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RAW MATERIALS

Burning
the mix
by Linda M Hills, Senior Scientist; Vagn Johansen, Senior Principal

A
comprehensive understanding of
the chemical and physical aspects Scientist; and F MacGregor Miller, Senior Principal Scientist
of raw material transformation Construction Technology Laboratories, Inc
into clinker is an important foun-
This paper, this year’s prizewinning presentation at the IEEE/PCA Meeting
dation to increasing production, reducing
costs, and improving quality at the cement in Florida, discusses clinker formation, its relation to kiln feed properties,
plant. Clinker formation relies on numerous and the importance of optimising burnability by careful mix control, good
kiln feed properties and pyroprocessing mix homogeneity, and tailoring the burning process to the raw mix. The
conditions. Understanding the influential burnability and kiln feed are discussed in relation to specific fuel
properties of the feed (chemistry, fineness, consumption. Emphasis is placed on the effects of changes in raw material
uniformity, and mineralogy) can lead to
burnability and clinker formation on kiln operations, finish mill productiv-
improvements in its burnability and there-
fore in the efficiency of plant operations. ity, and the properties of the resulting cement.
When the raw materials available make Given its relationship to both plant provide the information needed to make
it hard to achieve burnability goals, the operation efficiency and cement perfor- appropriate improvements. This approach
use of fluxes and/or mineralisers may be mance, the importance of clinker formation can also be used to anticipate changes
helpful. Fluxes and mineralisers indirectly cannot be overestimated. caused by the introduction of new raw
affect burnability promoting earlier clinker materials. Replacing raw materials with
phase formation; their effect on clinker Clinker others because they are less expensive, or
formation and cement quality is briefly Stated simply, the chemical aspect of to correct the chemical composition may
described here. Fluoride-containing com- clinker formation is the combination of change how difficult it is to burn the new
pounds have proven to be the most effec- silica with calcium to produce hydraulic kiln feed.
tive mineralisers in cement clinkering reac- compounds. However, the actual transfor-
tions. However, an excessive amount of mation of the raw materials into clinker Raw material properties and burnability
fluoride may delay cement setting time. involves a combination of chemical and The raw materials used are designed and
physical processes as the material passes proportioned to provide the appropriate
Transforming raw materials through the kiln system. The general amounts of the various clinker phases.
Plant management is constantly under process of clinker formation is described in Specific properties of the materials are
pressure to maintain or increase production Figure 1. The transformation concludes critical to plant efficiency and energy con-
rates and reduce costs, without sacrificing with the primary clinker phases: sumption, based on their burnability.
quality. These three are challenging goals, • alite: impure tricalcium silicate, gener- Burnability is the ease with which the
especially achieving all three simultane- ally termed C3S raw materials are transformed into the
ously. Understanding the process of clinker • belite: impure dicalcium silicate, nor- desired clinker phases, and is commonly
manufacture – how raw materials are trans- mally termed C2S measured by the amount of free (un-
formed into clinker – is the key. • aluminate: tricalcium aluminate, C3A reacted) lime remaining in the clinker (low
This transformation involves both • ferrite: nominally tetracalcium alumino- free lime indicates an easy-to-burn mix).
chemical and physical processes. The ferrite, C4AF Ordinarily, the burnability is a measure of
microstructure of clinker is a function of the ease of formation of alite from belite
kiln feed properties and the pyroprocessing Improving pyroprocessing and free lime, as formation of the other
conditions. Knowing what happens where, efficiency phases is normally much easier to achieve.
why, and how, can lead to optimising pro- The amount of energy needed to form The lower the temperature at which the
duction, costs, and quality. In turn, the clinker depends on various properties of targeted free lime can be obtained, the
clinker microstructure and composition the raw materials. Using a burnability better is the burnability of the kiln feed.
directly affect how the phases hydrate and equation such as that shown below can The burnability of a raw mix is deter-
contribute to cement performance in fresh identify the specific factors that influence mined by its chemical composition, the
and hardened concrete. burnability at a particular plant, and mineralogy of its component materials, and

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its fineness. There are a number of equa- free lime (clinker burnability) on a relative tants during a given time and therefore,
tions that relate the burnability of a feed basis. the burnability is improved. Note the rela-
to the composition and fineness of the The first part of the equation (first tive magnitude of the coefficients for LSF
minerals (Fundal 1979, Petersen and bracket) represents contribution from the and SR; the role of the liquid for the
Johansen 1979, Christensen 1979, Ludwig chemical properties of the raw mix. The LSF clinker reactions is important, not only for
1973). One example is the burnability (lime saturation factor) represents the CaO the chemical reactions but also for the for-
equation developed at FLSmidth (Theisen of the mix, while the SR (silica ratio or mation of clinker nodules (the physical
1992), provided below. The importance of modulus) is related to the amount of liquid aspect of clinker formation).
a burnability equation is not to provide an phase at the burning zone temperature. The second part of the burnability
exact value of the free lime of clinker made Decreasing the SR is equivalent to increas- equation (second bracket) represents the
from a given raw mixture; it is more impor- ing the amount of liquid phase; since the contribution to the burnability from the
tant that it gives insight into the effect of liquid is the transport medium for the reac- mineralogy and fineness of the raw mix.
raw material properties on the resulting tants, more liquid can transport more reac- The percentages of coarse particles repre-
sented by C125, Q45, and R45 are determined
Figure 1: a simplified view of the clinkering reactions in a Portland cement kiln (Hills 2000) by the overall fineness of the raw mix on
the one hand, and the mineralogical prop-
To 700˚C erties of the raw materials on the other.
• Water is lost from clay minerals Differences in the mineralogy of the mix
• Dehydrated clay recrystallises components leads to differences in grind-
• Some reactive silica may displace ability, which in turn will result in varia-
CO2 from CaCO3 tions in the chemical composition of the
different size fractions of the raw mix. For
700-900˚C example, since quartz is hard to grind, the
As calcination continues, free lime SiO2 content of the coarser fraction of the
increases. Calcination maintains feed mix will normally be higher than that of
temperature at around 850˚C. Lower- the finer fraction. Note that the quartz
limed aluminate and ferrite form. fineness is more significant than fineness
of other materials, as indicated by its
larger coefficient in the equation.
900-1150˚C The equation provides a ‘virtual burn-
Reactive silica combines with CaO to ability test’ to analyse the factors affecting
begin stages of C2S formation. burnability and free lime of the clinker.
There is a relation between the free lime
determined by the ‘virtual burnability test’
1150-1200˚C and the free lime of the clinker. Although
• When calcination is complete, tem- not identical, it can be assumed that the
perature increases rapidly. virtual burnability free lime will correspond
• Small belite crystals form from to a certain constant clinker free lime for a
combination of silicates and CaO. given constant kiln operation. Further, for
Round belite
a given kiln and set of raw materials, if the
crystals
1200-1350˚C virtual burnability free lime of the kiln
v Above 1250˚C, liquid phase is feed changes and the kiln process parame-
formed. ters remain the same, the clinker free lime
• Belite and free CaO form alite in will change in a way so the ratio between
Angular alite the liquid. the virtual free lime value and the clinker
crystals free lime remains the same as before the
change. For instance if the virtual free lime
1350-1450˚C is 3.2 per cent and the average clinker free
• Belite crystals decrease in number, lime is 1.4 per cent for a given steady
increase in size. state of kiln operation, the ratio is 2.3.
• Alite crystals increase in size and This defines a burning index and is a mea-
number. sure for how the kiln in that state of oper-
ation on average burns the kiln feed.
Cooling Reasons for variations in burnability could
• Upon cooling, the C3A and C4AF be insufficient raw mix control and/or
crystallise from the liquid phase. homogenisation of the kiln feed. The
• Lamellar structure appears in resulting clinker will vary in free lime con-
belite crystals. tent, and the normal reaction from kiln
operators is to burn harder and eventually
operate the kiln on the ‘hot side’ to avoid

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Figure 2: clinker silicate phases as observed to the average value and narrow the varia-
under a microscope (polished section with
nital etch)
tion in free lime, the burning index will
change from the original 2.3 to
Alite (C3S) normally hexagonal crystals 4.5/1.4=3.2. From Figure 5 such a change
observed in cross-section, 25-50mm in length. corresponds to an increase of about six per
cent in specific fuel consumption.
Belite (C2S) normally 25-40mm rounded
crystals with multidirectional lamellae.
Once again, an understanding of
burnability and free lime content is impor-
Figure 3: phases in clinker interstitial tant. There is a relation between the ‘vir-
(polished section with nital etch)
tual burnability’ free lime and the free lime
Tricalcium aluminate (C3A): observed in of the clinker from the kiln. This burning
etched and polished clinker as blue to gray index ratio can be used as a process para-
angular crystals in the interstitial. High meter. If the kiln is operated in steady
alumina ratio will produce greater amount state, the ratio is constant. However, if the
of aluminate than ferrite.
‘virtual burnability’ deteriorates (ie
Ferrite (C4AF) appears more reflective tan decrease in mix fineness or change in
C3A in an etched polished surface chemistry), and the kiln is kept in the
same steady state, then the clinker free
Figure 4: clinker photomicrograph demon-
lime will increase. The usual operator reac-
strates reaction between belite and free CaO
to form alite (polished section with nital tion to an increase in clinker free lime is
etch) to burn harder. However, if an examination
of the kiln feed were performed to identify
Either properties of the raw materials, mix
the cause for the increase in ‘virtual burn-
homogeneity, or the pyroprocessing condi-
tions did not allow the complete transfor- ability’ free lime, the corresponding
mation to alite to take place. increase in clinker free lime would be
anticipated. The kiln operators would
Belite crystals
therefore know what to expect, and would
large variations in the clinker free lime. Free CaO crystals not necessarily constantly operate the kiln
One penalty that results is increased spe- on the hot side. The examples given above
cific fuel consumption. are +/-0.6 per cent and +/-0.07 respec- also emphasize the importance of good raw
An example of the relation between the tively. Using the equation for the virtual mix control and kiln feed homogenisation
burnability index and the specific fuel con- burnability test given above, these varia- vis-à-vis the specific fuel consumption.
sumption is the result of analysis of data tions correspond to a variation of the vir- Most often, the mineralogy and fine-
from a 2000tpd kiln with planetary coolers, tual burnability test free lime between 3.8- ness change little compared to the chemi-
as shown in Figure 5. Based on averages of 2.6 per cent. For the steady state kiln cal composition unless the raw material
kiln feed chemical composition and fine- operation referred to above, with burning sources are changed. Therefore, using the
ness, the virtual burnability free lime was index = 2.3, this will result in clinker free chemical contribution portion of the burn-
determined and together with the average lime between 1.7-1.1 per cent. In the sec- ability equation is helpful. This calculation
clinker free lime for the same period, the ond example let the kiln feed composition will give an indication of feed burnability
burning index ratio calculated. vary +/-2 per cent in LSF and +/-0.23 in very quickly. An example of chemical analy-
An increasing burnability index means SR. This corresponds to variations in the sis and calculation of its contribution to
harder burning, resulting in higher specific virtual burnability free lime between 4.5 burnability is below. Note that the trend in
fuel consumption. Figure 5 can be used to and 1.9 per cent, and for constant kiln burnability is more easily detected when
analyse the effect of kiln feed homogeneity operation a variation of the clinker free looking at the calculated chemical contri-
on the specific fuel consumption. As an lime between 2-0.8 per cent. As a result of bution instead of the individual factors of
example, consider a kiln with average feed the less homogeneous kiln feed in the last LSF and SR alone.
composition corresponding to LSF = 98 per example, the clinker free lime will vary
cent and silica ratio, SR = 2.8 (correspond- within wider limits. If the operation is Fluxes and mineralisers
ing to about 66 per cent C3S), with virtual changed to harder burning in order to The use of fluxes and mineralisers can pro-
burnability free lime of 3.2 per cent and an bring the maximum clinker free lime down mote clinker phase formation, and there-
average clinker free lime 1.4 fore improve efficiency of the
per cent. For a steady state CaO1400˚C =[0.343(LSF-93) + 2.74(SR-2.3)] + [0.83Q45 + 0.10C125 +0.39R45] pyroprocessing system. By
kiln operation and a con- Where: definition, a flux promotes a
stant homogeneous kiln CaO1400˚C = is the free lime after burning for 30 minutes at 1400˚C reaction by increasing the
feed, the burning index is LSF = %CaO/(2.8% SiO2 + 1.18% Al2O3 + 0.65% Fe2O3) amount of liquid at a given
3.2/1.4=2.3. In reality the SR = % SiO2/(% Al2O3 + % Fe2O3) temperature; for example,
kiln feed composition will Q45 = % quartz grains coarser than 45µm Al2O3 and Fe2O3 are fluxes for
vary between certain limits. C125 = % calcite grains coarser than 125µm the formation of alite. A
In the first example, assume R45 = % other acid-insoluble minerals, (eg feldspar) coarser than 45µm mineraliser promotes the for-
the variations in LSF and SR mation of a particular solid

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phase through its incorporation in one or lime compacts had free lime levels around
more of the solid phases (normally either 13 per cent. The high lime and low lime
alite or belite). A general view demonstrat- compact cylinders were placed in intimate
ing the process of clinker formation using mutual contact, and the cylinders re-
a flux or mineraliser, contrasted with using burned at 1500˚C for one hour. Figure 7
neither is outlined in Figure 6. demonstrates this ‘sandwich’ technique.
Fluxes and mineralisers have been The resulting clinkers were cut, trans-
studied in laboratory experiments and in Figure 5: Burning Index Ratio (virtual burn- verse to the joint, etched with Nital
practice (Flint, 1939, Johansen and ability free lime/clinker free lime). Each point etchant, and examined under reflected light
represents the average over a 4-week period.
Christensen, 1979, Surana and Joshi 1990, No corrections were made for kiln downtime microscopy. The results, shown in Figures 8
Erhard, 1994, Altun, 1999). A series of dif- during the 4-week periods, which might and 9, illustrate the broadening of the
ferent compounds have been used; how- explain the outliers region near the joint where no belite or free
ever, the ones with the most practical lime exists – ie, where alite formation has
application are fluorides. ings in combination with gypsum/fluorspar occurred between the high and low lime
Fluoride-containing mineralisers have and others; all showed some effect either compacts. The much broader width in the
been used since the late 1800s (Bhatty, as fluxes or mineralisers but the studies fluoride-doped clinker (about twice as wide)
1996). Fluoride-containing compounds did not result in practical use. shows how much faster alite forms in the
such as CaF2, NaF, BaF2, and MgF2, are all The benefits of added fluoride in presence of 0.25 per cent fluoride.
effective primarily as mineralisers, achieving desired free lime levels at lower With regard to fluxes and mineralisers
although CaF2 has enjoyed the greatest temperatures are illustrated by a study in in general, Bhatty (1996) reports a survey
use. Alkali- and alkaline-earth fluorosili- which the same rather hard-burning raw regarding their use in the cement industry.
cate salts like Na2SiF6 and MgSiF6 can also mix was burned with and without the addi- The fluxes and mineralisers referred to were
achieve similar mineralising effects (Lea, tion of 0.25 per cent fluoride. In this par- fluoride-based (primarily fluorspar), and
1971). The effect of 5-10 per cent ticular case, the fluoride was added as a other non-fluoride-based materials. The
fluoride salt. The mixes were latter were industrial by-products or waste-
LSF SR Chemical contribution burned at 1450˚C (2640˚F) for 60 derived materials primarily used as correc-
[0.343(LSF-93) + 2.74(SR-2.3)] minutes. The resulting free lime tive materials in the mix. They contained
95.2 2.2 0.48 content of the control clinker iron oxide and alumina and resulted in
95.6 2.3 0.89 was 5.05 per cent, while that of decreasing of the silica ratio of the raw
94.9 2.8 2.02 the clinker to which fluoride was mix. This silica ratio reduction is equiva-
95.9 3.1 3.19 added was 2.31 per cent. A fur- lent to an increase of the clinker melt con-
95.8 3.2 3.43 ther demonstration of the bene- tent, and hence to an improvement of the
fits to burnability of added fluo- burnability. The study indicates that
Alite Alite Alite Alite ride was carried out using the cement plants outside North America use
Belite Free lime Alite so-called ‘sandwich’ technique. fluxes and mineralisers with better results
<0.12% 13% Belite Free lime In this technique, two compacts than do the North American plants. In
free lime free lime are prepared. The first is calcu- most cases improvements in burnability,
lated to be an alite/free lime kiln operation, energy savings, and cement
Figure 7: diagrams demonstrate the clinker ‘sandwich’ before mixture, while the second is cal- quality were noted. With the fluoride min-
(left) and after (right) re-burning
culated to be an alite/belite eraliser, setting time was reported to
mixture after clinkering. The compacts had increase in some cases. Christensen (1980)
fluorspar on the clinkering of two cement the compositions shown in the table suggested a mechanism for the effect of
compositions was reported (Klemm, 1976) below. mineralisers that implies increased setting
and as expected, these massive additions Pairs of compacts were made, with and time, which is in line with observations
resulted in both a reduction in clinkering without added fluoride. The individual with using fluoride compounds.
temperature and a consequent retardation compacts were burned at 1450˚C for 30 One must be aware of side-effects of
of cement setting. However, there was lit- minutes, cooled rapidly to room tempera- using some materials as fluxes or miner-
tle effect on the 28-day strength of ture, and the free lime levels determined. alisers. In North America, the most com-
hydrated cements. The low lime compacts had negligible free monly reported problem when using fluo-
Although fluoride-containing com- lime levels (<0.12 per cent), and the high ride-based fluxes/mineralisers is the
pounds have been proven to blockage of preheaters caused
be the most effective miner- Reagent High lime compact, % Low lime compact, % by fines and volatiles. To pre-
aliser in cement clinkering Calcium carbonate 78.9 74.3 vent these blockages, it is
reactions, a number of other Quartz (SiO2) 10.73 15.33 recommended to tightly con-
possible fluxes and miner- Alumina (Al2O3) 3.86 3.86 trol kiln temperature and the
alisers have been studied. Ferric oxide (Fe2O3) 1.93 1.93 thermal profile to prevent
These have included gypsum Magnesium hydroxide 3.05 3.05 overheating of the load and
and sulpate mineral tailings, Sodium carbonate (Na2CO3) 0.51 0.51 generation of additional
fluoro-gypsum, phosphorus- Potassium carbonate (K2CO3) 1.02 1.02 volatiles and fines. In other
containing calcareous tail- words, the burning zone tem-

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perature reduction that has now Figure 6: simplified clinkering reactions in a Portland cement kiln with further increasing fuel consumption
become possible because of the no additions, with mineraliser, and with flux and presenting handling problems.
use of mineralisers must be Clay particle Limestone particle The high temperature conditions
implemented. Normal clinkering Clinkering with mineraliser Clinkering with flux
may lead to reductions in clinker
Fluoride can also be a alkali and sulphate level, colour
retarder in cement hydration if variations, and increases in water
present at too high a level. In demand attributable to increased
the example provided below, a levels of aluminate. The reduced
particular plant produced two Liquid phase formation occurs earlier (at lower temperature) clinker alkali and sulphate will
Type I cements with differing affect setting time, decrease early
fluoride levels; the fluoride ratio strength and increase later-age
varied by a factor of four based strength; and fresh concrete might
on the raw materials. The high- develop admixture incompatibility
fluoride cement had an initial Mineralisers promote earlier silicate Increased liquid phase and changes in its rheological
setting time of 2.4 times longer phase formation (some enhance liquid allows more C3S behaviour.
than the low-fluoride cement. formation, some form intermediate phases) (alite) to form
The conduction calorimeter, Conclusion
which measures the hydration Specific properties of cement raw
profile of cement pastes at con- materials are critical to plant effi-
stant temperature, gave a very ciency and energy consumption,
Without mineraliser With mineralisers and fluxes, desired clinker
graphic picture of the difference based on burnability. This involves
or flux, clinker phases phases are formed earlier, and is discharged
in hydration of the two cements, are still forming from kiln. The result: residence time in the chemical properties of the raw
as shown in Figure 10. in kiln kiln is reduced, and less energy is required mix, along with the mineralogy and
The graphs demonstrate the fineness of the materials.
delay in the C3S peak for the Determining a ‘virtual burnability’
cement with high fluoride con- using these parameters identifies
tent. The maximum hydration the critical areas where changes
rate is delayed from about nine could be made to improve burnabil-
hours to about 17 hours. It appears from Figure 9: clinker ‘sandwich’ with fluoride after ity and lower fuel consumption.
these results that the amount of fluoride re-burning When the quarry and the raw materi-
present in the high-fluoride cement was als available make it hard to achieve burn-
too high for acceptable cement setting ability goals, the judicious use of fluxes
behaviour. The behaviour of cements with and/or mineralisers may be a prudent mea-
optimum fluoride addition may be consid- sure. Fluxes and mineralisers promote
ered somewhat analogous to that of clinker phase formation to occur earlier,
cements hydrated at low temperatures, or thereby improving the efficiency of the
to cements hydrated in the presence of increase the burning zone temperature to pyroprocessing system. Fluoride-containing
retarding admixtures. Although the early achieve the desired free lime level. Hard compounds appear the most effective min-
hydration is delayed, the ultimate hydra- burning will tend to cause low clinker eraliser in clinkering reactions. An experi-
tion may indeed lead to better late porosity, large crystals of alite, and often mental study demonstrated quicker alite
strengths (Moir, 1982). It is not unusual contributes to generation of dust and/or formation in the presence of 0.25 per cent
for cements experiencing slight retardation large clinker balls, instead of good, nodular fluoride.
in setting time to develop 28-day clinker. It also slows down the resulting Changes in raw materials and/or clinker
strengths higher than those of their faster- cooling process, both because the maxi- formation can influence what happens
setting counterparts. mum temperature is higher, and because through the kiln, the mill, all the way
the low porosity clinker is more difficult to through to the cement performance.
Operations and performance cool. This can often result in generation of This paper demonstrates the impor-
Changes in burnability and/or clinker for- cement with reduced strength potential tance of optimising burnability and clinker
mation can have important practical and increased water demand. Clinker tem- formation by careful mix control, good mix
impact on what happens in the kiln, the peratures exiting the cooler may increase, homogeneity, and tailoring the burning
mill, and the product. If the mix is hard to Figure 10: calorimeter results of high and low process to the raw mix. Real energy sav-
burn, the operator will be obliged to fluoride cements ings, potential production increases in kiln
and mill, and product enhancement are the
Figure 8: clinker ‘sandwich’ after re-burning rewards for following these principles.
_________________________❒

This paper has been edited and reprinted


with kind permission from Linda Hills —
‘Solving raw material challenges’ © 2002
IEEE, New York, NY.

84 INTERNATIONAL CEMENT REVIEW / SEPTEMBER 2002

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