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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 and valves ................................................................. 23
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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 available raw materials.
The behaviour of a new and untried raw mix in the kiln can to a large degree be predicted 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
In this module, three central concepts in the relation between raw meal characteristics
and kiln operation is treated, namely:
Each of these concepts serve to explain how various characteristics of the raw mix influence the kiln operation and explain what appropriate action can be taken in kiln operation.
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desired C3S during the clinkerisation, and therefore the unused CaO is present somewhere in the clinker as free lime.
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 content. So both coarse quartz and coarse calcite may result in poor burnability, with corresponding high free lime content and too little C3S in the clinker.
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+45 m
calcite:
+125 m
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 m leads to
(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 microscope. The coarse quartz is determined in the acid insoluble residue + 45 m and
coarse calcite is determined in the total sieving residue on 125m.
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The following formula may be used for estimating the free CaO after burning for 30
minutes at 1400C:
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 conditions. 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).
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It is shown in figure 4.4 that grinding to a 12% residue on the 90 m 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 m.
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 1250C. 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 promote the formation of the clinker minerals. Sulphate is often used as a fluxor and introduced as gypsum.
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Burnabilit y index =
C3 S
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 CaO1400C without regarding the contribution of coarse grains.
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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, particle 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.
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At the entrance to the burning zone a system of particulate material and a liquid is present. Figure 4.5 demonstrates the amount of liquid as a function of temperature. The liquid is formed in a narrow temperature interval at approximately 1330C. After this, the
amount of liquid increases very little with increasing temperature, and may be regarded
as constant; at this time, as long as the particles are not too coarse, nodulisation may
take place.
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.
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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 uppermost 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 formation 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.
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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.
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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 temperature 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.
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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 because 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.
CaO + CO2
calcination
CaO + SO2 + O2
sulphur reaction
CaSO4
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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 chloride in excess of alkali will combine with calcium to form CaCl2.
Alkalis not combined with chloride or sulphur will be present as Na2O and
K2O embedded in the clinker minerals.
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Evaporatio n factor =1
% within clinker
% at kiln inlet [LOI free basis ]
Evaporation
factor
KCl
Cl-free K2O
Na2O
Cl
Alkali SO3
Excess
SO3
0,990 0,996
0,10 0,40
0,10 0,25
0,990 0,996
0,30 0,90
0,75
0,05
0,15
0,05 0,20
0,05
0,05 0,25
0,42
0 0,10
0 0,10
0 0,15
0 0,10
0 0,20
0,80
Preheater
valve
Filter
valve
Chloride compounds KCl, NaCl and CaCl2 are seen to have an evaporation factor of
0,990 0,996 in the kiln. At approximately 800C these compounds are melted (Figure
4.10 and 4.11) and at 1200 1300C they are almost entirely evaporated.
K
Compound
Na
Melting point
Boiling point
Melting point
Boiling point
[C]
[C]
[C]
[C]
decomp.
350
sublim
1275
-Carbonate
894
decomp.
850
decomp.
-Sulphate
1074
1689
884
-Chloride
768
1411
801
1440
-Hydroxide
360
1320
328
1390
-Oxide
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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 sulphates 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 desirable that all sulphur is combined with alkalis to the widest extent. This can be investigated by looking at the molecular ratio of sulphur to alkalis.
SO3
80
SO3
=
1,1
K
O
Na
O
Alk
2
optimum
+ 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
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.
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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
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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 and the valves (V) are known.
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K 2O
Na2O
Cl
SO3
0,20 - 0,40
0,10 0,25
0,990 0,996
0,35 0,80
- 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
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
-1
-1
-1
-1
Evaporation factor
Kiln valve
- precalciner kiln
Cyclone preheater
valve
Vc
- 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
Vkt
0,60
0,70
0,50
0,55
Vt
0,60
0,80
0,70
0,30
-1
-1
-1
-1
0,40
0,70
0,30
0,50 0,80
Dedusting cyclone
valve
Raw mill valve
Cooling tower valve
Elec.precipitator valve
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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 sulphur are given different evaporation factors and valves. Excess sulphur is seen to evaporate more rapidly and furthermore to pass more willingly through the preheater tower
than alkali sulphates.
Operational aspects
Operational problems often arise when the circulating components reach high concentrations within a kiln system. In the kiln there is the formation of rings in the inlet section and formation of dusty clinker. Problems in the preheater cyclones include the formation of build-ups, unsteady material flow and frequent blockages of cyclones.
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1,5 %
SO3
1,6 %
Cl
0,1 %
0,6 %
SO3
1,6 %
Cl
0,1 %
where Na2Oeq =
Na2O + 1,5K2O
When the objective is to obtain a low content in the clinker of a certain volatile compound, 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 and preferably a large preheater valve
V.
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The first consequence of the reduced draft will often be that the maximum kiln production 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 formation of an unstable coating at the burning zone inlet.
The resulting kiln operation is poor with symptoms as:
maximum limit
(%)
(%)
3,7
Chlorine as Cl-
0,8
2,0
Sulphur as SO3
2,5
Figure 4.14
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maximum limit
(%)
(%)
1,5
Chlorine as Cl-
0,023
0,023
Sulphur as SO3
1,6
K2O + 0,65Na2O
Figure 4.15
Note!
In the expression for alkalis, it is not the K2Oeq that is calculated. Rather it is an empirical 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 system must be equipped with a bypass through which some of the kiln gas can be extracted from the system before reaching the preheater.
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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 ratio as discussed earlier is ideal.
maximum limit
(%)
(%)
1,5
0,015
0,015
0,8
1,2
K2O + 0,65Na2O
Chlorine as Cl
Sulphur as SO3
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.
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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
Alk-O + SO2 + 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 oxygen 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.
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CaO
Alk2SO4
Alk2O + SO2 + CO
+ SO2 + CO
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 circulation 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.
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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 chlorides 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 Authorities). A mass and volatile matter balance will help to clarify the effect on the internal
circulation of this measure.
= 0,10% Cl
= 10 %
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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:
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%
800/560010% = 1,4%
Outputs
Clinker:
Na2O :
0,24%
K2O
0,68%
SO3
0,90%
Cl
0,007%
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Kiln inlet.
Lowest cyclone Stage
Raw Meal 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%
K2O (%)
SO3 (%)
Cl (%)
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
Clinker
0,24
0,68
0,90
0,007
Total
0,24
0,68
0,90
0,007
Input
LOI free basis
Output
LOI free basis
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.
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Limit (%)
Actual (%)
K2O+0,65Na2O
1,0
0,85
0,023
0,010
1,0
0,93
Cl
SO3
SO3
Alk
0,93
80
0,69
0,24
+ 0,5
94
62
=1,25
The ratio is higher than the limit of 1,1 and therefore there is excess sulphur in the system present as CaSO4.
Excess Sulphur
E.S. = 10000,93 8500,69 6500,24 = 187 gram SO3/100 kg clinker
OK, not too much excess sulphur and no problems are expected.
Content in lower stage
(LOI free basis)
Limit (%)
Actual (%)
K2Oeq
3,5
2,0 + 1,50,29
OK
Cl
0,8
0,8
OK
SO3
2,5
4,70
High!
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Content in clinker
(LOI free basis)
Limit (%)
Actual (%)
Na2O+K2O
1,5
0,92
OK
Cl
0,1
0,007
OK
SO3
1,6
0,90
OK
Na O = 1
2
=1
2O
0, 24
= 0,17
0, 29
0,68
= 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.
SO = 1
3
Cl = 1
0,90
= 0,81
4,70
0 , 007
= 0 ,991
0 ,80
The evaporation factor for Na2O is seen to be in line with factor shown earlier. The
content 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.
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4.5 CONCLUSION
This module has related the characteristics of the raw mix to burnability clinker formation and the circulation phenomena of volatile matter in a kiln system. It has been demonstrated that the average burning zone temperature is dependent on raw mix characteristics and kiln operation. It has also been demonstrated that a high burning zone temperature may adversely affect the clinker formation and produce problems in the preheater 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 formation 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 corrections can be made. Other disturbances can to some extent be alleviated by taking appropriate measures in the kiln operation as has been discussed.
Finally, the volatile content of the raw material has been discussed and a model presented for analysing and evaluating the behaviour of the volatile matter.
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