14

Lime Calcination

Gupta Sudhir Kumar, Anushuya Ramakrishnan,

and Yung-Tse Hung

CONTENTS
INTRODUCTION
THE CHEMICAL REACTIONS
KINETICS OF CALCINATION
PROPERTIES OF LIMESTONES AND THEIR CALCINES
FACTORS AFFECTING LIME CALCINATION
CALCINATION OF INDUSTRIAL SOLID WASTES
CARBON DIOXIDE EMISSIONS FROM LIME CALCINATION
SOLAR LIME CALCINATION
CONCLUSIONS
NOMENCLATURE
REFERENCES

1. INTRODUCTION
Lime is one of the most widely used and cheapest alkalizing agents employed world-
wide. It is often applied in chemical processes in a slaked or calcium hydroxide or slurry
form. The term “calcinations of limestone” refers to the process of thermal decomposi-
tion into quick lime and carbon dioxide. It is frequently referred to as “calcinations.”
Decomposition of limestone is characterized by very simple chemical reactions.
Complexity is seen to arise when dealing with dolomite, which is believed to cause a
change in crystallography and microstructure. Kinetics of decomposition of granular
and lumped limestones has been found to be very complex. This has resulted in a lim-
ited validity to produce a unified theory on calcinations. This is controlled by many fac-
tors, which includes:
• One of the steps in calcinations may be rate limiting under specific circumstances.
• Differences exist in crystallography and microstructure of limestone, which are very difficult
to quantify, can have a marked effect.
• Microstructure and surface morphology of limestone are seen to have a significant effect on
calcinations and these are controlled by temperature, impurities, and time of exposure after
completion of the reaction.

From: Handbook of Environmental Engineering, Volume 5: Advanced Physicochemical Treatment Technologies

Edited by: L. K. Wang, Y. -T. Hung, and N. K. Shammas © The Humana Press Inc., Totowa, NJ

611
612 Gupta Sudhir Kumar et al.

Fig. 1. Variation of the dissociation pressure of calcite with temperature.

2. THE CHEMICAL REACTIONS

2.1. Calcium Carbonate
Limestone is calcined to produce unslaked lime, the reaction for the thermal decom-
position of calcium carbonate may be expressed as:

CaCO3 + Heat m 
o CaO + CO
 2
(1)
100 g 56 g 444 g

The variation of dissociation pressure of calcite with temperature is shown in Fig. 1.

It is seen to reach 1 atm (101.3 kPa) at approx 900°C. Recent work has pointed out a
value of 902.5°C unlike the earlier studies, which had reported a value of 898°C.
Calcination of limestone is accompanied by dissociation of heat. The heat of disso-
ciation of calcite relative to 25°C has been reported in the literature to range between
695 and 834 kcal/kg of CaO. An average value of 770 kcal/kg has been reported by
Boynton (1), whereas Schwarzkopf (2) has reported a value of 754 kcal/kg.
At 900°C, the heat of dissociation is 723 kcal/kg CaO based on the aforementioned
calculation. A difference of 37 kcal/kg CaO is because of the following fact. It should
be noted that 1.786 kg of calcium carbonate requires 431 kcal to be heated from 25°C
to 900°C, whereas the reaction products—1 kg of CaO and 0.786 kg of CO2—release
208 and 186 kcal, respectively, on cooling from 900 to 25°C, a total of 394 kcal.
Schwarzkopf (2) reports a value of 698 kcal/kg at 900°C.

2.2. Magnesium Carbonate

Thermal decomposition of magnesium carbonate is represented as:
MgCO + Heat m 
o MgO + CO
3 2
(2)
84 g 40 g 44 g
The dissociation pressure of MgCO3 has been reported to range between 402
and 550°C (1,2) at 1 atm. The heat of dissociation of MgCO3 has been reported to be
723 kcal/kg MgO (3).