7. Insufficient nodulisation takes place, and the
kiln produces a dusty clinker.
For certain kiln systems, the temperature profile and average burning zone temperature
is critical with respect to whether "good" or "bad" nodulisation is obtained.
The amount of fuel burned in the kiln will influence the average burning zone tempera-
ture and the material temperature profile. An elevated heat consumption may therefore
have a similarly adverse effect on the nodulisation process as that of a raw mix with
poor burnability.
4.4 THE BEHAVIOUR OF VOLATILE MATTER

Minor components introduced in the kiln system with raw materials and fuel can give
rise to difficulties in kiln operation when present in high concentrations within the sys-
tem. The minor components normally considered are the alkalis potassium and sodium
+ sulphur and chlorine, but other components such as fluorine and heavy metals, al-
though so far of less practical importance, follow a similar pattern.
The concentration of these components is increased in the kiln system due to internal
and external circulation as the components will evaporate at the burning zone tempera-
ture, condense when cooled in the kiln back end and be brought back to the burning
zone with the material. In many older plants, such problems are unknown because the
kiln system design allows the evaporated components to escape through the chimney.
However, in installations built in the eighties and nineties with efficient pre-heaters and
filters, it can become a problem.
4.4.1 Mechanism of circulation of volatile matter
4.4.1.1 Evaporation in the kiln

Upon approaching the burning zone in the rotary kiln, a fraction of the volatile compo-
nents will evaporate depending on the degree of volatility of the component and be
transported with the smoke gas back to the colder zones in the kiln system. Here the
components will condense on either the surrounding relatively colder surfaces or on the
raw meal and re-enter the burning zone with the raw meal where a fraction re-
evaporates. This repeated evaporation and condensation results in an internal circulation
where the concentration of some components can be increased in the kiln material up to
fifty times the input concentration. When an equilibrium state is reached, the output of
the volatile components is equal to the total input by the raw materials and the fuels.
Especially in a kiln system equipped with a preheater tower, almost all of the volatile
matter will finally leave the kiln with the clinker, as only a small fraction succeeds in
passing through the cyclones and escape with the exit gas. The concentration of the
component in the kiln system at this equilibrium state can be very high, depending on
the degree of volatility of the component.
If the concentration of volatile matter in the kiln system becomes too high, either be-
cause of a large input of volatile components or due to a high degree of volatility, the
installation of a kiln gas bypass is necessary to extract part of the volatile components
from the kiln system.
4.4.1.2 SO2 gas and volatile matter exiting the preheater

An often insignificant part of the volatile matter is discharged with the smoke gas into
the atmosphere. In the case of sulphur however, a part of the sulphur in the raw meal
can be present as pyrite, FeS, or organic sulphur. These are burned to SO2 gas in the
preheater upper cyclones in the temperature range of 400 – 600°C and a part of this gas
formed will be expelled as gas from the preheater tower. The small part of the volatile
matter that escapes the kiln preheater with the dust in the smoke gas is effectively pre-
cipitated in the filters and will normally be reintroduced with the kiln feed. This re-
circulation of volatile matter from the kiln system to the filter and back again to the kiln
is termed the external circulation.
4.4.1.3 Condensation in the preheater

The condensing of volatile matter vapour in the colder zones takes place on the raw
meal particles and on the surrounding walls. Condensation products are in part complex
compounds with low melting points and are therefore present as liquid in the preheater
tower. This presence of moisture in the raw meal has several consequences: it reduces
the flowability of raw meal and glues particles to the walls. This may cause build-ups
on cyclone walls and riser ducts, which in turn restricts the passage areas and causes
blockage of cyclones when pieces are loosened and sticks in the cyclone outlets. Strictly
speaking, the SO2 gas that is liberated in the kiln and passes from the kiln up through
the preheater does not condense. It combines with the calcined raw meal in the lower
cyclone stages where CaO is readily available as follows:
CaCO3 + heat → CaO + CO2 calcination
CaO + SO2 + ½O2 → CaSO4 sulphur reaction
4.4.2 Affinity between the volatile components

The volatility of the different compounds differs greatly, and with it the volatility of the
individual elements in the compounds. For instance, potassium combined with chloride
as KCl will evaporate nearly 100% in the burning zone while potassium combined with
sulphate as K2SO4, to a large extent, will leave the kiln with the clinker. Therefore it is
of great interest to know what compounds are present in the kiln system.
Below is given a schematic and simplified list indicating the order of which volatile
components have been observed to combine with other components.
• Chloride reacts primarily with the alkalis, forming NaCl and KCl. Any chlo-
ride in excess of alkali will combine with calcium to form CaCl2.
• A part of the alkalis in excess of chloride combine with sulphur to form
Na2SO4, K2SO4 and double salts such as Ca2K2(SO4)2.
• Alkalis not combined with chloride or sulphur will be present as Na2O and
K2O embedded in the clinker minerals.
• Sulphur in excess of alkali combines with CaO to form CaSO4.
4.4.3 Volatility of the compounds of volatile components
4.4.3.1 Definition of volatility

By volatility or evaporation factor ε of a volatile element or compound is understood
that fraction of the element that evaporates in the kiln burning zone instead of leaving
the kiln with the clinker as illustrated in figure 4.8.
Figure 4.8 Definition of evaporation factor E, valves V,
circulation factor K and residual component R

The evaporation factor is defined as;
% within clinker
Evaporatio n factor =1 −
% at kiln inlet [LOI free basis ]
ε = 1 means all evaporates and nothing leaves with the clinker

ε = 0 means nothing evaporates and all leaves with the clinker
4.4.3.2 Average evaporation factors:

Average values for the evaporation factor of various compounds is given in Figure 4.9
Excess
KCl Cl-free K2O Na2O Cl Alkali SO3
SO3
Evapora-
tion fac- 0,990 – 0,996 0,10 – 0,40 0,10 – 0,25 0,990 – 0,996 0,30 – 0,90 0,75
tor
Preheater
0,05 0,15 0,05 – 0,20 0,05 0,05 – 0,25 0,42
valve
Filter 0 – 0,10 0 – 0,10 0 – 0,15 0 – 0,10 0 – 0,20 0,80
valve
Figure 4.9 Evaporation factors and values
Chloride compounds KCl, NaCl and CaCl2 are seen to have an evaporation factor of
0,990 – 0,996 in the kiln. At approximately 800°C these compounds are melted (Figure
4.10 and 4.11) and at 1200 – 1300°C they are almost entirely evaporated.
K Na
Compound Melting point Boiling point Melting point Boiling point
[°C] [°C] [°C] [°C]
-Oxide decomp. 350 sublim 1275
-Carbonate 894 decomp. 850 decomp.
-Sulphate 1074 1689 884 -
-Chloride 768 1411 801 1440
-Hydroxide 360 1320 328 1390
Figure 4.10 Melting points and boiling points, °C.
Sulphate compounds with alkalis such as K2SO4 and Na2SO4 will in general be more
stable than CaSO4, which is the form that sulphur in excess of alkalis take. Alkali sul-
phates have evaporation factors in the range of 0,30 – 0,90 and are normally in the
lower part of the range, while excess sulphur has a value of 0,75. It is therefore desir-
able that all sulphur is combined with alkalis to the widest extent. This can be investi-
gated by looking at the molecular ratio of sulphur to alkalis.
4.4.3.3 Molecular ratio of sulphur and alkalis

The concentration of sulphur and alkali may increase to a point where it affects kiln op-
eration by causing build-ups. Both overall quantity and relative proportions may be the
cause. Individually they are more damaging to kiln operation than their sulphate com-
pounds. K2SO4 and Na2SO4, as K2SO4 has such a high evaporation temperature, that it
enters the clinker without evaporating. The same applies to approximately half the
Na2SO4, despite the fact that this sulphate begins to split into Na2O and SO3 at tempera-
tures as low as 900°C. Sulphur in excess of alkalis will form the more volatile CaSO4
which has a high evaporation factor in the kiln burning zone.
A number of equations have been developed for the estimation of the optimum molecu-
lar ratio between sulphur and alkalis in the kiln system. Two such equations are men-
tioned below:
1)
SO3
 SO3  80
  = ≈1,1
 Alk  optimum K O Na O
2
+ 0,5 ⋅ 2
94 62
The sulphur and alkalis is the total input. If the ratio exceeds 1,1 it is held that an
amount of sulphur is present in the kiln material which is not covered by alkalis, and as
"excess" sulphur will form CaSO4.
The amount of excess sulphur (E.S) is expressed in gram SO3 per 100 kg clinker and
calculated according to the equation
E.S . =1000 ⋅ SO3 − 850 ⋅ K 2 O − 650 ⋅ Na2 O [gr SO3 /100 kg clinker]
The limit on excess sulphur is given to be in the range of 250 – 600 g/100 kg clinker.
For easy burning raw mix the high value 600 gram SO3/100 kg clinker should present
no problems for the kiln operation, but for a hard burning raw mix the lower value is the
limit. Above these limits, the sulphur will give rise to coating problems in the preheater
tower.
2)
SO3
 SO3  80
  =
 Alk  optimum K 2 O + Na 2 O − Cl
94 62 71
The equation subtracts the chloride from the alkalis and states that the optimum range is
approximately 0,7 – 1,2
4.4.3.4 Vapour pressure

The equilibrium vapour pressure for compounds of volatile components is seen in Fig-
ure 4.11 as a function of the temperature. Recalling the principle of vapour pressure
curves, the equilibrium vapour pressure of a component is the partial pressure exerted
by the components gas phase when the liquid phase and gas phase are in equilibrium.
For instance, on the curve the vapour pressure for NaCl is seen to be 340 mmHg at
1300°C, which means that if we start with vacuum above an infinite amount of pure
NaCl(liquid) of 1300°C in a closed container, NaCl will evaporate until the NaCl(gas) has a
pressure of 340 mmHg. If we were to remove the NaCl(gas) as it is formed, NaCl(liquid)
will keep evaporating, striving to obtain the equilibrium vapour pressure. The driving
force for the evaporation is then proportional to the difference between the equilibrium
and the actual vapour pressure.
Inside the kiln, the vapour is constantly removed and the vapour pressure is therefore
practically zero. In this case, the volatility of the compound can be assumed to be pro-
portional to the equilibrium vapour pressure shown in figure 4.11.
A high equilibrium vapour pressure at a given temperature therefore indicates a high

evaporation factor. For instance, a vapour pressure of 760 mmHg means that the boiling
point is reached of the component.
The nature of the compounds in which the volatile matter is present is seen to be impor-
tant and it is inferred from the graph in figure 4.11 that the alkali chlorides will evapo-
rate before the alkali sulphates. This is in accordance with the experience that chlorides
evaporate nearly 100% in the burning zone and that chloride facilitates the evaporation
of alkalis.
Figure 4.11 Equilibrium vapour pressures of volatile compounds
Vapour pressures are seen to be exponential functions of the temperature, increasing

sharply with higher temperatures to the point where the vapour pressure can almost
double within 100°C. It follows that high temperatures in the kiln burning zone will
promote high evaporation factors and that small changes in the temperature will have
a big influence on the evaporation factor.
4.4.4 A mathematical model

For evaluating the behaviour of the volatile matter in an existing system and for predict-
ing, with reasonably accuracy, the behaviour of the matter in an installation where ma-
jor alterations are planned, a mathematical model can be used.
Rather pragmatically a simple model of the circulation circuit is established and then
this model is applied to actual measurements in order to obtain actual values for the fac-
tors in the formula.
4.4.4.1 Definitions; evaporation factor and valves

The definitions of the factors are given in figure 4.8. The fraction of the total, which
evaporates in the burning zone, is, as seen earlier, termed the "evaporation factor", ε.
The fraction escaping through the back end is termed the "valve", V, and the circulation
factor, K, is the factor by which the concentration in the burning zone of a component is
increased by circulation.
Figure 4.12 Rules of computation
Figure 4.12 shows that the circulation factor K and the content in the clinker, R, per
feed unit can be calculated when the evaporation factor ε and the valves (V) are known.
4.4.4.2 Rules of computations

Rules of computations are shown in figure 4.12 where valves in series are seen to be the
product of the individual valves. Hence the valve of a 4-stage preheater tower in theory
is a product of the four valves of each cyclone stage. The valve of the stack is a product
of a number of valves, namely one for each settling point, V-kiln, V-cyclones, V-raw
mill etc.
4.4.4.3 Average values for ε and valves

Average values for evaporation factors and valves are compiled in figures 4.13 and 4.9.
These values are based on a number of complete mass balances for circulating compo-
nents in various kiln systems. A valve of 1,0 means that nothing is retained, i.e. all
components leave the system with the gas. Figure 4.13 shows that values for kiln valves
can vary widely according to the kiln type. For instance, from 0,20 valves for a long dry
kiln to 1,0 for a precalciner kiln. The preheater valves are small and of course very
small for 4-stages of cyclones as the valves for each stage theoretically should be multi-
plied by each other to give the total valve.
VOLATILE MATTER Typical Values for ε and V

Symbol K 2O Na2O Cl SO3
Evaporation factor ε 0,20 - 0,40 0,10 – 0,25 0,990 – 0,996 0,35 – 0,80
Kiln valve
- wet module-op.kiln Vo 0,50 0,70 0,70 0,60
- wet dust-op.kiln Vo 0,40 0,60 0,60 0,40
- long dry kiln Vo 0,20 0,50 0,60 0,40
- 1 stage kiln Vo 0,55 0,80 0,60 0,35
- 2 stage kiln Vo 0,70 0,85 0,80 0,60
- 4 stage kiln Vo -1 -1 -1 -1
- precalciner kiln -1 -1 -1 -1
Cyclone preheater
Vc
valve
- 1 stage Vc 0,5 0,50 0,35 0,45
- 2 stages Vc 0,20 0,45 0,20 0,30
- 4 stages Vm 0,15 0,40 0,05 0,15 – 0,50
Dedusting cyclone
Vkt 0,60 0,70 0,50 0,55
valve
Raw mill valve Vt 0,60 0,80 0,70 0,30
Cooling tower valve -1 -1 -1 -1
Elec.precipitator valve 0,40 0,70 0,30 0,50 – 0,80
Figure 4.13 Typical values for ε and V.
In practice it is found that the above characteristics vary considerably due to their close
dependence on:
1. Calciner kilns tend to be in the lower end of the scale of evaporation factors
2. Burnability of raw mix (chem. comp., fineness, coarse silica, fluxes, etc.)
3. Nature of impurity-bearing compounds (sulphates-sulphides-organic S)
4. Sulphur/Alkali ratio
5. Presence of other non-volatile impurities (phosphates)
6. Operational Conditions (flame formation, excess air, etc.)
The valves and evaporation factor for sulphur are difficult to evaluate. As previously
discussed, sulphur combined with alkali has a different behaviour than sulphur existing
as excess sulphur. Therefore in figure 4.9 it is seen that alkali sulphur and excess sul-
phur are given different evaporation factors and valves. Excess sulphur is seen to evapo-
rate more rapidly and furthermore to pass more willingly through the preheater tower
than alkali sulphates.
4.4.5 Three aspects of volatile matter

There are three aspects to consider when regarding volatile matter
Content of volatile matter in clinker

The introduced alkali, sulphur and chloride will end up in the clinker if not removed
elsewhere. A high alkali content in the clinker may often not be desired and limitation
on the content of all such matter in the cement have to be taken into account.
Emission to the environment

Evaporated sulphur discharged through the stack as SO2 gas and the amount of enriched
dust from the EP that is either discarded or blown away, constitutes a troublesome emis-
sion source.
Operational aspects
Operational problems often arise when the circulating components reach high concen-
trations within a kiln system. In the kiln there is the formation of rings in the inlet sec-
tion and formation of dusty clinker. Problems in the preheater cyclones include the for-
mation of build-ups, unsteady material flow and frequent blockages of cyclones.
4.4.5.1 Content of volatile matter in clinker
To comply with the most common cement norms and for maintaining a high clinker
quality, the following limits on the content of volatile matter in the clinker apply:
Na2O + K2O : 1,5 %

SO3 : 1,6 %
Cl : 0,1 %
Low Alkali clinker

Limits for volatile matter in the clinker when producing low alkali clinker are often
given in the standards as:
Na2Oeq : 0,6 %
SO3 : 1,6 %
Cl : 0,1 %
where Na2Oeq = Na2O + 1,5·K2O
When the objective is to obtain a low content in the clinker of a certain volatile com-
pound, i.e. for the production of low alkali clinker, the ideal is to have raw materials
with a low content of volatile matter. If this is not the case, the volatile component will
have to be evaporated and removed in the kiln system. When producing low alkali
clinker with a raw material containing more alkali than can be tolerated in the clinker, it
is necessary to have a high evaporation factor ε and preferably a large preheater valve
V.
Increasing the evaporation factor

For the production of low alkali clinker, the evaporation factor can be increased by
various measures such as by increasing the temperature of the burning zone. This is
widely done by simply increasing the silica ratio of the raw meal and burning the
clinker hard to low free lime values. Other means of increasing the volatility of alkalis
is by reducing the sulphur input and by adding chloride to the system, such as CaCl2 or
by the burning of chlorinated organic solvents in the kiln.
When producing a clinker with a normal or low content of alkali from alkali rich raw
materials that contains more alkalis than desired in the clinker, it becomes necessary to
remove the alkalis with a kiln gas bypass. This is to avoid operational problems due to a
large circulation of alkalis in the kiln system.
4.4.5.2 Emission to the environment

Emission of particulate matter
When the particulate volatile matter is found as ultra fine particles it can escape through
the precipitator, but normally there is no substantial emission of solid circulating matter.
Emission of gaseous matter

The only gaseous volatile component in the preheater exit gas is SO2, of which a frac-
tion will escape through the stack. The amount escaping depends mostly on the kiln sys-
tem. SO2 gas is formed by the combustion process in the rotary kiln and in the calciner
vessel where the sulphur in the fuel will be liberated as SO2 gas. SO2 is also formed in
the burning zone by the thermal decomposition of the sulphates as described previously.
In a SP and calciner kiln the SO2 gas formed in the kiln is swept with the smoke gas
through the preheater tower where the SO2 is almost completely absorbed by the cal-
cined raw meal in the lower stages to form CaSO4. This is due to the good contact be-
tween the gas and the material. Investigations show that the SO2 gas formed in the cal-
ciner by the combustion process, is instantaneously and completely absorbed by the
CaO simultaneously formed in the calcining process.
In the raw meal a small part of the sulphur can be present as pyrite FeS or organic sul-
phur which combusts to SO2 gas in the upper cyclones in the temperature range of 400 –
600 °C. Part of this will be expelled as SO2 gas from the preheater. However, a consid-
erable part, 30 – 95 %, of the SO2 gas that exits the preheater is absorbed by the raw
meal in the raw mill installation. Thus the emission from the stack under normal operat-
ing conditions is minute.
For the wet and long dry kiln, the SO2 gas formed in the kiln will only to a very limited
degree be reabsorbed in the kiln due to a poor contact between material and gases. Here,
the amount of SO2 gas that escapes through the stack is normally in the range of 30 – 50
% of the total sulphur input to the system.
4.4.5.3 Operational aspects

Operational problems due to circulating components
The day to day kiln operation can become seriously hampered by formation of build-ups
in the system when the concentration of circulating components increases in the kiln
system.
As a consequence of the build-ups in riser pipes and cyclones, the pressure drop in the
system increases and maintaining the draft in the kiln becomes increasingly difficult.
The first consequence of the reduced draft will often be that the maximum kiln produc-
tion is reduced. It is very tempting to compensate for the reduced draft in the kiln by
operating with less excess air, but this will only make things worse as the circulation of
sulphur increases significantly at low oxygen levels.
Another consequence of high levels of sulphur circulation is an increasing tendency to

the formation of a very dusty clinker. The reason for this phenomenon is not very well
known. The operational problems encountered with a dusty clinker are foremost linked
with the moving of heat from the burning zone up towards the kiln inlet, as the hot dust
is transported with the smoke gas. This creates an undesired heating of the zones before
the burning zone and has a detrimental effect on the kiln coating, leading to the forma-
tion of an unstable coating at the burning zone inlet.
The resulting kiln operation is poor with symptoms as:
• Frequent kiln stops due to cyclone cleaning and clogging problems

• Higher heat consumption
• Reduced kiln production rate
Limits on volatile components within the SP kiln system

Experience shows that surpassing the normal limits of volatile matter, shown in the ta-
ble in Figure 4.14, will lead to a growing tendency of cyclone blockages and the forma-
tion of build-ups in exposed areas of the kiln system. Frequent cleaning must be ex-
pected.
Kiln operation frequently becomes impossible and frequent kiln stops are to be expected
for cleaning away deposits and blocked cyclones if values are beyond the maximum
limits shown in figure 4.14.
Limits on volatile matter in bottom cyclone stage

in a SP kiln system on LOI free basis
normal limit maximum limit
(%) (%)
K2Oeq = K2O + 1,5·Na2O 3,7 6
-
Chlorine as Cl 0,8 2,0
Sulphur as SO3 2,5 5
Figure 4.14
Limits on input of volatile matter to the SP kiln without bypass

The circulation process naturally sets an upper limit to the acceptable input of the dif-
ferent volatile components with the raw mix and the fuel for kiln system without by-
pass. These limits are given in Figure 4.15 with a normal and a high limit. The high
limit only applies when the raw mix is easy burned and the alkali/sulphur ratio, as dis-
cussed in Section 4.3.1 is ideal.
Maximum allowable input of volatile components

for SP kiln system without bypass on LOI free basis
(%) (%)
K2O + 0,65·Na2O 1 1,5
Chlorine as Cl- 0,023 0,023
Sulphur as SO3 1 1,6
Figure 4.15
Note!
In the expression for alkalis, it is not the K2Oeq that is calculated. Rather it is an em-
pirical formula where the sodium is given less weight in accordance with the volatility
of sodium being lower than the volatility of potassium.
If these limits are surpassed and the total input of volatile matter is higher, the kiln sys-
tem must be equipped with a bypass through which some of the kiln gas can be ex-
tracted from the system before reaching the preheater.
Limits on input of volatile matter to the Calciner kiln without bypass

As a consequence of the many different designs of precalciner kilns, some aspects re-
garding their behaviour with volatile matter is different for each calciner system. Cal-
ciner kilns and SP kilns, both without bypass, can tolerate equal amounts of alkalis.
However, the calciner kiln can tolerate less sulphur
The allowable limits on inputs are given in figure 4.16 with a normal and a high limit.
The high limit only applies when the raw mix is easy burning and the alkali/sulphur ra-
tio as discussed earlier is ideal.
Maximum allowable input of volatile components

for calciner kiln system without bypass on LOI free basis
(%) (%)
K2O + 0,65·Na2O 1 1,5
-
Chlorine as Cl 0,015 0,015
Sulphur as SO3 0,8 1,2
Figure 4.16
If these limits are surpassed and the total input of volatile matter is higher, the calciner
kiln system must be equipped with a bypass through which some of the kiln gas can be
extracted from the system before reaching the preheater.
Why Calciner kilns are more sensitive to Volatile matter

Calciner kiln systems will to a larger extent than SP kilns be sensitive to input of chlo-
ride and sulphur and will require kiln gas bypass installations for lower input levels of
these components than SP kilns.
The reason for this higher sensitivity is found in the lower kiln smoke gas to clinker ra-
tio [Nm3/kg clinker] in the calciner kiln where only 320 kcal/kg clinker or 40% of the
total combustion takes place. The concentration of the volatile matter in the smoke gas
from the calciner rotary kiln expressed as gram/Nm3 will therefore reach critical values
with less chloride and sulphur in the raw material.
Discarding filter dust

To reduce the level of circulating matter in the kiln system, the input of circulating mat-
ter can in some cases be reduced by discarding the fine fraction of the filter dust, which
is enriched with volatile matter. This is an interruption of the external circulation. The
impact on the internal circulation within the kiln will normally be very limited, but can
in every case be evaluated by establishing a mass and volatile balance as described un-
der the mathematical model.
More effective in combating high levels of circulating components, is the reduction of

the volatility of the component. This can be done by reducing the burning zone tempera-
ture and by other measures described in the following.
Reducing the volatility of compounds

When kiln operation is troubled by coating formations and high concentration of vola-
tile matter in the system, the aim is to reduce the circulation factor K. Such problems are
foremost found in 4-stage preheater kilns, which have small natural valves, combined
with high temperature in the kiln. Reducing the circulation factor can be achieved by
reducing the evaporation of the volatile components, for instance by lowering the burn-
ing zone temperature. Reducing the volatility is the most practical measure when deal-
ing with problems caused by excessive amounts of alkali and sulphur.
4.4.6 Solving problems with sulphur

Reducing burning zone temperature
Volatility of the sulphur compounds and especially of CaSO4 is an increasing function
of the temperature. CaSO4 will start to decompose slowly at temperatures above 1220°C
and this thermal decomposition is best avoided by lowering the burning zone tempera-
ture. This may be achieved by making the raw meal easy to burn, which means finer
grinding of the raw meal and if necessary changing the chemical composition, i.e. low-
ering the silica ratio, to make an easier burning raw mix. For kiln operation it also im-
plies that unnecessary overheating of the material has to be avoided and a higher free
lime content may have to be accepted.
Molecular ratio
Observing the optimum molecular ratio of sulphur to alkali and ensuring that the excess
sulphur is minimised are important steps for reducing the sulphur volatility.
Kiln atmosphere
Oxygen in kiln atmosphere

The dissociation of sulphur compounds can be described as
Alk-SO4 + heat → Alk-O + SO2 + ½ O2
The equilibrium of this balance is shifted to the left favouring the formation of Alk-SO4
with increasing O2 and SO2 partial pressure. It is therefore important that enough oxy-
gen is present in the kiln atmosphere. It is known that for increasing oxygen con-tent up
to approximately 2%, volatility of sulphur is progressively reduced while increasing the
oxygen beyond 2% has a limited effect.
Reducing conditions in kiln atmosphere

In a generally reducing atmosphere or with local reducing conditions in the charge due
to incomplete combustion of fuel, the presence of free carbon in the charge will give
rise to the following reactions:
CaSO4 + C → CaO + SO2 + CO

Alk2SO4 + C → Alk2O + SO2 + CO
This significantly increases the sulphur circulation as it promotes the decomposition of

the otherwise reasonably stable CaSO4, as well as the stable alkali sulphates. It is there-
fore important that oxidising conditions are maintained in the kiln with O2 > 1,5 – 2%
and CO < 0,1% at the kiln inlet. The incomplete combustion of fuel and coal dropping
out of the flame is strictly to be avoided.
Thermal load
Reducing the thermal load in the kiln has shown to have a positive effect on the sulphur
circulation. The use of a precalciner kiln system or implementing secondary firing in the
kiln riser will thus have a positive effect. Furthermore the implementation of firing in
the kiln riser pipe will increase the content of oxygen in the kiln atmosphere adding to
the positive effect.
Discarding EP dust
For dry process kilns with 4-stage preheaters, no perceptible reduction in sulphur circu-
lation can be achieved by discarding precipitator dust as there is only a relatively minor
amount of settlement due to the cleaning effect of the cyclones.
4.4.7 Solving problems with chloride

Reduction of volatility of chloride
Evaporation of chloride is always high and can hardly be significantly reduced due to
their extremely high volatilisation degree in the burning zone. Measures against chlo-
rides will therefore not be centred around the reduction of the evaporation. Other ways
of reducing the chloride content in the kiln system is therefore necessary.
Input from raw materials and other sources

As the evaporation factor of chloride is high, limiting the input is one of the few ways to
control the chloride cycle. While it may not be possible to avoid the chloride in the main
raw materials, avoiding a minor component with significant chloride content is often
feasible. The natural in-homogeneity of the raw materials can sometimes lead to sub-
stantial peaks in the input of chlorine to the system, which must be avoided. Here the
pre-homogenisation of the raw materials together with a good knowledge of the quarry
deposit can help to avoid such peaks.
Discarding of dust
In a preheater kiln, this measure is normally not very effective as the amount of chlo-
rides escaping the preheater is small. If there is a sizeable external circulation where the
filter dust is enriched with chloride, discarding this dust will have some effect (however,
environmental aspects must be carefully looked into and discussed with the Authori-
ties). A mass and volatile matter balance will help to clarify the effect on the internal
circulation of this measure.
Installation of a kiln gas bypass

If the total input of chloride to the SP kiln system exceeds 0,015% Cl on raw meal basis,
0,023 %Cl on clinker basis, the installation of a bypass is normally required and a kiln
gas bypass is most frequently used for the removal of chloride. For SP kilns the rule of
thumb applies that the percent bypass should be total input %Cl on raw meal basis times
100.
%bypass = % Cl in raw materials (raw meal basis) · 100
Example: In raw materials (raw meal basis) = 0,10% Cl

required bypass of kiln gas = 10 %
Reducing the sulphur evaporation

As the clogging of cyclones and formation of build-ups in riser ducts can be viewed as a
process where both sulphur and chloride is involved, the reduction of the sulphur evapo-
ration will probably enable the system to function with a higher level of chlorides.
4.4.8 Solving problems with alkali

Alkali volatility
If not covered with sulphur, the volatility of alkali is very high. In such cases the addi-
tion of sulphur to the kiln system in the form of gypsum can be contemplated to reduce
the volatility.
As the alkalis are normally combined with either sulphur or chloride they have been
dealt with under sections 4.4.6 and 4.4.7.
4.4.9 Setting up a mass and volatile matter balance

An example is provided below to illustrate a simple balance of volatile matter:
Inputs
Raw meal:
Raw meal basis: LOI free basis:
Na2O : 0,15% Na2O : 0,23%

K2O : 0,45% K2O : 0,69%
SO3 : 0,375% SO3 : 0,58%
Cl : 0,005% Cl : 0,008 %
LOI : 34,9%
Coal:
Coal Analysis
Coal basis: Coal Ash basis:
Na2O : 0,10% Na2O : 1,00%

K2O : 0,05% K2O : 0,50%
SO3 : 2,50% SO3 : 25,0%
Cl : 0,013% Cl : 0,13%
Net Value Hnet : 5600 kcal/kg

Ash content : 10%
Specific Heat Consumption : 800 kcal/kg clinker
Ash content in clinker : 800/5600·10% = 1,4%
Outputs
Clinker: Na2O : 0,24%
LOI free basis K2O : 0,68%
SO3 : 0,90%
Cl : 0,007%
Kiln inlet.
Lowest cyclone Stage
Raw Meal basis LOI free basis
Na2O : 0,24% Na2O : 0,29%

K2O : 1,64% K2O : 2,00%
SO3 : 3,85% SO3 : 4,70%
Cl : 0,66% Cl : 0,80%
LOI : 18%
Balance of inputs and outputs
Na2O (%) K2O (%) SO3 (%) Cl (%)

Input
LOI free basis
Raw meal 0,23 0,68 0,57 0,008
Coal 0,01 0,01 0,36 0,002
Total 0,24 0,69 0,93 0,010
Output
LOI free basis
Clinker 0,24 0,68 0,90 0,007
Total 0,24 0,68 0,90 0,007
The amount of K2O, SO3 and Cl leaving the kiln with the clinker is apparently smaller
than the input with the raw materials and the coal.
Small deviations are quite normal due to sampling not being representative. In the case
of sulphur, part of the sulphur in the raw meal could be sulphides which burns off in the
preheater tower and leaves as SO2 gas.
Checking the input of Volatile matter
(LOI free basis) Limit (%) Actual (%)

K2O+0,65·Na2O 1,0 0,85
Cl 0,023 0,010
SO3 1,0 0,93
All OK for operation without bypass and no problems expected.
Sulphur to Alkali ratio
0,93
SO3 80
= =1,25
Alk 0,69 0,24
+ 0,5 ⋅
94 62
The ratio is higher than the limit of 1,1 and therefore there is excess sulphur in the sys-
tem present as CaSO4.
Excess Sulphur
E.S. = 1000·0,93 – 850·0,69 – 650·0,24 = 187 gram SO3/100 kg clinker
OK, not too much excess sulphur and no problems are expected.
Content in lower stage

K2Oeq 3,5 2,0 + 1,5·0,29 OK
Cl 0,8 0,8 OK
SO3 2,5 4,70 High!
Content in clinker

Na2O+K2O 1,5 0,92 OK
Cl 0,1 0,007 OK
SO3 1,6 0,90 OK
Evaporation factors of volatile components
0, 24
ε Na O = 1 − = 0,17
2
0, 29
0,68
εK 2O
=1− = 0,66
2,00
The evaporation factor of K2O must for a more detailed study be calculated separately
for the evaporation of KCl and Cl-free K2O. The typical evaporation factors for these
compounds are seen in figure 3.9.
0,90
ε SO = 1 − = 0,81
3
4,70
0 , 007
ε Cl = 1 − = 0 ,991
0 ,80
The evaporation factor for Na2O is seen to be in line with factor shown earlier. The con-
tent of SO3 in the lower stage material is very high and is caused by a high evaporation
factor of 0,81 in the kiln. Operation of the kiln is expected to be very problematic with
many kiln stops for cleaning of the cyclones. The high evaporation factor of sulphur
must be investigated further to determine the cause.
4.5 CONCLUSION
This module has related the characteristics of the raw mix to burnability clinker forma-
tion and the circulation phenomena of volatile matter in a kiln system. It has been dem-
onstrated that the average burning zone temperature is dependent on raw mix character-
istics and kiln operation. It has also been demonstrated that a high burning zone tem-
perature may adversely affect the clinker formation and produce problems in the prehea-
ter tower as regards circulating volatile matter.
Further, it has been demonstrated that the specific choice of raw materials has a large
impact on the behaviour of the kiln. It may cause cyclone blockages or increase the need
for frequent cleaning in the riser ducts. It has likewise been shown that the coating for-
mation in the kiln and the clinker size may be greatly affected by the substitution of one
minor component by another, even if the chemical analysis of the two appears to be
practically identical. It can be difficult to identify the factors responsible for the change
in the kiln behaviour. Sometimes the use of a specific material has to be abandoned due
to the problems caused in the kiln system.
Some disturbances introduced in the kiln by changing the type of raw mix are difficult
to counter in the daily operation of the kiln. It is therefore important to learn to identify
the symptoms in kiln behaviour, which can be traced back to the raw mix so that correc-
tions can be made. Other disturbances can to some extent be alleviated by taking appro-
priate measures in the kiln operation as has been discussed.
Finally, the volatile content of the raw material has been discussed and a model pre-
sented for analysing and evaluating the behaviour of the volatile matter.

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Package P3: Kiln – Operation and Optimisation

Module 4: Raw Material Characteristics

Course name : Kiln operation and optimisation

Identify the influence of various raw mate-

Duration : 0,5 day

RAW MATERIAL MIXTURES AND THEIR CHARACTERISTICS .......................... 4

4.4.5 Three aspects of volatile matter ......................................................................... 24

RAW MATERIAL MIXTURES AND THEIR CHARACTERISTICS

To achieve this goal it is necessary to know

• which parameters in the raw mix influence the kiln operation

• the burnability of a raw mix,

4.2 BURNABILITY OF RAW MIX

The burnability is determined in the laboratory on a small representative sample of the

(1) Calcite and marl rich in CaCO3

4.2.1 Coarse grains

Figure 4.1 Homogenous Clinker

4.2.1.1 Coarse grains - determination

quartz and silicates: +45 µm

+1% quartz + 45 µm leads to +0,93% free CaO

4.2.2 Effects of chemical composition

CaO1400o C = 0,33 ⋅ (LSF − 95) +1,8 ⋅ (MS − 2)

As expected, an increase in LSF and MS will result in higher free lime.

Figure 4.3 Correlation between measured and estimated free lime

Figure 4.4 Effect of raw mix changes on resulting free lime

An alternative way of reducing the temperature at which clinkerisation takes place is by

4.2.3 Alternative burnability determination

CaO1400o C = 0,35⋅ (LSF − 96) +1,58⋅ (MS − 1,6)

4.2.3.1 Burnability index.

4.2.3.2 The burnability factor

Burnabilit y factor = x ⋅ LSF + y ⋅ MS + z ⋅ (MgO + alkalies )

4.3 CLINKER FORMATION

Reflections on clinker formation, especially regarding agglomeration, have led to a

1) One is the physical agglomeration and nodulisation of the material in the

Figure 4.5 % Liquid versus temperature

4.3.1 Effect of changes in chemistry

4.3.1.1 Reduction in the alumina/iron ratio

4.3.1.2 Lowering of the silica modulus

4.3.1.3 Lowering the lime saturation factor

Figure 4.7 Dependence of kiln temperature profile on mix burnability

4.4 THE BEHAVIOUR OF VOLATILE MATTER

4.4.1 Mechanism of circulation of volatile matter

4.4.1.1 Evaporation in the kiln

4.4.1.2 SO2 gas and volatile matter exiting the preheater

4.4.1.3 Condensation in the preheater

CaCO3 + heat → CaO + CO2 calcination

CaO + SO2 + ½O2 → CaSO4 sulphur reaction

4.4.2 Affinity between the volatile components

4.4.3 Volatility of the compounds of volatile components

4.4.3.1 Definition of volatility

Figure 4.8 Definition of evaporation factor E, valves V,

circulation factor K and residual component R

ε = 1 means all evaporates and nothing leaves with the clinker

4.4.3.2 Average evaporation factors:

4.4.3.3 Molecular ratio of sulphur and alkalis

4.4.3.4 Vapour pressure

A high equilibrium vapour pressure at a given temperature therefore indicates a high

Figure 4.11 Equilibrium vapour pressures of volatile compounds

Vapour pressures are seen to be exponential functions of the temperature, increasing

4.4.4 A mathematical model

4.4.4.1 Definitions; evaporation factor and valves

Figure 4.12 Rules of computation

4.4.4.2 Rules of computations

4.4.4.3 Average values for ε and valves