Concrete Technology (I) Lecture 2

Methods of cement manufacturing

General Manufacturing Process
The process of manufacture of cement consists essentially of grinding the raw
materials, mixing them intimately in certain proportions and burning in a large
rotary kiln at a temperature of up to about 1450 °C when the material sinters and
partially fuses into balls known as clinker. The clinker is cooled and ground to a
fine powder, with some gypsum added, and the resulting product is the commercial
Portland cement so widely used throughout the world.

Methods of cement manufacturing

1- Wet process : grinding and mixing of the raw materials in the existence of
water.
2- Dry process : grinding and mixing of the raw materials in their dry state.

 The process to be chosen, depend on the nature of the used raw materials. For
example, wet process used when the percentage of the moisture in the raw
materials is high, while, dry process used when:
 The raw materials is so hard (solid) that they do not disintegrate by water
 Cold countries, because the water might freeze in the mixture
 Shortage of the water needed for mixing process.

Wet process
When chalk is used, it is finely broken up and dispersed in water in a wash mill.
The clay is also broken up and mixed with water, usually in a similar wash mill.
The two mixtures are now pumped so as to mix in predetermined proportions and
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pass through a series of screens. The resulting – cement slurry – flows into storage
tanks.

When limestone is used, it has to be blasted, then crushed, usually in two

progressively smaller crushers (initial and secondary crushers), and then fed into a
ball mill with the clay dispersed in water. The resultant slurry is pumped into
storage tanks. From here onwards, the process is the same regardless of the original
nature of the raw materials.

The slurry is a liquid of creamy consistency, with water content of between 35

and 50%, and only a small fraction of material – about 2% - larger than a 90 µm
(sieve No. 170).

The slurry mix mechanically in the storage tanks, and the sedimentation of the
suspended solids being prevented by bubbling by compressed air pumped from
bottom of the tanks. The slurry analyze chemically to check the achievement of the
required chemical composition, and if necessary changing the mix constituents to
attain the required chemical composition.

Finally, the slurry with the desired lime content passes into the rotary kiln. This is
a large, refractory-lined steel cylinder, up to 8 m in diameter, sometimes as long as
230 m, which is slightly inclined to the horizontal. The slurry is fed in at the upper
end while pulverized coal (oil or natural gas also might be used as a fuel) is blown
in by an air blast at the lower end of the kiln, where the temperature reaches about
1450oC.

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The slurry, in its movement down the kiln, encounters a progressively higher
temperature. At first, the water is driven off and CO2 is liberated; further on, the
dry material undergoes a series of chemical reactions until finally, in the hottest
part of the kiln, some 20 to 30% of the material becomes liquid, and lime, silica
and alumina recombine. The mass then fuses into balls, 3 to 25 mm in diameter,
known as clinker. The clinker drops into coolers.

Fig (1.3) Diagrammatic representation of the wet process

Dry process
The raw materials are crushed and fed in the correct proportions into a grinding
mill, where they are dried and reduced in size to a fine powder. The dry powder,
called raw meal, is then pumped to a blending silo, and final adjustment is now
made in the proportions of the materials required for the manufacture of cement.

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To obtain a uniform mixture, the raw meal is blended in the silo, usually by means
of compressed air.

The blended meal is sieved and fed into a rotating dish called a granulator, water
weighing about 12% of the meal being added at the same time. In this manner,
hard pellets about 15 mm in diameter are formed.

The pellets are baked hard in a pre-heating grate by means of hot gases from the
kiln. The pellets then enter the kiln, and subsequence operations are the same as in
the wet process of manufacture.

Fig (1.4) Diagrammatic representation of the dry process

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Grinding of the clinker

The cool clinker (produced by wet or dry process), which is characteristically black
and hard, is interground with gypsum CaSO4.2H2O in order to prevent flash
setting of the cement, and to facilitate the grinding process. The grinding is done
in a ball mill. The cement discharged by the mill is passed through a separator, fine
particles being removed to the storage silo by an air current, while the coarser
particles are passed through the mill once again.

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Comparison between wet and dry process

Wet process Dry process
Moisture content of the Moisture content of the
1
slurry is 35-50% pellets is 12%
Size of the kiln needed to Size of the kiln needed to
2 manufacture the cement is manufacture the cement is
bigger smaller
The amount of heat The amount of heat required
required is higher, so the is lower, so the required fuel
3
required fuel amount is amount is lower
higher
4 Less economically More economically
The raw materials can be Difficult to control the mixing
mix easily, so a better of raw materials process, so
5
homogeneous material can it is difficult to obtain
be obtained homogeneous material
The machinery and The machinery and
6 equipment do not need equipment need more
much maintenance maintenance

Chemical composition of Portland cement

The raw materials used in the manufacture of Portland cement consist mainly of
lime, silica, alumina and iron oxide. These compounds interact with one another in
the kiln to form a series of more complex products and, apart from a small residue

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of uncombined lime which has not had sufficient time to react, a state of chemical
equilibrium is reached. The resultant of firing is the clinker.

1) Major Compounds
Four compounds are usually regarded as the major constituents of cement:
Table 1.1: Main Compounds of Portland Cement ‫مهم‬

Where each oxide symbol with one letter:

CaO – C
SiO2 – S
Al2O3 – A
Fe2O3 – F
H2O – H

The rate of cooling affect the degree of crystallization and the amount of
amorphous material present in the cooled clinker. The properties of this amorphous
material, known as glass, differ considerably from those of crystalline compounds
of a nominally similar chemical composition.
The percentage of the main composition of cement can be calculated according to
the Bogue equations, based on the assumption that the reactions reached the
chemical equilibrium state

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 C3S = 4.07 (CaO) – 7.6 (SiO2) – 6.72 (Al2O3) – 1.43 (Fe2O3) – 2.85 (SO3)
 C2S = 2.87(SiO2) – 0.754 (C3S)
 C3A = 2.65 (Al2O3) – 1.69 (Fe2O3)
 C4AF = 3.04 (Fe2O3)

Where, the terms in brackets represent the percentage of the given oxide in the
total mass of cement. Recently, these compositions are determined by x-ray
diffraction.

 C3S which is normally present in the largest amount occurs as small

equidimensional grains. On cooling below 1250oC, C3S decomposes slowly
but, if cooling is not too slow, C3S remains unchanged and is relatively stable
at ordinary temperatures.

 C2S is known to have three forms: α- C2S, which exists at high temperatures,
inverts to the β-form at about 1450oC. β-C2S undergoes further inversion to γ-
C2S at about 670oC but, at the rates of cooling of commercial cements, β-C2S is
preserved in the clinker.

Usually, silicates in the cement are not pure. It contains secondary oxides which
affect the atomic arrangement, the crystal form and properties of the cement
during the hydration process.

 C3A forms rectangular crystals, but C3A in frozen glass forms an amorphous
interstitial phase.

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 C4AF is solid solution ranging from C2F to C6A2F, but the description C4AF is
a convenient simplification.

2) Minor compounds
In addition to the main compounds mentioned above, there exist minor
compounds, such as MgO, TiO2, Mn2O3, K2O and Na2O. Two of the minor
compounds are of particular interest: K2O and Na2O, known as the alkalis
(about 0.4-1.3% by weight of cement). They have been found to react with the
reactive silica found in some aggregates, the products of the reaction causing
increase in volume leading to disintegration of the concrete. The increase in the
alkalis percentage has been observed to affect the setting time and the rate of the
gain of strength of cement.

SO3 form low percentage of cement weight. SO3 comes from

I. the gypsum added (2-6% by weight) during grinding of the clinker,
II. and from the impurities in the raw materials,
III. also from the fuel used through firing process.
Iraqi specification no. 5 limited max. SO3 by 2.5% when C3A ≤ 7%, and by 3%
when C3A> 7%.

MgO, present in the cement by 1-4%, which comes from the magnesia compounds
present in the raw materials. Iraqi specification no. 5 limited max. MgO by 5%, to
control the expansion resulted from the hydration of this compound in the
hardened concrete. When the magnesia is in amorphous form, it has no harmful
effect on the concrete.

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Other minor compounds such as TiO2, Mn2O3, P2O5 represent < 1%, and they
have little importance.

Usual Composition Limits of Portland Typical compound composition

Cement in ordinary Portland cement

Oxide Content, % Compound Content, %

CaO 60-67 C3S 54

SiO2 17-25 C2S 17
Al2O3 3-8 C3A 11
Fe2O3 0.5-6 C4AF 9
MgO 0.5-4
Alkalis (as Na2O) 0.3-1.2
SO3 2.0-3.5

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Examples of a Bogue calculation:

Example 1
Clinker Analysis

SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O SO3 LOI IR Total

21.5 5.2 2.8 66.6 1.0 0.6 0.2 1.0 1.5 0.5 98.9

Free lime = 1.0% CaO

Using the above analysis, the calculation is as follows: Combined CaO = (66.6% -
1.0% free lime) = 65.6% .This is the figure we use for CaO in the calculation.
From the analysis, we have:
CaO= 65.6%; SiO2=21.5%; Al2O3=5.2% and Fe2O3=2.8%
The Bogue calculation is therefore:
C3S = 4.0710(CaO) -7.6024(SiO2) -1.4297(Fe2O3)-6.7187(Al2O3)
C2S = 8.6024(SiO2) +1.1(Fe2O3)+5.0683(Al2O3) - 3.0710(CaO)
C3A = 2.6504(Al2O3) -1.6920(Fe2O3)
C4AF = 3.0432(Fe2O3)
Therefore:
C3S = (4.0710 x 65.6)-(7.6024 x 21.5)-(1.4297 x 2.8)-(6.718 x 5.2)
C2S = (8.6024 x 21.5)+(1.0785 x 2.8)+(5.0683 x 5.2)-(3.0710 x 65.6)
C3A = (2.6504 x 5.2)-(1.6920 x 2.8)
C4AF = 3.0432 x 2.8
So:
C3S = 64.67% , C2S = 13.17% , C3A = 9.04% , C4AF = 8.52%

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Example 2
A cement is manufactured with the following compound composition:
C3S = 45% : C2S = 41% : C3A = 3% : and C4AF = 2% .
By use of Bogue’s Equations, determine the typical blend of raw materials required
to produce this cement.

Solution
% F = 2 / 3.04 = 0.658
% A = [ 3 + 1.69 ( 0.658 ) ] / 2.65 = 1.552
45 = 4.07 (%C)-7.6(%S) -6.72 (1.552)-1.43 (0.658)
and
45 = -3.07 (%C)+8.6(%S) +5.10 (1.552)+1.08 (0.658)
% C + % S = 88.744
Finally % C = 62.624
And % S = 26.120

H.W:-
Calculate the Bouge composition of the cement with the oxide composition:
SiO2 = 25 %
CaO = 61 %
Fe2O3 = 3 %
Al2O3 = 4 %
SO3 = 2.5 %
Free lime = 1 %

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