CALCINATION OF LIMESTONE

POSTED BY SATYENDRA ON MAY 2, 2013 IN TECHNICAL | 3 COMMENTS

Calcination of Limestone
Calcination or calcining is a thermal treatment process to bring about a thermal decomposition. The
process takes place below the melting point of the product. The name calcination is derived from the
Latin word Calcinare which mean to burn lime. Limestone is a naturally occurring mineral. It exists
nearly all over the world. The chemical composition of this mineral varies greatly from region to region
as well as between different deposits in the same region. Therefore, the end product from each
natural deposit is different. Typically limestone is composed of calcium carbonate (CaCO3),
magnesium carbonate (MgCO3), silica (SiO2), alumina (Al2O3), iron (Fe), sulphur (S) and other trace
elements.
Limestone is one of the most basic raw materials employed in the steel industry and is used both in
iron making and steel making processes. Lime (CaO) is one of the oldest chemicals known to man
and the process of lime production is one of the oldest chemical industries. Quicklime was produced
in US as early as 1635 in Rhode Island. Technical progress which was non existing in centuries past,
has rapidly advanced the lime industry during the last fifty years in the area of process methods and
design.
Limestone deposits are wide distributed. The limestone from the various deposits differs in physical
chemical properties and can be classified according to their chemical composition, texture and
geological formation. Limestone is generally classified into the following types:

High calcium The carbonate content is composed mainly of calcium carbonate with a
magnesium carbonate content not more than 5 % (usually less).

Magnesium This contains magnesium carbonate to about 5 20%.

Dolomitic -This is also known as dolomite and contains over 20 % of MgCO3. However the
maximum MgCO3 content does not exceed 45.6%. The balance amount is calcium carbonate.
Limestones from different sources differ considerably in chemical compositions and physical
structures. The chemical reactivity of various limestones also shows a large variation due to the
difference in crystalline structure and the nature of impurities such as silica, alumina and iron etc. The
varying properties of the limestone have a big influence on the processing method. Hence it is
necessary to know comprehensive information of the limestone such as physical and chemical
properties, the burning characteristics and kinetic parameters for the calcination of the limestone. This
aids optimal design and operation at lime kilns.
Calcination process
Calcination reactions usually take place at or above the thermal decomposition temperature. This
temperature is usually defined as the temperature at which the standard Gibbs free energy is equal to
zero. In case of limestone calcination, a decomposition process, the chemical reaction for
decomposition of the limestone is
CaCO3= CaO + CO2 (g)
The standard Gibbs free energy of reaction is approximated as ?Gr = 177,100 ? 158 T (J/mol). The
standard free energy of reaction is zero in this case when the temperature T is equal to 1121 K or 848
deg C. Hence the chemical decomposition reaction for pure CaCO3 will start at 850 deg C.
Calcination of calcium carbonate is a highly endothermic reaction, requiring 755 M Cal of heat input to
produce a ton of lime. The reaction begins when the temperature is above the dissociation
temperature of the carbonates in the limestone. This typically is between 850 deg C and 1340 deg C.
Once the reaction starts the temperature must be maintained above the dissociation temperature, and
carbon dioxide evolved in the reaction must be removed. Dissociation of the calcium carbonate

proceeds gradually from the outer surface of the particle inward, and a porous layer of calcium oxide,
the desired product, remains. The following factors affect the calcination.
Crystalline structure affects the rate of calcination, internal strength of limestone and resultant crystal
size of lime after calcination. The smaller crystals agglomerate during calcination and forms larger
crystals which in turn cause shrinkage and volume reduction.
Calcination at higher temperature means higher agglomeration and more shrinkage. Also the density
of limestone is related to the crystal structure. The shape of crystals determines the void space
between crystals, and hence the density of the limestone. Larger voids allow easy passage for CO2
gases during calcination and it results in a reduction of volume during calcination. Some limestone,
due to its crystalline structure, disintegrates during the calcination process. This type of limestone is
not useful for calcining. There is some other limestone whose behavior is the opposite. This type of
limestone become so dense during calcination that it prevents the escape of CO2 and become non
porous. This type of limestone is also not suitable for calcination.
The smaller size limestone is more suitable for calcination in rotary kilns and it allows optimum
residence time. The lower calcining temperature also allows less fuel consumption. In contrast, larger
size limestone and low calcining temperature is needed for vertical kilns. If the temperature rise is too
rapid, the outer layer of the limestone pieces is calcined very fast. As the temperature rises, the
surface of the limestone shrinks and closes the pores created by the escape of CO2. This causes
increased internal pressure within the limestone. Since the CO2 gas cannot escape, the limestone
explodes and disintegrates producing unwanted fines thus reduces the quality of the lime.
The production of good quality lime depends upon the type of kiln, conditions of calcination and the
nature of the raw material i.e. limestone. At relatively low calcination temperatures, products formed in
the kiln contain both unburnt carbonate and lime and is called underburnt lime. As the temperature
increases, soft burnt or high reactive lime is produced. At still higher temperatures, dead burnt or
low reactive lime is produced. Soft burnt lime is produced when the reaction front reaches the core of
the charged limestone and converts all carbonate present to lime. A high productive product is
relatively soft, contains small lime crystallites and has open porous structure with an easily
assessable interior. Such lime has the optimum properties of high reactivity, high surface area and low
bulk density. Increasing the degree of calcination beyond this stage makes formed lime crystallites to
grow larger, agglomerate and sinter. This results in a decrease in surface area, porosity and reactivity
and an increase in bulk density. This product is known as dead burnt or low reactive lime.
Calcining kilns
Calcining kilns are basically comes in two categories. They are i) rotary kilns and ii) vertical kilns. Both
the types of kilns can be designed with any of the solid, liquid or gaseous fuels. Rotary kilns can be
long kilns with straight rotary coolers while verticals kilns can be several types. Calcining kilns need
lime stone with decrepitation index. Decrepitation index of limestone is a measure of its susceptibility
to disintegration during calcination. Low value of decrepitation decreases the porosity of the bed thus
impeding the flow of the gases and reducing the kiln efficiency. Rotary kilns also need limestone with
good tumbling index. A rotary kiln with preheater and contact cooler is shown in Fig 1

Fig 1 Rotary kiln with preheater and contact cooler

The schematics of a preheater is shown in Fig 2

Fig 2 Schematics of a preheater

The most popular vertical kilns are PFR (Parallel Flow Regenerative) type. Different types of kilns for
calcining limestone are shown in Fig 3. Various features of these kilns are tabulated in Tab 1.

Fig 3 Different types of kilns for limestone calcination

Tab 1 Comparison of various types of calcining kilns

tpd

mm

Specific fuel
consumption
Kcal/Kg

Rectangular PFR kiln

100-400

30-120

810-870

Circular PFR kiln

300-800

30-160

810-870

Fine lime kiln

200-400

15-40

790-850

Annular shaft kiln

200-600

15-200

910-980

Single shaft kiln

50-300

10-100

980-1100

Rotary kiln with

preheater

300-1200

10-50

1150-1350

Long rotary kilns

without preheater

300-1000

20-50

1600-1700

Suspension calcining

300-1200

0.03-2

1300-1400

Type of calcining kiln Kiln capacity Limestone size

Remarks

Highly reactive lime is

produced
Highly reactive lime is
produced
Highly reactive lime is
produced
High CO2 content in off
gas
Medium hard burnt lime
is produced
Highly reactive lime is
produced, high
production rate and low
sulphur production
high production rates,
reactive lime and low
sulphur
Very fine raw material

Clinker: reactions in the kiln

The milled and blended raw materials go to a silo and then to the kiln.
Reactions which take place as the feed passes through the kiln are
reviewed below.
They can be considered under three broad headings:

Decomposition of raw materials - temperatures up to about 1300 C.

Alite formation and other reactions at 1300 C-1450 C in the burning
zone.

Cooling of the clinker.

Decomposition of raw materials reactions at temperatures up to about

1300 C
This includes:

Water evaporation in the raw feed, if any.

Loss of carbon dioxide from the limestone (ie: calcining).

Decomposition of the siliceous and aluminosilicate fractions of the

feed.

Formation of a sulfate melt phase.

The decomposition products react with lime to form intermediate

compounds which in turn form other compounds as clinkering proceeds.
Water evaporation
In wet-process kilns, and their derivatives, water must first be driven off. In
a wet-process kiln, calcining takes place after the water has been driven
off, about a third of the way down the kiln. In the more modern pre-calciner
kilns, the feed is calcined prior to entering the kiln.
Calcining
In isolation, decarbonation of calcium carbonate at 1 atmosphere takes

place at 894 C. This temperature is reduced to 500 C - 600 C if the

reaction takes place in contact with quartz or the decomposition products of
clay minerals, which react with the calcium oxide as it forms.
In a wet-process or preheater system without a pre-calciner, most of the
calcination takes place in the rotary kiln within a moving mass of feed. This
situation is not ideal for calcination because heat transfer has to take place
through a large mass of material and CO2 has to escape outwards as heat
moves inwards.
A pre-calciner calcines the raw material much more efficiently than a wetprocess kiln. Raw meal is dispersed in the hot gas and calcination takes
place in seconds, rather than the half an hour or so inside a kiln at the
same temperature.
Formation of early and intermediate compounds
During calcination, the lime produced starts to react with other components
of the raw feed. The initial silicate product is belite. Some calcium
aluminate and ferrite phases also start to form.
A number of phases are formed in the clinker feed before the burning zone
proper is reached. These intermediate phases dissociate in the burning
zone and are not therefore found in clinker but assist in forming the final
clinker minerals.
Sulfate melt phase
At intermediate temperatures, sulfates combined with calcium and alkalis
form a liquid phase. This is separate from the aluminate and aluminoferritebased liquid formed in the burning zone - the two liquids are immiscible.
As with the main liquid phase, the sulfate liquid phase contributes to ion
mobility and promotes combination.

Alite formation and other reactions at

1300 C - 1450 C in the burning zone
In the burning zone, above about 1300 C, reactions take place quickly.
The clinker is in the burning zone for perhaps 10-20 minutes but in this time
a lot happens:

The proportion of clinker liquid increases and nodules form.

Intermediate phases dissociate to form liquid and belite.

Belite reacts with free lime to form alite.

Some volatile phases evaporate.

Clinker liquid and nodule formation

Above about 1300 C the proportion of liquid starts to increase - by 1450
C, perhaps 20-30% of the mix is liquid. The liquid forms from melting
ferrite and aluminate phases and some belite. The liquid content is more
than the sum of the aluminate and ferrite phases in the cooled clinker
because of the dissolved lime and silica.
The additional liquid causes coalescence of clinker particles, leading to the
formation of nodules.
Dissociation of intermediate phases
The intermediate phases dissociate to form mainly belite and liquid.
Alite formation
Alite forms by the transition of some of the belite to alite and also directly
from free lime and silica to alite. This occurs rapidly once the clinker
temperature is above about 1400 C.
Evaporation of volatiles
Volatile phases in the cement kiln are principally alkali sulfates, with a much
smaller proportion of alkali chlorides. As the part-burned feed approaches
the burning zone, these volatile phases are in liquid form and a proportion
volatilizes, the remainder passing out of the kiln in the clinker as inclusions
within the pores.
The volatilized material passes back down the kiln, where it condenses on
the relatively cool incoming feed. It again becomes part of the sulfate melt
phase, promoting reactions, and is once again carried within the clinker
towards the burning zone.
This recirculating load of alkali and sulfate can occasionally become
excessively high. Large quantities of condensing volatiles can then cause
blockages in the kiln or in the preheater as the condensed liquid sticks feed
particles together, forming accretions.

Cooling of the clinker

As the clinker cools, the main liquid phase crystallizes to form aluminate
phase, ferrite and a little belite.
Fast cooling of clinker is advantageous - it makes for more hydraulicallyreactive silicates and lots of small, intergrown, aluminate and ferrite
crystals.
Slow cooling gives less hydraulically-reactive silicates and produces coarse
crystals of aluminate and ferrite. Over-large aluminate crystals can lead to
erratic cement setting characteristics. Very slow cooling allows alite to
decompose to belite and free lime.

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WHAT IS FREE LIME

Hai , Normally free lime( calcium oxide) is present in clinker whereas in the cement a major
portion of it is present as Calcium hydroxide.
Free Lime is Calcium oxide (CaO) as in clinker and cement that has not combined with
SiO2, Al2O3 or Fe2O3 during the burning process, because of underburning,
insufficient grinding of the raw mix, or the presence of traces of inhibitors.
FREE LIME IN CLINKER
Calcination of cement raw materials in the kiln produces a material called clinker.Free
lime (CaO) in clinkers has to be closely monitored to ensure the quality of cement.
Excess free lime results in undesirable effects such as volume expansion, increased setting
time or reduced strength.
FREE LIME IN CEMENT

An increase in clinker free lime reduces the total silicates (C3S + C2S). Both C3S and C2S
are involved in the hydration to produce the C-S-H gel which is the main strength forming
phase in hardened Portland cement concrete.Jan 4, 2012