The Relation between Limestone Properties and Quicklime Reactivity

Author: Sonja Hogewoning, Research Institute of Lime and Mortar, Cologne/Germany

Summary:
Within the scope of a research project supported by the German Federation of Industrial Cooperative
Research Associations "Otto von Guericke" (AiF) the influence of limestone properties on the reactivity
of quicklime is analysed and described. In a further step the forecast of quicklime reactivity in
dependence on the limestone used will be attempted.
Samples from 25 limestone deposits are analysed petrographically and chemically. The samples are
burned in a laboratory kiln with a subsequent sinter process with varying temperatures and durations
after calcination. The physical properties of the quicklime obtained by this process are analysed. The
present results are in contradiction to the theory that reactivity primarily is determined by the chemical
composition and that a higher amount of non calcite minerals speeds up the sinter process. Instead it
has to be assumed that there is a much stronger correlation between petrographical parameters and
reactivity.
The subsumption of samples in petrographical groups leads to a temperature-time-model that should
make possible a forecast of quicklime reactivity in dependence on limestone type and burning
conditions.

The presentation is based upon the output of a joint research project between the Research
Institute of Lime and Mortar in Cologne and the Institute of Non-Metallic Materials of the Clausthal
University (workgroup building materials, Prof. Dr. Wolter) which is supported by the German
Federation of Industrial Cooperative Research Associations "Otto von Guericke" (AiF).
Mr. Dipl.-Ing. Bonar Marbun has contributed to the success of this work within the scope of this
project and his dissertation The kinetic of the hydration of CaO and MgO, who among other things
developed the improvement of the analysis method of the wet slaking curve.
The project aims at describing the influence of limestone properties on the reactivity of produced
quicklime, with an emphasis on an adjacent sintering after sample calcination. This knowledge will
be used to pave the way to the development of a prediction model of quicklime reactivity based on
quantified limestone parameters. Therefore samples from different limestone will be burnt and
sintered in a modified laboratory kiln and quicklime reactivity and limestone parameters will be
determined and described. The results will be used for modelling the quicklime reactivity (figure 1).

Figure 1:

Method of resolution

Consideration of the present standard of knowledge leads to questions about the calcination and
sintering of lime and the influence of the limestone properties on the quicklime reactivity.
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The reactivity as an important product parameter has been the object of many research projects in
the past. The relation between reactivity and other quicklime properties have been examined
intensively. Correlations have been made with porosity or apparent density, as well as with the
primary size of the CaO-crystallites. So the theories about the calcination processes are well
known and described in the technical literature. Therefore the actual research project can be based
on the existing findings about these matters. But this knowledge covers primarily the calcination,
though adjacent sintering processes of limestone are more or less unexplored. It is true that the
occurring processes during the sintering of ceramic materials are well know, but to which extend
this can be transferred to the sintering of limestone is yet unknown.
The question about the influence of the limestone properties on the quicklime reactivity has been
worked on only in a few studies and even they are limited on singular limestone deposits and dont
provide comprehensive evidences. Comparison of different projects often leads to contradicting
finings as the following example with results from WUHRER (1953) and ANDERSON (1973) shows.
Both studies examine the influence of the burning regime on the apparent density of the quicklime.
These works give indirect evidence about the influence of the burning regime on the reactivity, as it
is known that higher apparent density indicates a lower reactivity. Generally spoken both authors
note a density gain towards higher burning temperatures and longer periods due to accumulative
crystallisation of the CaO-crystallites.
But WUHRERS results show a stagnation of increasing densities after a certain burning time. This
means that even after a longer burning time the density of the lime wont increase anymore after
reaching its certain point of temperature-time-setting. Furthermore the value of the apparent
density shows a sudden leap between 1200C and 1300C. There seems to be a critical
temperature within this range, where material parameters are abruptly changing. Interestingly
comparisons with ANDERSONS data show a completely different picture. The values of the apparent
density are consistently lower for same burning regimes. Also densities evolve unlikely WUHRERS
results approximately linear. There is no stagnation towards longer burning times and there is no
evidence for a critical temperature at all, too. Even the growing of the density is absolutely constant
towards higher temperatures.
Assumingly these contradicting data are a direct result of the different limestone sources and
therewith a result of the different limestone parameters and their influence on the quicklime
properties.

Figure 2:

Development of the apparent density in dependence of the burning regime

(after WUHRER (1953) and ANDERSON (1973))

Wuhrer analysed 1958 the influence of the burning regime on the quicklimes primary size of the
CaO-crystallites (figure 3). Alike the apparent density the size of the crystallites can be correlated
to the reactivity of the quicklime. Decreasing reactivity is linked to increasing crystallite sizes.
Mainly relevant for the actual research project is the huge range of test results delivered by the
same burning regime. This can also be interpreted as an outcome of varying influence factors from
different limestone properties and is therefore the starting point of the following, actual studies.

Figure 3:

Influence of the burning regime on the primarily crystallite sizes (WUHRER 1958)

Within the context of the presented project analyses and examinations with samples from five
different limestone deposits have been accomplished. Following the details of the project will be
presented with two most distinctive limestones considering as example. Subsequent a synopsis of
the results of all limestone samples will be given.
The limestone samples will be described and characterised with their genesis and their chemical
composition.
From the geological view the limestone A represents a marly, layered limestone from the Cenoman
of the Upper Cretaceous. A global rise of the sea level caused the sedimentation of marl, marly
limestone and limestone as an expression of a marine but shallow sedimentation area. The
combination with a proceeding global warming led to sediments with increasing carbonate
concentration.
The limestone B is a marly-free masslime which attracts attention mainly because of its conformity.
It originates from a reef complex in the Middle and Upper Devon which has been deformed
tectonically in subsequent times. The complex evolved into an atoll with central lagoon and typical
back reef- and reef breccia sediments on top of an offshore barrier.
Figure 4 displays the chemical composition of both samples. The CaCO 3 content of the samples is
a result of their geological genesis. Due to the marly compound of limestone A the sample
possesses with 91,6% a significant lower CaCO3 concentration as the mass lime of sample B with
99,5% CaCO3.The minor components are spread in accordance to the CaCO 3 concentration. They
clearly enriched in sample A. Mainly the SiO 2 content of 4,59% reflects the increase of the minor
components, though aluminium and iron are enriched, too. In contrast the minor components of
sample B are low in all categories. Only MgO is a noticeable parameter as it shows low
concentrations even for sample A.
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We can state, that the two samples represent chemical opposites: a marly limestone sample A with
enriched contents of silicon, iron and aluminium and on the other hand a mass lime sample B that
consist of nearly pure calcium carbonate with close to no minor components.

Figure 4:

Chemical composition of the limestone samples

The used laboratory kiln (Figure 5) is an adapted rotary kiln, operated with a static ceramic inner
tube without incline. It features two burning zones with electric heating elements to be regulated
and operated apart from each other. Both temperature zones in the inner tube are separated from
each other with relocatable insulating firebricks and observed by thermocouples. The samples are
transported through the kiln in ceramic cups which are pushed through the tube. The samples are
calcinated at 1050C in the first temperature zone within one hour and then moved onward into the
second temperature zone for sintering. The temperature in the sintering zone during the tests is set
to 1100C, 1200C or 1400C. The samples are sintered 0,5 to 16 hours at 1100C and 1200C
and 0,5 to 4 hours at 1400C. The test times are scaled on a logarithmic basis (Figure 6).

Figure 5:

Cross-section of the laboratory kiln

Figure 6:

Programme of the sintering tests

The following details are limited to sintering tests at 1200C and 4-8 mm graining and show the
trend of all results in a representable way. Nevertheless the .. o
Before all sintering tests the samples are calcinated at 1050C for one hour in the first temperature
zone of the kiln.
Analyses of the sintering tests are based on determination of quicklime reactivity. The
determination of the wet slaking curve according to EN 459 is the elementary method for
measuring the quicklime reactivity. It quantifies the velocity of the temperature increase during the
slaking reaction after the addition of the quicklime to a defined volume of water in an isolated
container. The results are interpreted by plotting temperature development per time in a linear
scaled diagram.
The determination of the quicklime reactivity in this project has been modified and advanced
(Figure 7). At first the time axis has been displayed in a logarithmic scale. Thereby changes of the
hydration reaction can be detected visually via the curve progression. Though the reaction takes
place in an isolated container heat emission towards the environment can not be completely
avoided and the endpoint may be detected too early. Therefore the emitted heat flow has been
determined to evaluate a correction factor that transfers the measured data into an adiabatic 1
curve. Comparison of the measured and the transferred data in Figure 7 shows the difference
between measured and real reaction ending.
In the following the corrected adiabatic curve has been differentiated by the time, which means that
every differentiated point expresses the gradient of the adiabatic curve in this certain point. So the
maximum value of the differentiation curve illustrates the point of highest hydration reaction
velocity. The differentiated curve follows a Gaussian distribution and hence allows quantifying the
maximum point by adapting gauss distributions to it.

system without heat flow beyond its borders

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Maximum slaking rate

Figure 7:

Modified interpretation method of the wet slaking curve of a CL 90-S as an example

This improved interpretation method of the wet slaking curve is used to determine the reactivity of
the quicklime samples after sintering. Figure 8 shows reactivity evolvement for sample A and B
depending on the duration of sintering at 1200C. The diagram plots the point of the maximum
reaction velocity against the sintering duration.
Low reactivity velocities are symptomatic for high reactive quicklime, while high velocities indicate
a slow hydration reaction.
Sample A (91,6% CaCO3) is very reactive in the beginning and reduces its reactivity not very much
even with sintering duration increasing up to 16 hours. The 30 minutes sintered sample A reaches
its maximum reactivity velocity after 6 minutes. Even after 16 hours of sintering it reaches its
maximum reactivity velocity in only 12 minutes.
In contrary the reactivity of sample B with 99,5% CaCO 3 evolves quite differently. It is reasonably
reactive with 34 minutes after 0,5 hours of sintering, reduces to 148 minutes after one hour but
then speeds up again and finally slows down after 8 hours.

Figure 8:

Reactivity of sample A and B (sintering temperature: 1200C / graining: 4-8mm)

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Figure 9:

Pictures taken by scanning electron microscopy (SEM) after 4 hours of sintering at 1200C

Examination of the quicklime samples with scanning electron microscope (SEM) after 4 hours of
sintering shows the highly reactive lime sample A with microcrystalline and disordered crystal
structures. This generates a large surface of CaO-crystallites available for reaction with water
molecules. In contrary lime sample B with the slower reactivity consist of large CaO-crystallites and
therefore reduced surfaces. Beginning development of vicinal surfaces and increasing grain
coarsening at the crystallite contact areas show up. These are expressions of an increasing order
within the crystallites. The general acceptance assumes that quicker hydration reactions are
promoted by lager surfaces as well as by higher amounts of surface defects. Therefore the pictures
of the SEM are clearly reflecting the results of the reactivity determination.
The measured reactiveness show a completely other picture then it has been anticipated for the
samples A and B. The assumption said that sample B would have resulted in a higher reactive
quicklime then sample A since the limestone B with 99,5% CaCO 3 can allocate a considerable
higher amount of CaO. But the findings are showing exactly the contrary pattern (Table 1). The
sample A has a faster hydration reaction then sample B. Additionally the sample B passes through
different reaction stages with increasing sintering duration.
The simplification of this observation has to be pointed out. On closer examination the comparison
of reactiveness resulting from same sintering temperatures steps back behind the meaning of the
reactivity degradation subjected to time and temperature.

Limestone

low
(91,6%)

high
(99,5%)

expected

Slow

Fast

measured

Fast

Slow

CaCO3
Quicklime reactivity:

Table 1:

Anticipated and measured reactivity depending on chemical composite

(constant sintering temperature)
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As demonstrated the chemical composition of the limestone is not the dominating parameter
regarding the quicklime reactivity. It is needed to examine further limestone properties.
The petrographical properties of the limestone samples are examined with polarising microscopy.
Transparent cuts are viewed in normal scattered transmitted light and in directed, polarized
light. The waves of the polarized light oscillate only in one direction and allow to detect certain
optical properties of the minerals.
Figure 10 shows pictures of transparent cuts of both limestone samples viewed in transmitted light.
Sample A has a fine-grained, dark calcitic matrix, called micrit. Within the micrit rounded
microfossils are spread. Fine fissures have been partial closed afterwards with calcitic material.
Sample B shows coarser sparitic calcite crystals. In the centre is a micritic area located.
Altogether the sample B displays a somehow more inhomogeneous limestone. When examined
with polarised light (Figure 11) sample A does not reveal more details. But the transparent cut of
the sample B shows an area with large singular calcitic crystals in the left part of the picture. They
display a lamellation due to the formation of calcitic twins. The lamellae are detected by the
parallel, dark stripes in the crystals. Assumedly these calcitic twins are the reason for the
unexpected reactivity of sample B, as they are possibly causing specific thermodynamic
interactions during calcination which are abetting the sintering process.

Figure 10:

Polarising microscopy transparent cuts with transmitted light

Figure 11:

Polarising microscopy transparent cuts with polarized light

Obviously the calcium carbonate concentration is not the main influence factor on quicklime
reactivity but it is primarily a function of the petrography of the limestone. The following summary of
the results from the other samples (Figure 12) will clarify that this conclusion is not only limited to
the samples A and B.
Sample C represents a mass lime with high CaCO 3 concentration of nearly 99% and hence a
chemical composite that is comparable to sample B. But the development of the reactivity follows
the trend of the sample A. When viewing the transparent cut with polarisation microscopy the
limestone shows some singular large calcite crystals, too, but these are not showing twin lamellas
like those in sample B.
The mass lime of sample D consists of high calcium carbonate content, too. But the development
of the reactivity of this sample provides a different picture then the samples already seen. It
displays nearly a mirror image of sample B. The 30 minutes sintered quicklime reaches its
reactivity maximum velocity after 110 minutes, then speeds up to a reactivity of 13 minutes with
increasing sintering duration, slows down again and stagnates at values of 80 110 minutes for
the rest of the tests. Using polarisation microscopy an inhomogeneous limestone with sparitic and
micritic sections as well as some larger singular calcits without twin sections analogical to sample
C can be seen.
Only sample E with 99,6% CaCO 3 displays a reactivity development as has been expected based
on the chemical composite. The quicklime is highly reactive at the beginning of the sintering,
decreases with longer duration and stagnates when reaching 4 hours of sintering duration. The
limestone is a reef breccia with a fine-grained sparitic texture and a high content of fossil rests.

Figure 12:

Reactivity of all sample

(sintering temperature: 1200C / graining: 4-8mm)

Therewith the results of the project can be summarised by now as follows:

1) the interpretation method for determining the quicklime reactivity has been modified and
improved
2) the exclusive view on the chemical content of the limestone is not sufficient for correlation
of limestone properties and quicklime reactivity
3) the hitherto underestimated influence of the petrography becomes distinct
4) the working hypothesis for the future tests is the assumption that the existence of calcitic
twins reduces the reactivity
5) the reasons for the non-linear development of the reactivity have to be examined
For clarification of these questions the project will be extended with 20 other samples to receive an
enlarged data base which will enable a statistical analysis of the results. For modelling the samples
will be grouped by their sintering-/reactivity behaviour. Groups can be e.g.:
- high CaCO2 content fine grained slowly sintering
or
- low CaCO2 content coarse grained quick sintering
The details of the grouping have to be discussed after further examinations on basis of the
enlarged database. Modelling will be done with multiple regression analysis whereas the actual
model attempt considers the sintering duration as an exponential factor. An increasing sintering
duration will cause a decreasing reactivity with the value depending on the sintering temperature.
The loading of the petrographical parameters will be part of the following examinations, too.
Recapitulatory can be stated that the prediction of the quicklime reactivity needs the chemical
composite as well as the petrograpical parameters of the limestone for future descriptions of the
raw limestone influence on the quicklime reactivity to enable the development of a quicklime
reactivity prediction model.

Sources:
ANDERSON, L.C. (1973): Resume of ICI Work on Limestone Calcination, Lime Reactivity and
Apparent Density. - Internal Report.
MARBUN, B. (2006): The kinetic of the hydration of CaO and MgO. Dissertation. in print.
WUHRER, J. (1958): Wissenschaftliche und verfahrenstechnische Probleme des Kalkbrennens. Chemie-Ing.-Techn., 30: 19-30.
WUHRER, J. (1953): Physikalisch-chemische Untersuchungen ber den Zustand des Branntkalkes
und ber die Vorgnge und Einflsse beim Brennen. Zement-Kalk-Gips 6(10): 354-368.

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