ROW MATERIAL PREPARATION IN CEMENT MANUFACTURING

Definition and mineralogy

The first step in the manufacture of portland cement is to combine a variety of

raw ingredients so that the resulting cement will have the desired chemical
composition. These ingredients are ground into small particles to make them
more reactive, blended together, and then the resulting raw mix is fed into a
cement kiln which heats them to extremely high temperatures.

While it is important to have the correct proportions of the raw ingredients and
the overall chemical composition and structure of the individual raw ingredients
can vary considerably. The reason for this is that at the very high temperatures in
the kiln, many chemical components in the raw ingredients are burned off and
replaced with oxygen from the air. Table 3.3 lists just some of the many possible
raw ingredients that can be used to provide each of the main cement elements.

Table -1 Examples of raw materials for portland cement manufacture

Calcium Silicon Aluminum Iron

Limestone Clay Clay Clay
Marl Marl Shale Iron ore
Calcite Sand Fly ash Mill scale
Aragonite Shale Aluminum ore refuse Shale
Blast furnace
Shale Fly ash
dust
Sea Shells Rice hull ash
Cement kiln dust Slag

The ingredients listed above include both naturally occurring materials such as
limestone and clay, and industrial byproduct materials such as slag and fly ash.

Cement is therefore essentially a mixture of calcium silicates and smaller

amounts of calcium aluminates that react with water and cause the cement to
set.

OPC consists mainly of lime (CaO), silica (SiO2) , alumina (AL2O3) , iron (Fe2O3)
and sulphur trioxide (SO3). Magnesium (MgO) and other Oxide elements are
present in small quantities as an impurity associated with raw materials.

The requirement for calcium is met by using high calcium limestone (or its
equivalent calcareous raw material) and clay, mudstone or shale as the source of
most of the silica and alumina. Finished cement is produced by finely grinding
together around 95% cement clinker with 5% gypsum (or anhydrite) which helps
to retard the setting time of the cement. The quality of cement clinker is directly
related to the chemistry of the raw materials used. Around 8090% of raw
material for the kiln feed is limestone. Clayey raw material accounts for between
1015%, although the precise amounts will vary.
Free lime and periclase (a cubic form of magnesium oxide (MgO)) both have a
deleterious effect on cement properties and manufacturers minimize the amount
produced, but it is not possible to eliminate them altogether. Both tend to
hydrate when cement mixes with water, and the resulting hydroxide occupies
more space than the original, dense oxide. as long as hydration occurs while the
concrete mix is still fluid or plastic, but, once structure and strength have started
to form, the formation of hydroxides tends to have a destructive effect - and
more so if it occurs after strength development is complete. The onset of an
expansive reaction after the cement has gained strength is known as
unsoundness, and has been a feature of poorly-manufactured Portland cement
throughout its history. Magnesium carbonate, which may be present in limestone,
is the main undesirable impurity.

Free lime exists in the clinker if the finishing reaction of lime with belite to form
alite is not completed, if there are large unreactive particles of calcium carbonate
in the rawmix, or if the mix contained too much lime.

The level of magnesia (MgO) in the clinker should not exceed 5% and many
producers favour a maximum of 3%; this rules out dolomite or dolomitic
limestones for cement manufacture.

Control of free lime improved in the 20th century due to better mix control and
the arrival of the rotary kiln, which allowed much better control of burning
conditions, so that for the last century or so, unsoundness due to free lime has
become an entirely avoidable condition.

Other deleterious materials include excessive alkalis (sodium oxide, Na2O or soda
and potassium oxide, K2O) which would be unacceptable because of durability
problems with the concrete (due to the reaction of alkalis with some siliceous
aggregates to form a swelling gel).

Portland cement clinker contains four main minerals:

Alite: approximately tricalcium silicate (Ca3SiO5 or

Belite: approximately dicalcium silicate (Ca2SiO4 or

Aluminate: very approximately tricalcium aluminate (Ca3Al2O6 or

Ferrite: very approximately tetracalcium aluminoferrite (Ca2(Al,Fe)2O5 or

A typical modern good-quality general purpose grey clinker might contain 72%
alite, 9% belite, 7% tricalcium aluminate, 10 % tetracalcium aluminoferrite, 1%
salt phases and 1% free calcium oxide, but depending on the properties desired,
clinkers with markedly different compositions may be made.

Table -2 Main Compounds of Portland Cement

Common Usual Range
Chemical
Compound Formula by Weight
Formula
(%)
Tricalcium Silicate
3
CaO . SiO 2 C3 S 45-60

Dicalcium Silicate
2
CaO . SiO 2 C2 S 15-30

Tricalcium Aluminate 3 CaO . Al 2 O3 C3 A 6-12

Tetracalcium 4 CaO . Al 2 O3 . Fe2 O3 C 4 AF 6-8

Aluminoferrite

C3 S and
C2 S when hydrated, provide the desired characteristics of the

concrete. Alumina and iron, which produce

C3 S and
C 4 AF , are included

with the other raw materials to reduce the temperature required to produce
C3 S from 2000C to 1350C (3500F to 2500F).

Raw Material Preparation

The raw materials used in the manufacture of cement (as approximately 80%
calcium carbonate and shale, sand and iron ore) are crushed to less than 25mm
in size. Due to the variable nature of these components, they are pre-blended
prior to their use. It is crushed and stored in a pre-blending hall, utilizing the
chevron pile stacking method. In this method, stacking takes place at one end of
the pile. At the other end of the pile the material is reclaimed and then stored in
a feeding hopper which is ready for use.

Raw Material Proportioning & Grinding

The raw materials are extracted from the hoppers via weigh-feeders. The
materials are conveyed to the grinding mill and are ground to a suitable fineness,
called raw meal at this stage. This is then stored in a blending silo and blended to
ensure homogeneity. The proportions of the 4 components are controlled by the
continuous sampling and testing of this raw meal. The raw meal chemical
composition is determined by the use of an x-ray fluorescence analyzer. This is
linked to the computer which will automatically adjust the weigh-feeders, so that
the resultant raw meal stored in the blending silo meets the preset parameters.
After blending, the blended material is ready for the next phase of production.
The parameters used in the control of the raw meal are lime saturation factor,
silica modulus and iron modulus. These are actually proportions of the various
chemical components which are desired in the resultant clinker.

Lime Saturation Factor

The LSF is a ratio of CaO to the other three main oxides. Applied to clinker, it is
calculated as:

LSF=CaO/(2.8SiO2 + 1.2Al2O3 + 0.65Fe2O3)

Often, this is referred to as a percentage and therefore multiplied by 100.

The LSF controls the ratio of alite to belite in the clinker. A clinker with a higher
LSF will have a higher proportion of alite to belite than will a clinker with a low
LSF.

Typical LSF values in modern clinkers are 0.92-0.98, or 92%-98%.

Values above 1.0 indicate that free lime is likely to be present in the clinker. This
is because, in principle, at LSF=1.0 all the free lime should have combined with
belite to form alite. If the LSF is higher than 1.0, the surplus free lime has nothing
with which to combine and will remain as free lime.

Silica Ratio (SR)

The silica ratio (also known as the Silica Modulus) is defined as:

SR = SiO2/(Al2O3 + Fe2O3)

A high silica ratio means that more calcium silicates are present in the clinker and
less aluminate and ferrite. SR is typically between 2.0 and 3.0.

Alumina Ratio (AR)

The alumina ratio is defined as:

AR=(Al2O3/(Fe2O3)

This determines the potential relative proportions of aluminate and ferrite phase
in the clinker. An increase in clinker AR (also sometimes written as A/F) means
there will be proportionally more luminate and less ferrite in the clinker. In
ordinary Portland cement clinker, the AR is usually between 1 and 4.

Chemical Considerations
The raw material preparation stage of cement manufacture results in the
production of a rawmix that is in a suitable state for feeding to the kiln in which it
is converted by heat into clinker. This is a chemical transformation. The rawmix
consists of a mixture of materials that will react together to form the calcium
silicates that confer on the clinker its strength-giving properties. In order to get
these to react together effectively, a number of rules must be followed - rules
that have been understood from the earliest times in the development of the
industry:

The chemical reactions in the kiln largely take place at the surface of the
mineral particles, so to make these reactions take place quickly and at low
temperature,

The mix must be very finely ground.

The different solid mineral particles must approach very close to one
another for reaction to take place, and the composition of the mix must be
correct, not only en masse but also on the microscopic scale in other
words
 The mix must be thoroughly homogenised.

The properties of the clinker are extremely sensitive to the amount of each
mineral component in the mix, so to make a consistent product,

The composition of the mix must be tightly controlled

Effect of Fineness

Small mineral particles are needed in order to form the silicates without having to
burn the mix at an excessive temperature or to burn for an excessively long time.
In this way, the cost of manufacture and wastage of energy are minimised. The
different minerals in a rawmix have different grinding requirements.

Calcium carbonate (calcite) decomposes in the kiln, evolving carbon

dioxide, and the decomposition "opens up" the crystal structure, making it
more reactive, so particles less than 150 m are satisfactory. Particles
larger than this, unless burned very hard, leave particles of "free lime"
(unreacted calcium oxide) in the clinker, which result in less alite formation
and cause unsoundness (destructive expansion) in the cement.
Clay minerals such as kaolinite (Si2Al2O5(OH)4) also decompose on
moderate heating (by de-hydroxylation) and so become more reactive. But
unreacted particles have a more serious effect, by leaving an excess of
calcium oxide in the rest of the mix. Particles less than 90 m are
considered satisfactory. Larger particles, unless burned very hard, leave
masses of small belite crystals, interspersed with melt phases, that are too
large for free lime to penetrate from the outside and convert them to alite.
Silicon dioxide (quartz) is unreactive unless very fine, and particles need to
be less than 45 m for easy reaction. Larger particles leave dense masses
of belite that are impenetrable to attack by free lime to form alite, and may
be unstable enough to invert to inert -calcium orthosilicate.

Effect of Homogeneity
When heated to the peak temperature in the kiln, "clinkering" takes place. This
consists of partial melting, the total amount of liquid produced being typically 20-
30% of the mass. The liquid acts as a solvent through which ions can be
exchanged between the solid particles. It also has the effect of drawing the
loosely consolidated solid particles closer together by surface tension. To ensure
easy formation of the desired clinker minerals, ions must diffuse a minimum
distance through the liquid. These means ensuring that each aluminosilicate or
quartz particle must have the required number of calcite particles in close
proximity (i.e. within a few tens of micrometres), and requires a high degree of
homogeneity.

In general, if the requirements for composition and fineness are met, and the
components are ground together, the homogeneity follows naturally.
Effect of Composition

Despite the apparent similarity of the chemical analyses of the components, their
mineralogical compositions vary considerably. It should be noted that even small
compositional changes in rawmix composition have a large effect upon the
cement's properties. For example the amount of silicate compositions can affect
the rate of cement strength by increasing or decreasing the amount of Alite and
Belite. Alite (approximately Ca3SiO5) provides almost all the "early strength"
(strength up to seven days of curing) of cement and a moderate amount of late
(>7 days) strength. Belite (approximately Ca2SiO4) provides very little "early
strength" and a large amount of late strength. In order to control cement
properties, its necessary to pay attention to responsive chemical control system
and elaborate blending processes.

Rawmix Chemical Control

The chemical control of rawmix is required in order to ensure that the rawmix
components (at their simplest, limestone and clay) are in the right ratio to make
clinker of the desired alite content. To achieve this, a feedback control system is
almost always used. This consists of taking a sample of the rawmill product,
analysing it, and depending upon the deviation of the result from the "set point"
value, to make a change to the feeder(s) up-stream of the mill. The strategy for
making changes to the mill feed varies considerably with the system of plant
employed, but the objective is always to keep the chemistry close to the target
value, and equal to the target value on average, without any excessive "cycling".