Write down the Chemical Reactions

take place in the kiln or rotary kiln

• The chemical reactions take place in the kiln are given below:
– Evaporation of free water up to 100°C. the reaction is endothermic.
– Dehydration of clay at 500°C. the reaction is endothermic.
– Dissociation of 𝑀𝑔𝐶𝑂3 between 400-500°C. the reaction is
endothermic.
– Crystallization of dehydration products at 900°C and the reaction is
exothermic.
– At 900°C and above, there is evolution of 𝐶𝑂2 from the
decomposition of limestone. The reaction is endothermic.
– Main reaction between lime and clay takes place between 900-
1200°C and 2CaO.𝑆𝑖𝑂2 is formed. The reaction is exothermic.
– Formation of 3CaO. 𝐴𝑙2 𝑂3 at 1200-1300°C. the reaction is
exothermic.
– The charge starts melting at 1260°C. the reaction is endothermic.
– Cement formation between 1260-1500°C with the disappearance of
lime.
 What is gypsum and why it is used in
Cement?
• Gypsum is a non-metallic natural mineral and found in
the sedimentary rocks such as limestone, sandstone,
shales etc.
• It is obtained as a by product during the manufacture of
salt from brines and sea water.
• Pure gypsum is colourless to white, but due to mixing of
impurities, it may be grey, brown, red or pink in colour.
• On heating gypsum to 120°C, it gets converted into plaster of
1
paris (𝐶𝑎𝑆𝑂4 . 𝐻2 O).
2
• Gypsum (𝐶𝑎𝑆𝑂4 . 2𝐻2 O) is a minor component of cement.
• In grinding machine, 2-3% gypsum is added to cement
because it prevents the rapid setting of the cement and
actually enhances the initial setting time of cement.
 How is Rapid Setting of Cement
Retarded by Gypsum
• In grinding machine, 2-3% gypsum is added to
the clinker.
• 3CaO.𝐴𝑙2 𝑂3 is a fast setting material reacts with
gypsum to form the crystals of calcium sulpho
aluminate.
• 3CaO. 𝐴𝑙2 𝑂3 + 3(𝐶𝑎𝑆𝑂4 . 2𝐻2 O) + 25𝐻2 O → 3CaO.
𝐴𝑙2 𝑂3 .3𝐶𝑎𝑆𝑂4 . 31𝐻2 O.
• Thus the addition of gypsum removes the fast
setting 3CaO. 𝐴𝑙2 𝑂3 as 3CaO.
𝐴𝑙2 𝑂3 .3𝐶𝑎𝑆𝑂4 . 31𝐻2 O and hence the process of
setting cement gets retarded.
 Plasters of paris
1
• Chemically plasters of paris is 𝐶𝑎𝑆𝑂4 . 𝐻2 O.
2
• It is a white powder.
• It quickly sets to a hard mass when made into a thin
paste with water.
• A slight expansion takes place in the process and
heat is evolved.
• The setting takes place in two stages.
1 𝑆𝑒𝑡𝑡𝑖𝑛𝑔
– 𝐶𝑎𝑆𝑂4 . 𝐻2 O 𝐶𝑎𝑆𝑂4 . 2𝐻2 O (Orthorhombic)
2 𝐻2 𝑂
𝐻𝑎𝑟𝑑𝑒𝑛𝑖𝑛𝑔
𝐶𝑎𝑆𝑂4 (Monorhombic gypsum)
 Explain of plaster of paris from
gypsum
120°𝐶 200°𝐶
 2𝐶𝑎𝑆𝑂4 . 2𝐻2 𝑂 (𝐶𝑎𝑆𝑂4 )2. 𝐻2 𝑂 (𝑝𝑙𝑎𝑠𝑡𝑒𝑟 𝑜𝑓 𝑝𝑎𝑟𝑖𝑠) + 3𝐻2 𝑂
𝐶𝑎𝑆𝑂4
• On heating gypsum to 120°C, it gets converted into plaster of paris.
• The temperature should not exceed above 120°C, otherwise 200°C,
gypsum is fully dehydrated.
• it is then called dead burnt gypsum.
• Gypsum is used in the preparation of plasters of paris, chalk pencils or
crayons etc.,
• It is also used in the manufacture of cement to prevent rapid setting.
• It is used in the preparation of tiles, plasters, baking powder and for
the treatment of soil.
• Gypsum is used in paints, pharmaceuticals, paper filling, insecticides,
water treatment etc.,
• It is used to lower the pH of water brewery.
 Difference between
Dry process
• In dry process, no water is
added in the treatment of the
raw materials.
• It is slow , costly and low
quality cement.
• The fuel consumption is low.
• It can only be used when the
raw materials are quite hard.
• Cement can easily be dried.
• It is very profitable.
Wet process
• In wet process, raw materials
are treated with water.
• It is comparatively faster,
cheaper and superior quality
cement.
• The fuel consumption is high.
• It can be used for hard as well
as soft raw materials.
• Drying of cement is very
tough.
• It is not very profitable.
 Describe a modern rotary kiln for the manufacture of
cement/describe a rotary kiln for the manufacture of
cement and discuss the chemical events taking place
during its operation
• A rotary kiln consists of an inclined cylinder made of sheet steel. The
cylinder is about 200-350 ft long and 7-12 ft in diameter. The lower end of
the cylinder is provided with a fire proof hood, to which is attached a short
rotating cylinder inclined in the opposite direction for the passing out of
the hot clinker and for cooling it. The charge slowly moves forward due to
the rotary motion (30-60 turns per hour) given to the kiln by means of
girth gear situated near its middle and a train of reducing gears. The upper
portion of the kiln is usually bare or lined with ordinary brick, while the
middle portion is lined with thick fire brick lining and the lower firing
zone is lined with fire clay bricks.
Describe a modern rotary kiln for the
manufacture of cement (Cont..)

Fig: Rotary cement kiln

 Describe a modern rotary kiln for the
manufacture of cement (Cont..)
• Reactions taking place in the rotary kiln can be divided into the following
three parts.
– Reaction taking place in the first zone:
• This zone is called drying zone. Moisture present in the materials is eliminated as
in this region, the temperature remains at about 750°C.
– Reaction taking place in the second zone:
• This zone is known as calcining zone. When the charge enters in this zone, the
temperature rises to about 1000°C. At this temp, limestone is decomposed into
CaO and 𝐶𝑂2.
» 𝐶𝑎𝐶𝑂3 → 𝐶𝑎𝑂 + 𝐶𝑂2
– Reaction taking place in the third zone:
• The third zone is known as hottest zone or cement forming zone. In this zone,
temperature further rises to about 1400-1500°C. at this temp, the mixture is partly
fused and the chemical reaction between calcium oxide and aluminum silicate
takes place resulting in the formation of calcium silicate and aluminates.
– 2CaO + 𝑆𝑖𝑂2 → 2𝐶𝑎𝑂. 𝑆𝑖𝑂2
– 3CaO + 𝑆𝑖𝑂2 → 3CaO. 𝑆𝑖𝑂2
– 3CaO + 𝐴𝑙2 𝑂3 → 3𝐶𝑎𝑂. 𝐴𝑙2 𝑂3
– 4CaO + 𝐹𝑒2 𝑂3 + 𝐴𝑙2 𝑂3 → 4𝐶𝑎𝑂. 𝐴𝑙2 𝑂3 . 𝐹𝑒2 𝑂3
• The resultant product is known as cement clinker.
 What is Clinker?

• The raw slurry which is introduced into the hopper

provided on the upper part of a rotary kiln travel
slowly to the lower firing end.
• In the rotary kiln, it is heated at temp between
1400°C-1500°C.
• At this temp, the mixture is partly fused and the
chemical reaction between calcium oxide and
aluminum silicate (clay) takes place resulting in the
formation of calcium silicates and aluminates.
• The resulting greenish black or grey coloured, hard
granular masses are called clinker.
 Testing of cement
• The quality of a sample cement is determined from a number of
measurements. For example.
– Tensile strength: it should not be less than 300
lbs/sq.inch after 3 days and not less than 2500 lbs/sq.inch
after 7 days.
– Compressive strength: it should not be less than 1600
lbs/sq.inch after 3 days and not less than 2500 lbs/sq.inch
after 7 days.
– Soundness: it is estimated by the Le-chatelier technique
and expresses of cement set for 24 hours, between 80°F
and the boiling point of water.
– Fineness: According to Turbidimetric method, the
fineness of ordinary cement should be 1600 sq.cm/g.
– Specific gravity: It should be 3.1 to 3.2.