CHAPTER IX

CEMENT MANUFACTURING

PREAMBLE

A cement is a binder, a substance used in construction that sets, hardens and adheres to other
materials, binding them together. Cement is seldom used solely, but is used to bind sand and
gravel (aggregate) together. Cement is used with fine aggregate to produce mortar for masonry,
or with sand and gravel aggregates to produce concrete.

Cements used in construction are usually inorganic, often lime or calcium silicate based, and can
be characterized as being either non-hydraulic or hydraulic depending upon the ability of the
cement to set in the presence of water.

Non-hydraulic cement will not set in wet conditions or underwater; rather, it sets as it dries and
reacts with carbon dioxide in the air. It is resistant to attack by chemicals after setting.

Hydraulic cements e.g. Portland cement set and become adhesive due to a chemical reaction
between the dry ingredients and water. The chemical reaction results in mineral hydrates that are
not very water-soluble and so are quite durable in water and safe from chemical attack. This
allows setting in wet condition or underwater and further protects the hardened material from
chemical attack. The chemical process for hydraulic cement found by ancient Romans used
volcanic ash – pozzolana - with added lime, calcium oxide (CaO).

The word "cement" can be traced back to the Romam term opus caementicium, used to describe
masonry resembling modern concrete that was made from crushed rock with burnt lime as
binder. The volcanic ash and pulverized brick supplements that were added to the burnt lime, to
obtain a hydraulic binder, were later referred to as cementum, cimentum, cäment, and cement. In
modern times, organic polymers are sometimes used as cements in concrete.

We have no means of knowing when the discovery of cementing material was first made, but it
must have been discovered soon after the first intelligent use of fire.

The cement employed by the early Egyptians was calcined impure gypsum; calcined limestone
was not used until the Greek and Roman periods.

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Portland cement was developed from natural cements made in Britain beginning in the middle of
the 18th century. Its name is derived from its similarity to Portland stone, a type of building
stone quarried on the Isle of Portland in Dorset, England.

The development of modern Portland cement, sometimes called ordinary or normal Portland
cement, began in 1756 when John Smeaton experimented with combinations of different
limestones and additives, including trass and pozzolanas, relating to the planned construction of
a lighthouse now known as Smeaton's Tower. In the late 18th century, Roman cement was
developed and patented in 1796 by James Parker. Roman cement quickly became popular, but
was largely replaced by Portland cement in the 1850s. In 1811 James Frost produced a cement he
called British cement. James Frost is reported to have erected a manufactory for making of an
artificial cement in 1826. In 1818, French engineer Louis Vicat invented an artificial hydraulic
lime considered the "principal forerunner" of Portland cement and " Edgar Dobbs of Southwark
patented a cement of this kind in 1811. Portland cement was used by Joseph Aspdin in his
cement patent in 1824 because of the cements' resemblance to Portland stone. The name
"Portland cement" is also recorded in a directory published in 1823 being associated with
William Lockwood, Dave Stewart, and possibly others. However, Aspdins' cement was nothing
like modern Portland cement but was a first step in the development of modern Portland cement,
called a “proto-Portland cement”. William Aspdin had left his father's company and in his
cement manufacturing apparently accidentally produced calcium silicates in the 1840s, a middle
step in the development of Portland cement. In 1848, William Aspdin further improved his
cement; in 1853, he moved to Germany, where he was involved in cement making. William
Aspdin made what could be called “meso-Portland cement” a mix of Portland cement and
hydraulic lime. Isaac Charles Johnson further refined the production of “meso-Portland cement”
middle stage of development and claimed to be the real father of Portland cement. John Grant of
the Metropolitan Board of Works in 1859 set out requirements for cement to be used in the
London sewer project. This became a specification for Portland cement. The next development
with the manufacture of Portland cement was the introduction of the rotary kiln patented by
German Friedrich Hoffmann called a Hoffmann kiln for brick making in 1858 and then
Frederick Ransome in 1885 (U.K.) and 1886 (U.S.) which allowed a stronger, more
homogeneous mixture and a continuous manufacturing process. The Hoffman "endless kiln”
which gave "perfect control over combustion" was tested in 1860 and showed the process
produced a better grade of cement. This cement was made at the Portland Cementfabrik Stern at
Stettin, which was the first to use a Hoffman kiln. It is thought that the first modern Portland
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cement was made there. The Association of German Cement Manufacturers issued a standard on
Portland cement in 1878.

Portland cement had been imported into the United States from Germany and England and in the
1870s and 1880s it was being produced by Eagle Portland cement near Kalamazoo, Michigan,
and in 1875 the first Portland cement was produced by Coplay Cement Company under the
direction of David O. Saylor in Coplay Pennsylvania. By the early 20th century American-made
Portland cement had displaced most of the imported Portland cement.

Portland cement is the most common type of cement in general use around the world, used as a
basic ingredient of concrete, mortar, stucco, and most non-speciality grout. It was developed
from other types of hydraulic lime in England in the mid 19th century and usually originates
from limestone. It is a fine powder produced by heating materials in a kiln to form what is called
clinker, grinding the clinker, and adding small amounts of other materials. Several types of
Portland cement are available, with the most common being called ordinary Portland cement
(OPC) which is grey in color, but a white Portland cement is also available.

Portland cement is caustic, so it can cause chemical burns. The powder can cause irritation or,
with severe exposure, lung cancer and can contain some hazardous components such as
crystalline silica and hexavalent chromium.

Environmental concerns are the high energy consumption required to mine, manufacture, and
transport the cement and the related air pollution, including the release of greenhouse gases e.g.,
carbon dioxide, dioxin, NOx, SO2, and particulates.

The low cost and widespread availability of the limestone, shales, and other naturally occurring
materials used in Portland cement make it one of the lowest-cost materials widely used over the
last century throughout the world. Concrete produced from Portland cement is one of the most
versatile construction materials available in the world.

The hard clinker resulting from burning a mixture of clay and limestone or similar materials is
known by the terms Portland cement to distinguish it from natural or pozzolan and other
cements. Cement and concrete are not synonymous terms. Concrete is artificial stone made from
a controlled mix of cement water and aggregate.

As per today, the world’s five largest cement producers are Lafarge, Holcim, Cemex, Heidelberg
Cement and Italcementi. Apart from producing cement, these companies have also diversified

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into several other building material sectors such as aggregates, concrete products, plasterboard,
etc.

Portland Cement has been defined as the product obtained by pulverizing clinker, which consists
of essentially hydraulic calcium silicates, with calcium sulfate as an interground addition. Here,
with the term hydraulic it is meant that; when the product is mixed with water, with air or under
water it settles and hardens.

Non-hydraulic cement, such as slaked lime (calcium hydroxide mixed with water), hardens by
carbonation in the presence of carbon dioxide which is naturally present in the air. Calcium
oxide (lime) is produced from calcium carbonate (limestone or chalk) by calcination at
temperatures above 825 °C for about 10 hours at atmospheric pressure
CaCO3 → CaO + CO2
The calcium oxide is then spent (slaked) mixing it with water to make slaked lime (calcium
hydroxide):
CaO + H2O → Ca(OH)2
Once the excess water is completely evaporated (this process is technically called setting), the
carbonation starts:
Ca(OH)2 + CO2 → CaCO3 + H2O
This reaction takes a significant amount of time because the partial pressure of carbon dioxide in
the air is low. The carbonation reaction requires the dry cement to be exposed to air, and for this
reason the slaked lime is a non-hydraulic cement and cannot be used under water. This whole
process is called the lime cycle.

Hydraulic cement hardens by hydration when water is added. Hydraulic cements such as
Portland cement is the most common type of cement in general use around the world, used as a
basic ingredient of concrete, mortar, stucco, and most non-speciality grout. It is a fine powder
produced by heating materials in a kiln to form what is called clinker, grinding the clinker, and
adding small amounts of other materials. Several types of Portland cement are available, with the
most common being called ordinary Portland cement (OPC) which is grey in color, but a white
Portland cement is also available.
Portland cement are made of a mixture of silicates and oxides whereas the four main
components are;
Belite (2CaO·SiO2)
Alite (3CaO·SiO2)

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 Celite or Tricalcium aluminate (3CaO·Al2O3)
Brownmillerite (4CaO·Al2O3·Fe2O3).

The silicates belite and alite are responsible for the mechanical properties of the cement, the
tricalcium aluminate and the brownmillerite are essential to allow the formation of the
liquid phase during the kiln sintering (firing). The chemistry of the above listed reactions is
not completely clear and is still the object of research.

At the high temperatures present in a cement kiln, all of the constituents of the raw ingredients
are either driven off as a gas or converted to an oxide form. To make the formulas of cement
minerals, compounds, and reactions shorter and easier to read, it is traditional to use a shorthand
notation that leaves out the oxygen. This system is listed in Table 1.

Table 1: Cement chemistry notation based on oxides.

Oxide form Notation

CaO C

SiO2 S

Al2O3 A

Fe2O3 F

SO3

H2O H

In cement technology, other abbreviations are also in use, such as MgO=M and Na2O = N,
besides those listed in Table 1. Also cement technology have to deal with chemical and mineral
names for solid phases. The chemical name of a solid compound is simply the word version of
the chemical formula, for example “calcium hydroxide”, the mineral name is“portlandite” meant
to represent either a particular crystal structure or a potentially impure form of the phase.

The various ways of describing some of the main solid phases associated with cement chemistry
are summarized in Table 2. Names such as alite and belite indicate a particular crystal
structure as well as the fact that these phases contain a variety of impurities when found in
cement.

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 Table 2: The Different ways to Represent Cement Minerals and Products.

Chemical Name Chemical Oxide Formula Cement Mineral

Formula Notation Name

Tricalcium Silicate Ca3SiO5 3CaO.SiO2 C3 S Alite

Dicalcium Silicate Ca2SiO4 2CaO.SiO2 C2 S Belite
Tricalcium Aluminate Ca3Al2O6 3CaO.Al2O3 C3 A Aluminate
Tetracalcium Ca2AlFeO5 4CaO.Al2O3.Fe2O3 C4AF Ferrite
Calcium hydroxide
Aluminoferrite Ca(OH)2 CaO.H2O CH Portlandite
Calcium sulfate dihydrate CaSO4.2H2O CaO.SO3.2H2O C H2 Gypsum
Calcium oxide CaO CaO C Lime
The ASTM has designated five types of portland cement, designated Types I-V. Physically and
chemically, these cement types differ primarily in their content of C3A and in their fineness. In
terms of performance, they differ primarily in the rate of early hydration and in their ability to
resist sulfate attack. The general characteristics of these types are listed in Table 3.

Table 3: ASTM, General Features of the Main Types of Portland Cement

Classification Characteristics Applications

Type I General purpose Fairly high C3S content for General construction
good early strength (mostbuildings, bridges,
development pavements, precast units, etc)
Type II Moderate sulfate Low C3A content (<8%) Structures exposed to soil or
resistance water containing sulfate ions
Type III High early strength Ground more finely, may have Rapid construction, cold
slightly more C3S weather concreting
Type IV Low heat of hydration Low content of C3S (<50%) Massive structures such as
(slow reacting) and C3A dams. Now rare.
Type V High sulfate resistance Very low C3A content (<5%) Structures exposed to high
levels of sulfate ions
White White color No C4AF, low MgO Decorative (otherwise has
properties similar to Type I)
The differences between these cement types are rather subtle. All five types contain about 75
wt% calcium silicate minerals, and the properties of mature concretes made with all five are
quite similar. Thus these five types are often described by the term “ordinary portland cement”,
or OPC.

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Types II and V OPC are designed to be resistant to sulfate attack. Sulfate attack is an
important phenomenon that can cause severe damage to concrete structures. It is a chemical
reaction between the hydration products of C3A and sulfate ions that enter the concrete from the
outside environment. The products generated by this reaction have a larger volume than the
reactants, and this creates stresses which force the concrete to expand and crack. Although
hydration products of C4AF are similar to those of C3A, they are less vulnerable to expansion, so
the designations for Type II and Type V cement focus on keeping the C3A content low. There is
actually little difference between Type I and Type II cement, and it is common to see cements
meeting both designations labeled as “Type I/II”. It should be noted here that the most effective
way to prevent sulfate attack is to keep the sulfate ions from entering the concrete in the first
place. This can be done by using mix designs that give a low permeability (mainly by keeping
the w/c ratio low) and, if practical, by putting physical barriers such as sheets of plastic between
the concrete and the soil.

Type III cement is designed to develop early strength more quickly than a Type I cement.
This is useful for maintaining a rapid pace of construction, since it allows cast-in-place concrete
to bear loads sooner and it reduces the time that precast concrete elements must remain in their
forms. These advantages are particularly important in cold weather, which significantly reduces
the rate of hydration (and thus strength gain) of all portland cements. The downsides of rapid-
reacting cements are a shorter period of workability, greater heat of hydration, and a slightly
lower ultimate strength.

Type IV cement is designed to release heat more slowly than a Type I cement, meaning of
course that it also gains strength more slowly. A slower rate of heat release limits the increase
in the core temperature of a concrete element. The maximum temperature scales with the size of
the structure, and Type III concrete was developed because of the problem of excessive
temperature rise in the interior of very large concrete structures such as dams. Type IV cement
is rarely used today, because similar properties can be obtained by using a blended cement.

White portland cement (WPC) is made with raw ingredients that are low in iron and
magnesium, the elements that give cement its grey color. These elements contribute
essentially nothing to the properties of cement paste, so white portland cement actually has quite
good properties. It tends to be significantly more expensive than OPC, however, so it is typically
confined to architectural applications. WPC is sometimes used for basic cements research

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because the lack of iron improves the resolution of nuclear magnetic resonance (NMR)
measurements.

Whereas, The European standard (EN 197-1) for common cement lists 27 different cement types
in five main groups. In addition, there is a range of special cements produced for particular
applications. The products in the family of common cements, covered by EN 197-1 are grouped
into five main cement types as follows:
 CEM I Portland cement,
 CEM II Portland-composite cement,
 CEM III Blast furnace cement,
 CEM IV Pozzolanic cement,
 CEM V Composite cement.

The notation applied to them indicates: the main cement type; the proportion of Portland cement
clinker; the second main constituent; the standard (i.e.28-day) strength class and the rate of early
strength gain. For example, a particular Portland-slag cement to EN 197-1 is denoted by
СЕМII/A-S 42.5 N
 N; indicates normal early strength, R indicates rapid early strength.
 42.5; Standard strength class
 S; Sub-type indicates the second main constituent, in this case, blastfurnace slag
 A; Indicates higher (A), medium (B) and lower (C) proportion of Portland cement clinker
 CEM II; Main Cement Type
Table 4: General Features of EN 197-1

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CEMENT MANUFACTURE

The basic chemistry of the cement manufacturing process begins with the decomposition of
calcium carbonate (CaCO3) at about 900 °C to calcium oxide (CaO) lime and liberated gaseous
carbon dioxide (CO2); this process is known as calcination. This is followed by the clinkering
process in which the calcium oxide reacts at a high temperature (typically 1400 – 1500 °C) with
silica, alumina, and ferrous oxide to form the silicates, aluminates, and ferrites of calcium which
comprise the clinker. The clinker is then ground or milled together with gypsum and other
additives to produce cement.

There are four main process routes for the manufacture of cement: dry, semi-dry, semi-wet and
wet processes.

 The dry process, in which the raw materials are ground and dried to raw meal in the form
of a flowable powder. The dry raw meal is fed to the preheater or precalciner kiln or,
more rarely, to a long dry kiln.

 The semi-dry process, in which the dry raw meal is pelletised with water and fed into a
grate preheater before the kiln or to a long kiln equipped with crosses.

 The semi-wet process, in which the slurry is first dewatered in filter presses. The
resulting filter cake is extruded into pellets and then fed either to a grate preheater or
directly to a filter cake dryer for raw meal production

 The wet process, in which the raw materials (often with a high moisture content) are
ground in water to form a pumpable slurry. The slurry then is either fed directly into the
kiln or first to a slurry dryer.

The choice of process is, to a large extent, determined by the state of the raw materials (dry or
wet). In Europe, more than 90 % of production is based on dry processes thanks to the
availability of dry raw materials. Wet processes are more energy consuming, and thus more
expensive. Plants using semi-dry processes are likely to change to dry techniques whenever
expansion or major improvement is required. Plants using wet or semi-wet processes normally
only have access to moist raw materials, as is the situation in Denmark and Belgium, and to
some extent in the UK.

The process of manufacturing white cement is similar to grey Portland cement production. The
process includes the selection of raw materials, storage and preparation, fuel storage and

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preparation, firing of clinker in a kiln system, whitening/cooling, and grinding under precisely
controlled conditions through each stage of the process in order to avoid contamination and
undesired changes of the product. However, the combination of cooling and whitening is the
main technological difference. These steps are used and needed in order to improve the
whiteness of this special type of cement and to provide a uniform colour.

Production of cement completes after passing of raw materials from the following four phases:
1. Raw materials Quarrying and Crushing
2. Proportioning of Raw Mix, Grinding, Homogenization
3. Pyroprocessing-Clinkerization and Cooling
4. Cement Grinding and Packing
A typical process flow diagram from a cement plant is shown in Figure 1.

Figure 1: Cement Manufacture Flow Sheet

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 1. Raw Materials Quarrying and Crushing

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. The cement manufacturing
process starts from the mining of raw materials that are used in cement manufacturing, mainly
limestone and clays. 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 calcium, silicon, aluminum, and iron, 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 5
lists just some of the many possible raw ingredients that can be used to provide each of the main
cement elements.

Table 5: 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

Shale Fly ash Blast furnace 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. Materials that contain more
than minor or in some cases trace amounts of metallic elements such as magnesium, sodium,
potassium, strontium, and various heavy metals cannot be used, as these will not burn off in the
kiln and will negatively affect the cement. Another consideration is the reactivity, which is a
function of both the chemical structure and the fineness. Clays are ideal because they are made
of fine particles already and thus need little processing prior to use, and are the most common

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source of silica and alumina. Calcium is most often obtained from quarried rock, particularly
limestone (calcium carbonate) which must be crushed and ground before entering the kiln. The
most readily abundant source of silica is quartz, but pure quartz is very unreactive even at the
maximum kiln temperature and cannot be used.

The raw materials for cement manufacture which are the subject of geological exploration are
mainly limestone and clays.

Sometimes the two are mixed by nature either by sedimentation rocks or deposits of
Precretaceous period and called as lime marl or marl.

The clay mineral component used for cement manufacture will generally be a soft or loose-
textured material: clays, silts or sands with high content of clay minerals. Additive materials for
clinker production may be needed for correction of the chemical composition of raw mix, e.g.,
materials providing Fe, SiO2 or Al2O3.

Raw materials for the cement industry are usually obtained by large-scale “open cast or open pit”
surface mining. The most widely used method of quarrying is based on the conventional
benching technique, in which the material in the deposit is quarried in several benches one
above the other, with predetermined heights of face.

Drilling and blasting continue to be the favored combination for breaking out the material,
dislodging it from the quarry face and fragmenting it. For drilling, rotary drilling machines with
hydraulic drive systems are preferred. For blasting, inexpensive explosives as ANC –
ammonium nitrate/carbon or ANFO – ammonium nitrate/fuel oil are used with suitable fuses.
The other methods used are tunneling and blasting and ripping with heavy tractor crawlers.

Generally cement plants are fixed where the quarry of limestone is near bye. This saves the extra
fuel cost and makes cement somehow economical. A limestone quarry is inside the plant area
and a clays quarry may be far from the plant area at a distance which will pay the transportation
cost. The limestone is excavated from open cast mines after drilling and blasting and loaded onto
dumpers which transport the materials and unload into hoppers of limestone crushers. The clays
are excavated from open cast mines and loaded onto dumpers which transport the materials and
unload into open yard storage. Then it is transported by trucks and unloaded into the hopper of a
clay crusher. They are three types of clay used in cement manufacturing, namely silty clay and
kaolin.

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 Figure 2: Typical Cement Raw Material Quarry

Crushing of raw materials is a must to suit subsequent milling operations. There are two distinct
crushing systems: Open circuit and Closed circuit. Out of the two, open - circuit system with one
pass is widely used.

The selection of crusher type depends upon the abrasiveness and stickiness (moisture content) of
the raw materials. Most raw materials are non- abrasive and Hammer- Crusher (Figure 3) with
outlet grates is employed. It can crush limestone from a lump size of 1- 2 m down to 35 mm.
Fineness of this degree is necessary if the subsequent raw mill is a ball mill, a high pressure

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roller press or a combination of the two. For sticky materials such as clay, Roll crushers with
single or double rolls are most suitable.

Figure 3: Hammer Crusher

The discharged raw material is fed onto a belt conveyor and passed across a bulk material
analyzer. The raw mix is fed into a circular storage unit called a raw mix storage. Then, the mix
is extracted transversely from the stockpile by reclaimers and conveyed to a raw mill bin called
the raw mix bin for grinding.(Figure 4)

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 Figure 4: Raw Material Storage Hall

2. Proportioning of Raw Mix, Grinding, Homogenization

Grinding and blending prior to entering the kiln can be performed with the raw ingredients in
the form of a slurry (the wet process) or in dry form –farine (the dry process). The addition of
water facilitates uniform mixing and grinding. However, the water must then be removed by
evaporation as the first step in the burning process, which requires additional energy. The wet
process, which was once standard, has now been rendered obsolete by the development of
efficient dry grinding equipment, and all modern cement plants use the dry process.

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The purpose of the preparatory processing of raw materials is to convert these chemically and
mineralogically different materials, usually supplied to the plant in form of coarse lumps, into
raw meal or slurry of homogenized composition. Reducing the raw material to a fine powder
conventionally called “raw meal” is necessary in order to produce a homogenous mixture which
will quickly be converted in the kiln into a homogenized clinker.

The assessment of the suitability of raw materials for cement manufacture is based chiefly on
their chemical composition (Table 6). For limestone components the so called “lime standard” is
used as a criterion giving information on the CaO content as well as on the “hydraulic”
constituents SiO2, Al2O3 and Fe2O3. The rocks to be used as clay mineral components can most
suitably be assessed by calculation of silica ratio and alumina ratio.

Table 6: Typical Chemical Analyses of Raw Materials and Cement Raw Meal

Cement manufacture needs the knowledge about the raw materials. An oxide analysis of the raw
materials is the first step, which provides input for a wide variety of ratios and moduli that relate
oxide compositions to one another. These include: LSF (lime saturation factor), SM (silica
modulus or ratio), AR (alumina-to-iron ratio), and other lesser-used formulas like the hydraulic
modulus. These are the most considered are the three most critical control parameters.

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The oxides present in the raw materials when subjected to high clinkering temperature combine
with each other to form complex compounds.

The silica ratio represents the burnability of a raw mix. The burnability impacts how much
energy is put into the system. As the ratio of silica to alumina plus iron increases, it becomes
harder to “burn” — harder to combine the raw materials into the phases wanted. As the ratio
decreases, the tendency for fluxing (the ability of the solid materials to become liquid) increases,
and the combining reactions become easier. Another consideration is that silica present as quartz
is generally more difficult to combine than silica present as silicates.
 Silica Ratio or Silica Modulus - SR or SM = SiO2/Al2O3 + Fe2O3
For conventional portland cement it was advisable to maintain silica ratio between 1,8 to 2,7.
More the silica ratio, then lesser the coating tendency in kiln due to low liquid formation
resulting hard burning of clinker with increase in fuel consumption, also causes slow setting and
slow hardening of cement. Lesser the silica ratio, then more the liquid formation and coating
tendency in kiln and improves good burnability of clinker with less fuel consumption.

The alumina-to-iron ratio is important because it controls the potential C3A/C4AF ratio in the
finished cement, which is important because of sulfate resistance, heat generation, and admixture
compatibility issues.
 Alumina-iron ratio - AR = Al2O3/Fe2O3
Generally the alumina ratio for portland cements to be maintained between 1,5 to 2,5 to have a
good liquid phase composition in the clinker. Clinker with higher the Alumina modulus results in
cement with high early strength.

The lime saturation factor controls the potential C3S to C2S ratio in the finished cement. C3S
governs the early age strength development while C2S governs the later age strength. The
importance of the lime factor is that it includes all four of the ingredients necessary for clinker
production.
 Lime factor -LF
C – (1.65A + 0.315F) / S
 Lime saturation factor - LSF
100(CaO + 0.75Mg) / (2.85SiO2) + (1.18Al2O3) + (0.65Fe2O3)

Typical range is 92-105% . When the LSF approaches unity, the clinker is hard to burn and
often shows the excessive free lime contents

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The Bogue equations provide a simple and convenient method to find out the final and potential
composition of a clinker. Technically, they indicate the potential composition since not all of the
reactions that occur in the kiln will go to completion and since the cement phases are not ideal
compounds. Plant chemists have used these equations for years, sometimes adjusting them based
on their own raw materials and their own experience. Today’s manufacturing environment uses
rapid, in-stream sampling and analysis coupled with computerized proportioning to make almost
continuous process improvements.

Bogue Equations for Potential Composition

C3S = 4.071C – 7.6S – 6.718a – 1.43F
C3A = 2.65A – 1.692F
C2S = -3.071C + 8.6S + 5.068A + 1.079F
C4AF = 3.043F

By substituting the three moduli (lime factor, silica ratio, and alumina-iron ratio) into the Bogue
equations and performing some basic algebra, one can define the four clinker phases by
specifying just three control parameters.

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.

The mineral particles in the rawmix usually consist principally of calcium carbonate from the
limestone component of the mix, and aluminosilicates from the clay or shale components,
together with a certain amount of quartz (silicon dioxide).
 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 μm 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 μm are considered satisfactory. Larger particles, unless burned very hard, leave

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 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
μm 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 γ-calcium
orthosilicate.

In these particle size requirements, a profound processing problem arises - although quartz needs
to be more finely ground than the other minerals it is by far the hardest mineral present, and this
difficulty, recognised from the outset, had a major effect upon the evolution of the industry, by
mandating the use of rather rare raw materials in which quartz is fine from the outset.

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 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.
 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 as mass but also on
the microscopic scale – in other words the mix must be thoroughly homogenised.

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.

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.

19
In general, if the requirements for composition and fineness are met, and the components are
ground together, the homogeneity follows naturally. However, there is always the distinct
possibility that the well-homogenised components may separate or “settle out” during storage or
manipulation of the mix, and dealing with this effect is a major preoccupation, particularly in the
“dry process”.

Effect of Composition; The importance of the first of these rules can be exemplified by looking
at a simple binary mixture such as Portland cement manufacturers used from the earliest times.
Expressing the chemical analyses in the way usual in the cement industry, typical raw materials
might be characterised as follows:
 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.

So it can be seen that these small compositional changes have a large effect upon the cement's
properties. In order to control cement properties, cement manufacturers aim to control alite
content within ± 2 %, and it can be seen that, even if there are no sources of variability in the
individual components to achieve this, the percentage of clay in the rawmix must be controlled
within ±0.14%.

Bearing in mind that the raw materials are natural products dug out of a hole in the ground, such
control can't be achieved merely by weighing the components very accurately. The problem is
only solved by a responsive chemical control system and an elaborate blending process.

The raw mix, high grade limestone, clay, sand, and iron ore are fed from their bins to raw mills,
called air swept mills, for drying and fine grinding (Figure 5).

The ball mill consists of a hollow cylindrical shell rotating about its axis. The axis of the shell
may be either horizontal or at a small angle to the horizontal. It is partially filled with balls. The
grinding media is the balls, which may be made of steel (chrome steel), stainless steel, ceramic.
The inner surface of the cylindrical shell is usually lined with an abrasion-resistant material such
as manganese steel. Less wear takes place in rubber lined mills.

The ball mill contains two chambers, separated by diaphragm, namely a drying chamber and a
grinding chamber. The hot gases coming from a preheater (preheater / kiln system) or hot gas
generator enter the mill and are used in raw mills for drying. Then the drying materials enter the

20
grinding chamber of raw mills for fine grinding. The grinding chamber contains a certain
quantity of ball charge in a different sizes ranging from 30mm to 90mm. The hot gas and
grinding materials mill outlet feeds to a separator which separates fine and course product. The
latter, called reject, is sent to the mill inlet via an air slide for regrinding.

The hot gas and fine materials enter a multistage "cyclone" to separate a fine materials and gases.
The fine material, called raw meal, is collected from the multi-cyclone and then fed into an air
slide for lifting called an airlift. The hot gases with very fine materials enter an electrostatic
precipitator or a bag filter (Figure 6) to separate the fine materials from gases. The very fine
materials called preheater dust or electrostatic separator dust is collected from filters and fed into
screw conveyors and are then mixed with the fine material in an air slide and transported to an
air lift vessel via air slide. In the airlift, the raw meal is lifted to the silo by compressed air to the
air slide and then stored and homogenized in a concrete silo. Raw meal extracted from the silo,
now called kiln feed, is fed to the top of the preheater via an air lift.
The efficiencies of seperation systems used for removal of particles from a gas stream either for
recovery or for gas cleaning are given in Table 7 are as follows;
 Cyclones and wet separators are typically used as primary separation devices (pre-
cleaning).
 Filters are frequently used downstream of cyclones as they are more efficient at lower
concentrations and smaller particle sizes.
 Similarly, wet separators and electrostatic precipitators are often combined.

Figure 5: Air Swept Ball Mill

21
Figure 6: Cyclone, Electrostatic and Bag/Fabric Filters

22
Table 7: Filter Type and Separation Eficiencies

Bag Filter

23
 Electrostatic Precipitator / Electro Filter

The vertical roller mills are now more preferred because of its low energy consumption
(Figure7). The grinding process in ball mills and vertical roller mills differ fundamentally. In a
ball mill the comminution takes place by impact and attrition. The comminution in the vertical
roller mill takes place by exposing a bed of material to a pressure sufficiently high to cause
fracture of the individual particles in the bed, although the majority of the particles in the bed are
considerably smaller than the thickness of the bed. It is thus necessary that a stable and
consistent grinding bed is formed between the rollers and the table of the vertical roller mill, able
to sustain such a pressure without the material being squeezed away from the pressure zone. A
stable grinding bed is usually easily obtained in raw material grinding in a vertical roller mill
with a high efficiency separator.

24
 Figure 7: The vertical roller mills

It gathers grinding, drying and powder selecting as a whole, with high grinding efficiency and
high drying capacity, the maximum handling material moisture is up to 20%. The vertical roller
mill adopts dynamic powder selecting device, which comes with high powder-selecting
efficiency and convenient adjustment of fineness

The material falls to grinding disc from the feed opening. The materials are driven to the edge of
disc by the centrifugal force and crushed into fine powders by rollers. Then, the hot air from the
nozzle take the fine powder to high effiency classsifer.

The qualified powder are taken by the air to the powder collector to be collected, while the
unqualified powder are sent back for regrinding. The exit dust laden gases are seperated in bag
filter and/or electrostatic precipitator.

25
Dry Raw Meal Homogenization; The final product of the raw grinding plant such as slurry and
dry raw meal is essentially to be homogenized effectively due to stringent requirements of the
kiln plants i.e. for:
 Stable operation of the pyro - processing plant for sustained production
 Quality cement clinker production

Compressed air is used widely for homogenizing the raw meal. The storage capacity of the
section is designed to meet the requirement of the pyro - processing plant for 3 to 4 days.

There are two basic homogenizing processes for dry raw meal, batch process and continuous
process.In the batch process, at least two pairs of double deck silos, each consisting of a
blending silo at the top and a storage silo below are used. Sequence of operation of the silo i.e.
filling, blending and storing is made independently. In continuous process, one or more single
deck silo is used and compressed air is used only for the aeration pads for the extraction of the
raw meal from the silo. Cylindrical silo with inverted cone design for its bottom is preferred due
to low specific energy (electrical) consumption (Figure 8).

Aerating system at the bottom of silo is designed to assist the raw material flowing through after
aerating to show an oblique and radial distribution. The ring area is divided into eight areas
generally, and aerating system works alternately every five minutes. Then the raw material is
disposed into the centre zone because of its loosening and leading from air flow. Thirdly raw
material in different level of silo is cut vertically to achieve a homogenization of raw material.
The raw material from time to time entering into the central area of silo finally is mixed by a
strong gas to achieve the desired homogenized effect.
The advantages and disadvantages of the these two processes are as mentioned here
 Investment cost for civil work is more in batch type than continuous type.
 Energy consumption in compressed air supply for fluidization is much higher in batch
type resulting in increased operating cost.
 Blending effect is higher in batch type (1: 12 to 15) as compared to continuous type.

26
Figure 8: Controlled Flow Raw Meal Silo and Discharge

27
28
 3. Pyroprocessing-Clinkerization and Cooling

Pyroprocessing (from Greek Πυρος = fire) is a process in which materials are subjected to high
temperatures, typically over 800 °C, in order to bring about a chemical or physical change.
Pyroprocessing includes such terms as ore-roasting, calcination and sintering. Equipment for
pyroprocessing includes kilns, electric arc furnaces and reverberatory furnaces.

Cement manufacturing is a very common example of pyroprocessing. The raw material mix,
raw meal, is fed to a kiln where pyroprocessing takes place. As with most industries,
pyroprocessing is the most energy-intensive part of the industrial process. The rawmix enters a
kiln system at a temperature close to ambient, and the temperature rises as it passes through the
kiln system until it reaches a peak temperature in the sintering zone, after which the chemical
state of the clinker is frozen by rapid cooling. During the process of temperature rise, chemical
reactions take place in sequence.

The common component in all production of cement is the use of huge rotating furnaces (kilns)
to calcinate and sintering the raw materials. All kilns are made of steel lined with firebrick, have
a horizontal layout with a slight slope (2.5 to 4 %) and turn at about 0.5 to 5.0 revolutions per
minute. Kiln shell is made from rolled mild steel plate, usually between 15 and 30 mm thick,
welded to form a cylinder which may be up to 230 m in length and up to 6 m in diameter.

The refractory lining is to insulate the steel shell from the high temperatures inside the kiln, and
to protect it from the corrosive properties of the process material. It may consist of refractory
bricks or cast refractory concrete. The refractory selected depends upon the temperature inside
the kiln and the chemical nature of the material being processed. The thickness of the lining is
generally in the range 80 to 300 mm. A typical refractory will be capable of maintaining a
temperature drop of 1000 °C or more between its hot and cold faces. The shell temperature needs
to be maintained below around 350 °C in order to protect the steel from damage, and continuous
infrared scanners are used to give early warning of "hot-spots" indicative of refractory failure.

The oxides of aluminium (alumina), silicon (silica) and magnesium (magnesia) are the most
important materials used in the manufacturing of refractories. Another oxide usually found in
refractories is the oxide of calcium (lime). Fire clays are also widely used in the manufacture of
refractories. Refractories must be chosen according to the conditions they face. Some
applications require special refractory materials. Zirconia is used when the material must
withstand extremely high temperatures (Figure 9).

29
 Figure 9: Refractory for Cement Industry

The sketch of a rotary kiln system is given in Figure 10. Kilns are fed from their upper end and
the raw materials tumble towards the lower end, progressively increasing temperature. At the

30
lower end, where the combustion takes place, the combustion gases reach 2000°C and the
material temperature reaches around 1450°C.

Figure 10: The Preheater, Precalciner, Rotary Kiln, Clinker Cooler

31
The rawmix enters a kiln system at a temperature close to ambient, and the temperature rises as it
passes through the kiln system until it reaches a peak temperature in the sintering zone, after
which the chemical state of the clinker is frozen by rapid cooling. During the process of
temperature rise, chemical reactions take place in sequence. This intense heat triggers chemical
and physical changes that produce the clinker; the calcium oxide reacts with silica, alumina and
ferrous oxide to form silicates, aluminates and ferrites.

Depending on the technology, the different stages prior to sintering can take place in the kiln
itself or elsewhere. No matter which technology is used, sintering / clinkering reactions take
place in the kiln. Many complex phenomena are involved, but an approximate net reaction
to form clinker in simplified notation is as follows.

29 C + 8S + 2A + F —> 6C3S + 2C2S + C3A + C4AF.

Preheater towers (Cyclones) provide a more efficient way to recover the heat of the
combustion gases. They consist of a series of vertical cyclone chambers supported in a tower of
more than 60 m. Hot exit gases from the kiln heat the raw meal as they swirl through the
cyclones. Cyclone preheater kilns have developed rapidly since the 1950s. The four-stage
cyclone preheater kiln system was a standard technique in the ’70s. In kilns with preheaters, by
the time the meal is fed in calcination is already about 30 % completed, because the meal is
already heated to a temperature of around 850°C using the exhaust gases. Kiln gas is cooled
typically from 1150°C to 350°C.

The latest development in modern kilns has been the addition of a pre-calciner between the
rotary kiln and the preheater. Additional combustion takes place in this chamber. Up to 65 % of
the total fuel can be burned at this level. Calcination levels of well above 90 % can be achieved.
The pre-calciner has made it possible to shorten the length of the kiln by half and at the same
time allowed scaling-up of production to over 3.5 Mt.

It is convenient to treat these reactions as if they occur within sharply-defined temperature

ranges, although in practice the reaction stages often overlap considerably.

The detail of the stages are as follows:

 65-125°C: Evaporation of free water. Water, of course, boils at 100°C, but can be
evaporated at lower temperatures by a current of gas, provided that the partial pressure of water
in the gas is below water's vapour pressure

32
  400-650°C: Clay decomposition. There are many clay minerals in cement rawmixes,
but their behaviour can be adequately modelled by focusing on the most common one - kaolinite,
Si2Al2O5(OH)2. Although the thermal behaviour of kaolinite is complex, from the cement
manufacturing point of view, the effective formula is:
Si2Al2O5(OH)2 → 2 SiO2 + Al2O3 + 2 H2O (vapour)
Clay minerals also accommodate most of the alkalis in a rawmix. Again, the situation is
complex, but an adequate account can be based on the assumption that they exist as alkali
feldspars. In isolation, feldspars do not decompose at such a low temperature, but in the
conditions of the cement kiln, alkalis become detached and will usually react immediately with
the acid gases of the kiln atmosphere. An equation describing this might be:
KAlSi3O8 (orthoclase) + 0.5 SO2 + 0.25 O2 → 3 SiO2 + 0.5 Al2O3 + 0.5 K2SO4
 500-650°C: Dolomite decomposition. Dolomite - CaMg(CO3)2 - is the mineral
containing the part of the rawmix magnesia existing as carbonates. Dolomite is a distinct
compound, thermodynamically more stable than the corresponding mixture of carbonates.
However, its thermal decomposition proceeds in a manner indistinguishable from that of a
mixture decomposition begins at essentially the same temperature as magnesite (MgCO3) and
leaves calcium carbonate:
CaMg(CO3)2 → CaCO3 + MgO + CO2
For convenience, non-carbonate magnesium compounds can be thought of as reacting in this
temperature range as well. For example, phlogopite might react as follows:
KMg3AlSi3O10(OH)2 + 0.5 SO2 + 0.25 O2 → 0.5 K2SO4 + 3 MgO + 0.5 Al2O3 + 3 SiO2 +
H2O
 650-900°C: Low temperature calcite decomposition. Calcite is the usual form of
calcium carbonate in cement raw mixes. It evolves carbon dioxide in quantities exceeding half
the mass of the finished clinker, and requires a large energy input. The large scale of the
reaction's endotherm means that this stage of the process takes up a major part of the cement
kiln, and the efficiency with which the reaction is achieved is a major factor in defining the
output and heat consumption of the kiln.

Pure calcite decomposes i.e. the pressure of carbon dioxide in equilibrium with it reaches
atmospheric at approximately 896°C. A current of hot air, with a CO2 partial pressure of 40 Pa,
can remove carbon dioxide at 536°C, but kiln gases contain about 35% CO2, and would
decompose pure calcite only above 829°C. In reality, in a kiln burning a normal cement rawmix,

33
decomposition begins at around 650°C. This is because the clay components (or their
decomposition products) act as an acid. The reaction is:
2 CaCO3 + SiO2 → Ca2SiO4 + 2 CO2
The product of the reaction is "incipient belite" - so called because the early reaction products
are "amorphous", and not identifiable as crystalline species by microscopy or x-ray diffraction.
It should be understood that dicalcium silicate is very stable, and can easily be made at
temperatures much lower than 500°C from a mixture of fine silica and a low-temperature lime
source such as calcium oxalate.

Key to this reaction is the availability of reactive clay decomposition products, and of small
amounts of alkali sulfate/chloride melt, which draw the reactants together by surface tension and
act as an ion transfer medium. An important point to note is that at this stage, no free calcium
oxide forms, provided that the rawmix is reasonably fine.

A certain amount of magnesia ends up in the silicate phases, and the MgO produced in the last
stage can be thought of as reacting here with silica to produce forsterite, which will go into solid
solution in the belite:
2 MgO + SiO2 → Mg2SiO4
Phosphorus usually exists in the rawmix as apatite. This will also react with a little free silica,
producing whitlockite, which will also actually go into solid solution in the belite:
Ca5(PO4)3OH + 0.25 SiO2 → 1.5 Ca3(PO4)2 + 0.25 Ca2SiO4 + 0.5 H2O (vapour)

700-900°C: Alumina and iron oxide react. Here calcium carbonate continues to react in a
concerted manner with the other oxides, without any intervening calcium oxide formation.
Although tricalcium aluminate is stable in this temperature range, mayenite (Ca12Al14O33) seems
to be the mineral formed, although it is poorly crystallized. The behaviour of manganese is
indistinguishable from that of iron.
12 CaCO3 + 7 Al2O3 → Ca12Al14O33 + 12 CO2
4 CaCO3 + Al2O3 + Fe2O3 → Ca4Al2Fe2O10 + 4 CO2
4 CaCO3 + Al2O3 + Mn2O3 → Ca4Al2Mn2O10 + 4 CO2
900-1050°C: The remaining calcite decomposes thermally. By this stage, only small
amount carbonate remain, and decomposition proceeds, forming, for the first time, free lime:
CaCO3 → CaO + CO2

1300-1425°C: Sintering. After the previous stage, nothing significant happens until a
temperature of about 1300°C is reached. This is the eutectic melting point of the aluminate,
34
ferrite and silicate mixture that forms the clinker "flux". The actual melting point varies: in the
absence of "minor" oxides, particularly MgO and alkalis, the melting point is 1338°C, but in
most mixes the MgO concentration is sufficient to lower the melting point to 1300°C. If the mix
has the "eutectic composition" with an Al2O3/Fe2O3 ratio of 1.4-1.5 (depending on MgO
content), most of the liquid forms at the melting point, but if the ratio deviates on either side of
this value, melting is progressive as temperature rises. Only one chemical reaction occurs, belite
reacts with free lime to form alite:
Ca2SiO4 + CaO → Ca3SiO5

Alite, C3S starts to form at around 1250 to 1400°C, but in the absence of Al2O3 or Fe2O3 the
process is extremely slow, even at 1500°C. The presence of C3A and, especially, C3AF notably
decreases the temperature at which C3S is formed, allowing meaningful production of C3S in the
temperature range of 1400-1450°C.

Alite becomes stable above 1250°C, but only begins to form when liquid is formed. With the low
temperature melts in above stages, and the liquid physically draws the reactant particles
together by surface tension, and a feed that was before powdery or granular now quickly
consolidates into spherical nodules of clinker.

This is the defining reaction of Portland cement manufacture. The enthalpy change for this
reaction at 25°C is +13.4 kJ/mol, at 1360°C (a typical "half-way" temperature) it is +24.2
kJ/mol. 1 kg of the example clinker contains 0.6538 kg (2.8935 mol) of notional Ca3SiO5, and
so requires a heat input of 69.3 kJ.

The minor phases mostly end up in the melt, and emerge from that, after cooling,
metamorphosed, so for instance the original aluminate enters as Ca12Al14O33 but emerges as
Ca3Al2O6. Several such disproportionations take place with complex interactions, but the nett
effect is almost thermally neutral: the nett effect of these for 1 kg of the example clinker is a heat
input of 32.0 kJ, but this is drowned in the major endotherm required for the latent heat of
fusion. The latent heats of individual components of the melt seem never to have been
determined, but the overall latent heat of melt-formation in real-world clinkers can be deduced
from empirical "sensible heat" curves, and is around 440 kJ per kg of liquid or around 110 kJ per
kg of clinker if liquid formation is a typical 25%. The nett effect of these heat flows is a heat
input of 69.3 + 32.0 + 110 = 211.3 kJ/kg during the rise from 1300°C to the peak
temperature, and an outflow of 110 kJ/kg (the latent heat) as the temperature falls back to
1300°C.
35
In addition to the reaction endotherms, the sensible heat required to raise the feed temperature
must be taken into account. The total sensible heat transferred to the feed in rising from 25 to
1425°C is 2134 kJ/kg, while the sum of the reaction endotherms at the reaction
temperatures is 1695 kJ/kg1. In an efficient kiln system, most of the sensible heat is
subsequently recuperated and re-cycled.
The temperature needed for reactions ane enthalpy changes are given in below table, the reaction
zones in the figure below.

1
1 kilojoule = 0.239 kilocalorie
36
The mass balance is given in Figure 11 for 800 g clinker and 1000 g of cement production in a
rotary kiln with preheater, precalciner, grate cooler. The raw mill used is vertical type. The fuel
used is petroleum coke with calorific value of 8000 kCal/kg. Heat energy consumed as total 788
kCal/Kg clinker. Usually the total heat requirement with new dry precalciner kiln systems ranges
from 850 to 900 kcal/kg.

Today’s new cement plants are all based on the dry process as the wet process requires
approximately 56 to 66% more energy. For dry processes, current state-of-the-art technologies
are kiln systems with multistage cyclone preheaters and precalciner. Capacities of up to 12,000
tonnes clinker per day are achievable and unit consumption as low as 788 kCal/kg clinker.2

Depending on the type of raw mill and cement mill used and cooling technology, 90-150 kWh/t
cement electric energy are used in the process. In a dry process, the electricity consumption share
is 38% for cement grinding, 24% for raw material grinding, 22% for clinker production

2
http://www.tlzjchina.com/
37
including grinding of solid fuels, 6% for raw material homogenisation, 5% for raw material
extraction and blending, and 5% for conveying, packing and loading.

Figure 11: Mass Balance for the Production of 1 kg Cement

The first temperature of clinker melt occurrence varied slightly depending on the type of raw
meal used. The influence of different heating profiles on clinker formation was studied, and it
was observed that C3S formation is more complete, the faster the sample was heated to a
temperature >1400 °C.

It was concluded, the maximum temperature of 1450 °C, as is often stated in literature, is likely
often not applicable. Agglomeration of the raw meal was observed to start already at 900 °C. The
agglomerates formed are first rather weak, but increase in hardness with increasing
temperature. The size of the agglomerates as well as the amount formed is found to be
dependent on the rotation velocity: the higher the rotation velocity, the higher is the amount
of agglomerates <1mm. But, the higher rotation velocity also resulted in a decrease of the total
amount of agglomerates, whereas the amount of material lining on the kiln walls increased.
Clinker occurs as 3 millimeters (0.12 in) to 25 millimeters (0.98 in) in diameter, produced by
sintering, fused together without melting to the point of liquefaction, limestone and alumino-

38
silicate materials such as clay during the cement kiln stage. The picture of clinker and clinker
mineralogy under microscope is given below.

Firing of rotary kilns; irrespective of the fuel used, the most obvious common feature of the
firing system is the firing pipe (burner pipe) which passes through the kiln hood at the kiln's hot
end, arranged more or less along the kiln's centre line, and through which the fuel is projected
into the kiln at high velocity (Figure 12).

Burner pipes are used to convey and introduce fuels into the pyroprocess. Fuel is conveyed
pneumatically through the inside of the burner pipe and blown into the kiln, where it ignites,
providing the necessary heat for the process.

The effect is rather like a bunsen burner, producing a flame that extends some way up the kiln.
Burner pipes are used to convey and introduce fuels into the pyroprocess. Fuel is conveyed
pneumatically through the inside of the burner pipe and blown into the kiln, where it ignites,
providing the necessary heat for the process.

The process environment is subject to thermal shock (the result of a sudden loss of flame), alkali
attack (alkali from the fuels), and severe abrasion (from dust-laden air entering the kiln from the
cooler). Burner pipes are typically “zoned” with a higher-quality refractory material at the flame
end, and the balance of the burner body has a standard low-cement castable.

Primary air is high-velocity air that passes up the firing pipe with the fuel, and gives the fuel
momentum. Generally speaking, the primary air stream contains only a small fraction of the air
needed to burn the fuel. The hot air-stream passing into the kiln outside the firing pipe coming
from the cooler is the secondary air, and this supplies the bulk of the oxygen needed for
combustion.

Although this was not always appreciated in the early days of rotary kiln operation, it is
important that the flame should not impinge upon the clinker bed in the bottom of the kiln, or on
39
the walls of the kiln. The flame should be throughout its length aligned with the centre line of the
kiln. The flame consists of a mass of incandescent gas, the outside of which contains excess
oxygen, which transfers heat solely by radiation. In the case of liquid and gas fuels, the firing
equipment consists of not much more than a firing pipe and firing fan. However, solid fuels have
to be dried and finely ground before they can be used, and are conveyed into the kiln as fine
powder suspended in the primary air stream.

Figure 12: Kiln Hood and Burner Pipe

The primary air is pressurized by the firing fan. The secondary air usually comes mainly from
the clinker cooler, and is at a high temperature (300-800°C). The ignition distance, the distance
between the end of the firing pipe and the start of the flame and the flame length are controlled
by the flowrates and temperatures of the primary and secondary air.

The firing systems employed fall into two categories - indirect firing and direct firing, although
a hybrid of the two - semi-indirect firing - is also encountered.

Direct firing uses the fuel from the fuel mill swept by the primary air, which then immediately
conveys the fuel into the kiln without any intermediate storage of the finely ground fuel. Thus,
with only a small time delay, the fuel feed to the kiln is controlled by the feed-rate of raw fuel to
the mill.

40
Indirect firing uses a fuel mill that is not connected to the firing fan. The fine fuel is stored in a
hopper for use as required.

Burner Pipe

Direct fired systems have a number of advantages:

• The system is simpler in design.
• Finely ground fuel is hazardous: the air/fuel mixture is explosive, and the stored fuel is
susceptible to spontaneous combustion. Immediately conveying the fine fuel into the kiln
largely avoids these problems.

Modern indirect systems used on precalciner kilns solve the explosion hazard problem by
heating and sweeping the mill with preheater gases, which are high in CO2 and low in oxygen.

Clinker Cooler: The clinker is cooled by air flowing through the hot granulated solids. The
heated air is recirculated as combustion air (secondary air) into the burner of the rotary kiln
and/or into the burner of the pre-calcination chamber (tertiary air). The higher the cooling rate,
the higher the heat recovery and therefore the energy efficiency of the cement production
process.

41
The clinker cooler decreases the temperature from 1200°C at which the clinker leaves the kiln to
100°C. This cooling not only allows safe handling of the clinker but also stops further changes of
the clinker mineral.

The adjustment of the clinker cooler radically affects the energy efficiency of the plant and, due
to the high thermal load that occurs, determines the reliability of the entire kiln system.

The trend in cooler design is related to the main technological challenges: thermal expansion,
wear, incorrect air flows and availability. Of the two big groups of coolers ─ rotary and grate
coolers ─ the former is no longer used and is being replaced by the latest designs of grate
coolers.

In travelling grate coolers, the oldest design, the clinker is transported by a travelling grate.
This technology ceased to be used in new installations in around 1980. In the second generation
of grate coolers, reciprocating grate coolers, the clinker is moved by pushing the clinker bed,
step by step, by the front edges of alternate rows of plates.

The essential characteristic of a grate cooler (Figure 13) is a layer of clinker spread on a more-
or-less horizontal perforated stationary and moving grate, through which cold air is blown. The
grate is made of steel, and the cold air keeps it sufficiently cool to avoid melting or burning. The
clinker progresses through the cooler by moving more-or-less horizontally along the grate, and
so the direction of the cooling air is roughly at right angles to the direction of movement of the
clinker, and the cooler functions as a cross-current heat exchanger. This mechanism is
inherently less efficient than a counter-current heat exchanger such as a rotary or planetary
cooler, but there are distinct advantages:
 the hot clinker at the inlet is treated with cold air rather than partially heated air, so that a
rapid quenching effect is possible, improving clinker quality by preserving reactive high-
temperature silicate polymorphs.
 by using air in excess of that needed for combustion, the clinker can readily be cooled
below 200°C.
 it is easy to tap off exhaust hot air streams in desired temperature ranges for use in other
processes - e.g. calciner tertiary air or drying air for fuel or raw materials.
The types of grate cooler are differentiated according to the method whereby the clinker is
moved along the grate, and are treated in chronological order of their introduction.

42
In the Reciprocating Grate Cooler, (Figure 14) ,cooler grate is composed of overlapping rows
of perforated grate plates. Half of the rows are static, fixed to the casing of the cooler. The
alternate rows are carried on a movable frame to which a reciprocating movement is imparted by
an eccentric drive or hydraulic rams. The overlying bed of clinker is pushed forward on the
forward stroke, and the plates slide beneath the bed on the return stroke. Fine clinker can fall
though the grate holes, and so the under-grate chamber contains drag-chain conveyor(s) to move
the spillage to the outlet end of the cooler. For most of its history, a crusher, usually in the form
of a hammer mill, has been placed at the end of the cooler. Larger clinker lumps, are less
effectively cooled, and having been crushed, the rotary action of the hammer mill hurls the
fragments back up the cooler for further cooling.

Figure 13: Grate (Fuller) Cooler for Klinker

43
Figure 14: Reciprocating Grate Cooler

44
The under-grate chamber is generally divided into a number of compartments, each with its own
fan, which can be separately pressurised. The chamber above the grate is refractory lined. Areas
of cold, "dead" clinker are provided at the sides of the grate to protect those areas from over-
heating. The hot air emerging from the bed passes out to the kiln, and the hot-end grate pressure
is controlled to provide a small negative pressure in the kiln hood. Because, in general, more air
passes through the grate than can be used by the kiln, outlet ducts are provided on the side of the
cooler parts of the over-grate chamber. The hot air passing out through these may be used
productively for process operations - e.g. for fuel or raw material drying - or may simply be run
to waste through an exhaust stack. The hot air is inevitably heavily loaded with fine clinker grit,
and so some sort of gas cleaning multi cyclone + fabric filter or electrostatic precipitator is
provided prior to the stack.

Through the 1950s and 60s both grate and planetary coolers were installed, but with the arrival
of precalciners in the 1970s, needing a hot air supply that by-passes the kiln ("tertiary air"),
reciprocating grate coolers became the only viable option, and subsequent developments were
based upon the reciprocating grate design.

The Planetary coolers (Figure 15), sometimes called satellite coolers can be grouped with the
more general class of integral coolers, the common feature of which is that they are a rigidly-
attached part of the structure of the rotary kiln, and rotate with it. Rotary and planetary coolers
operate under suction and although noisy, produce little atmospheric pollution. The obvious
demerits of the in-line cooler were tackled by allowing the clinker to run into tubes outside, and

45
parallel with, the kiln tube. The major disadvantage that access to the front of the kiln could only
be achieved by means of a cantilevered tubular steel tunnel. This feature was all the more
inconvenient if it was necessary to withdraw hot air from the kiln for coal drying. The problem
of supporting the much larger cooling tubes was solved by extending the kiln tube and providing
another tyre downhill from the cooler outlet, but at the expense of an extremely long access
tunnel.

Figure 15: Planertary Cooler

4. Cement Grinding, Storage and Packing

Cement grinding is the end process of the cement manufacturing , is also the most power
consumption process. Its main function is grinding the cement clinker (and gelatinizer,

46
performance adjustment material, etc.) to appropriate particle size (fineness against specific
surface area), to form a certain size distribution, increase its hydration area, accelerate the
hydration speed and satisfies the requirement of setting and hardening cement paste.

Once the clinker is cooled, it may be blended with clinker substitutes and then ground into
finished cement in a cement mill. The final cement is much finer than cosmetic talcum
powder. The fineness of cement is determined using tests that measure the total surface area of a
given unit of mass of cement powder. The fineness of cement is usually expressed relative to the
Blaine air- permeability test, in cm2/g. The fineness of the final product normally ranges from
3000 to 4000 cm2/g. The final grinding of the cement involves the highest power consumption in
cement manufacturing. The chemistry of the clinker and the burning conditions have great
influence over the clinker grindabilty: the higher the belite (C2S) content, the harder the clinker
is to grind.

The clinker is ground with an amount of gypsum to a fine powder in order to regulate the setting
time of cement and to gain the most important property of cement, which is compressive
strength. To produce different types of cement (e.g. Portland Pozzolana Cement), the required
additives are ground with clinker and gypsum to a very fine powder and then used as desired.

Portland clinker is the main constituent of Portland Cement. Calcium sulfate-gypsum 3-10% is
added in order to retard the hydration of tricalcium aluminate. The calcium sulfate may consist
of natural gypsum, anhydrite, or synthetic wastes such as flue-gas desulfurization gypsum. In
addition, up to 5% calcium carbonate and up to 1% of other minerals may be added. It is normal
to add a certain amount of water, and small quantities of organic grinding aids and performance
enhancers.

Blended cements and Masonry cements may include large additions (up to 40%) of natural
pozzolans, fly ash, limestone, silica fume or metakaolin. Blastfurnace slag cement may include
up to 70% ground granulated blast furnace slag. Gypsum and calcium carbonate are relatively
soft minerals, and rapidly grind to ultra-fine particles.

Grinding aids are typically chemicals added at a rate of 0.01-0.03% that coat the newly formed
surfaces of broken mineral particles and prevent re-agglomeration. They include 1,2-
propanediol, acetic acid, triethanolamine and lignosulfonates.Once the clinker is cooled, it may
be blended with clinker substitutes and then ground into finished cement in a cement mill. The
final cement is much finer than cosmetic talcum powder. The fineness of cement is

47
determined using tests that measure the total surface area of a given unit of mass of cement
powder. The fineness of cement is usually expressed relative to the Blaine air- permeability test,
in cm2/g. The fineness of the final product normally ranges from 3000 to 4000 cm2/g. The final
grinding of the cement involves the highest power consumption in cement manufacturing. The
chemistry of the clinker and the burning conditions have great influence over the clinker
grindabilty: the higher the belite (C2S) content, the harder the clinker is to grind.

A Ball Mill is a horizontal cylinder partly filled with steel balls or occasionally other shapes that
rotates on its axis, imparting a tumbling and cascading action to the balls and the media to be
ground (Figure 16). Material fed through the mill is crushed by impact and ground by attrition
between the balls.

The mill is usually divided into at least two chambers, allowing the use of different sizes of
grinding media. Large balls are used at the inlet, to crush clinker nodules (which can be over
25 mm in diameter). Ball diameter here is in the range 60–80 mm. In a two-chamber mill, the
media in the second chamber are typically in the range 15–40 mm, although media down to
5 mm are sometimes encountered. The smaller grades are occasionally cylindrical
"pebs/cylpebs" (Figure 17) rather than spherical. As a general rule, the size of media has to
match the size of material being ground: large media can't produce the ultra-fine particles
required in the finished cement, but small media can't break large clinker particles.

Figure 16: Ball Mill

48
There exists a speed of rotation (the "critical speed") at which the contents of the mill would
simply ride over the roof of the mill due to centrifugal action. The critical speed (rpm) is given
by: nC = 42.29/√d, where d is the internal diameter in metres. Ball mills are normally operated at
around 75% of critical speed to avoid the ride over of the mill content. So a mill with diameter 5
metres will turn at around 14 rpm.

A current of air is passed through the mill. This helps keep the mill cool, and sweeps out
evaporated moisture which would otherwise cause hydration and disrupt material flow. The
dusty exhaust air is cleaned, usually with bag filters.

Figure 17: Ball and Cylpebs

Closed-circuit systems
In the closed-circuit grinding system, all ground materials are led into a separator and classified
into refined powder (products) and coarse powder (return powder). The coarse powder is
returned to the ball mill and ground again with newly-fed raw materials (Figure 18).
Following benefits can be realized with this technology:
 Grinding capacity increases;
 Grain size distribution of refined powder becomes sharp;
 Refined powder temperature is reduced;
 Power consumption rate decreases;
 The abrasion of liners and balls is suppressed;
 Grain size distribution of products can be adjusted by changing the circulation ratio and
the classifier’s run status.

49
The efficiency of the early stages of grinding in a ball mill is much greater than that for
formation of ultra-fine particles, so ball mills operate most efficiently by making a coarse
product, the fine fractions of this then being separated, and the coarse part being returned to the
mill inlet.

The proportion of the mill-exit material returned to the inlet may vary from 10-30% when
ordinary cement is being ground to 85-95% for extremely fine cement products. It is important
for system efficiency that the minimum amount of material of finished-product fineness is
returned to the inlet.
Closed-circuit systems, because of their tight particle size control, lead to cements with relatively
narrow particle size distributions i.e. for a given mean particle size, they have fewer large and
small particles.

Closed circuit grinding plants consist of the tube mill, the elevators, the separators and the fan
These auxiliary units require additional energy which amounts to 10-20 % of the mill’s energy
requirement. It is hard to prove that the separator mill requires a lower specific grinding energy.
At higher Blaine numbers however, the energy requirement for a closed circuit grinding mill is
more advantageous.

In the finish grinding process, the Blaine-number is not the only consideration; the cement must
also have a characteristic granulometric composition.

High Blaine numbers are mostly determined by the fractions of finest particles. However, the
finest particle fractions alone do not effect the hardening capacity of the cement. In closed circuit
grinding the grinding process takes place in the range of coarser particle sizes; by this means, the
grinding of unwanted finest particle sizes – which commonly are generated when grinding in
open circuit – is being prevented. Closed circuit grinding mills generate a range of particle sizes
classified as medium broad to narrow. This demonstrates the superiority of the separator
mill over the compound mill. Modern separators are capable of making a very precise size
"cut" and contribute significantly to the reduction of energy consumption, and have the
additional advantage that they cool both the product and the returned material, thus minimizing
overheating.

As a rule of thumb, only the outer 7 μm "skin" of each particle hydrates in concrete, so any
particle over 14 μm diameter always leaves an un-reacted core. However, the lack of ultra-fine
particles can be a disadvantage. These particles normally pack the spaces between the larger

50
particles in a cement paste, and if absent the deficit is made up with extra water, leading to lower
strength.

Figure 18: Typical Closed Mill/Separator circuit

Roller mills

These have been used for many years for the less exacting raw-milling process, but recently
roller mills, in combination with high-efficiency separators, have been used for cement grinding.
The grinding action employs much greater stress on the material than in a ball mill, and is
therefore more efficient. Energy consumption is typically half that of a ball mill. However, the
narrowness of the particle size distribution of the cement is problematic, and the process
has yet to receive wide acceptance.

51
High-pressure roll presses

These consist of a pair of rollers set 8–30 mm apart and counter-rotating with surface speed
around 0.9 - 1.8 m.s−1. The bearings of the rollers are designed to deliver a pressure of 50 MPa or
more. The bed of material drawn between the rollers emerges as a slab-like agglomeration of
highly fractured particles. The energy efficiency of this process is comparatively high. Systems
have been designed, including a de-agglomerator and separator, that will deliver material of
cement fineness. However, particle size distribution is again a problem, and roll presses are now
increasingly popular as a "pre-grind" process, with the cement finished in a single chamber ball
mill. This gives good cement performance, and reduces energy consumption by 20-40%
compared with a standard ball mill system.

Capacity of cement mills

The cement mills on a cement plant are usually sized for a clinker consumption considerably
greater than the output of the plant's kilns. This is for two reasons:

 The mills are sized to cope with peaks in market demand for cement. In temperate countries,
the summer demand for cement is usually much higher than that in winter. Excess clinker
produced in winter goes into storage in readiness for summer demand peaks. For this reason,
plants with highly seasonal demand usually have very large clinker stores.
 Cement milling is the largest user of electric power on a cement plant, and because they can
easily be started and stopped, it often pays to operate cement mills only during "off-peak"
periods when cheaper power is available. This is also favourable for electricity producers,
who can negotiate power prices with major users in order to balance their generating capacity
over 24 hours. More sophisticated arrangements such as "power shedding" are often
employed. This consists of the cement manufacturer shutting down the plant at short notice
when the power supplier expects a critical demand peak, in return for favourable prices.
Clearly, plenty of excess cement milling capacity is needed in order to "catch up" after such
interruptions.

Temperature control

Heat generated in the grinding process causes gypsum (CaSO4.2H2O) to lose water, forming
bassanite (CaSO4.0.2-0.7H2O) or γ-anhydrite (CaSO4.~0.05H2O). The latter minerals are rapidly
soluble, and about 2% of these in cement is needed to control tricalcium aluminate hydration. If
more than this amount forms, crystallization of gypsum on their re-hydration causes "false set" -

52
a sudden thickening of the cement mix a few minutes after mixing, which thins out on re-mixing.
High milling temperature causes this. If milling temperature is too low, insufficient rapidly
soluble sulfate is available and this causes "flash set" - an irreversible stiffening of the mix.
Obtaining the optimum amount of rapidly soluble sulfate requires milling with a mill exit
temperature within a few degrees of 115 °C. Where the milling system is too hot, some
manufacturers use 2.5% gypsum and the remaining calcium sulfate as natural α-anhydrite
(CaSO4). Complete dehydration of this mixture yields the optimum 2% γ-anhydrite. In the case
of some efficient modern mills, insufficient heat is generated. This is corrected by recirculating
part of the hot exhaust air to the mill inlet.

Energy consumption and output

The hardness of clinker is important for the energy cost of the grinding process. It depends both
on the clinker's mineral composition and its thermal history. The easiest-ground clinker mineral
is alite, so high-alite clinkers reduce grinding costs, although they are more expensive to make in
the kiln. The toughest mineral is belite, because it is harder, and is somewhat plastic, so that
crystals tend to flatten rather than shatter when impacted in the mill. The mode of burning of the
clinker is also important. Clinker rapidly burned at the minimum temperature for
combination, then rapidly cooled, contains small, defective crystals that grind easily. These
crystals are usually also optimal for reactivity. On the other hand, long burning at excess
temperature, and slow cooling, lead to large, well-formed crystals that are hard to grind and un-
reactive. The effect of such a clinker can be to double milling costs.

Control of product quality

In addition to control of temperature (mentioned above), the main requirement is to obtain a

consistent fineness of the product. From the earliest times, fineness was measured by sieving the
cement. As cements have become finer, the use of sieves is less applicable, but the amount
retained on a 45 μm sieve is still measured, usually by air-jet sieving or wet-sieving. The amount
passing this sieve (typically 95% in modern general-purpose cements) is related to the overall
strength-development potential of the cement, because the larger particles are essentially
unreactive.

The main measure of fineness today is specific surface. Because cement particles react with
water at their surface, the specific surface area is directly related to the cement's initial reactivity.
By adjusting the fineness of grind, the manufacture can produce a range of products from a

53
single clinker. Tight control of fineness is necessary in order to obtain cement with the desired
consistent day-to-day performance, so round-the-clock measurements are made on the cement as
it is produced, and mill feed-rates and separator settings are adjusted to maintain constant
specific surface.

A more comprehensive picture of fineness is given by particle size analysis, yielding a measure
of the amount of each size range present, from sub-micrometer upwards. This used to be mainly
a research tool, but with the advent of cheap, industrialized laser-diffraction analyzers, its use for
routine control is becoming more frequent. This may take the form of a desk-top analyzer fed
with automatically gathered samples in a robotized laboratory, or, increasingly commonly,
instruments attached directly to the output ducts of the mill. In either case, the results can be fed
directly into the mill control system, allowing complete automation of fineness control.

In addition to fineness, added materials in the cement must be controlled. In the case of gypsum
addition, the material used is frequently of variable quality, and it is normal practise to measure
the sulfate content of the cement regularly, typically by x-ray fluorescence, using the results to
adjust the gypsum feed rate. Again, this process is often completely automated. Similar
measurement and control protocols are applied to other materials added, such as limestone, slag
and fly-ash.

Cement Storage and Packing

The cement is housed in storage silos, from where it is hydraulically or mechanically extracted
and transported to facilities where it will be packaged in sacks or supplied in bulk.
In either case, it can be shipped by rail car, freighter truck or ship.

Packing system adopts a cement packing line produced. This system is arranged with packing
machine, electric calibration scale, bag destroyer and bag air remover, and its strong points
include high weighing precision, good sealing performance, little flying dust, high automation
and easy operation.

There are many dust collection points in the packing system. This system is installed with four
dust collectors, which collect dust from each dust collection point. The collected cement dust is
returned to bucket-type elevator through screw conveyor (Figure 19).

54
Figure 19: Typical Packing Unit, Packing Machines,-Rotary and Double

55
THE CHEMISTRY OF CLINKER FORMATION

Thus, in order to maintain or even improve clinker quality and output, one needs a better
understanding of the development of clinker properties inside the kiln to react upon the
impact of process changes. Information on raw meal composition and required kiln conditions
may be obtained from equilibrium phase diagrams. Minor components have a small influence
on equilibria but approximations can be made using the CaO-Al2O3-SiO2-Fe2O3 diagram
although it is perhaps preferable to restrict initial considerations to phase relations in the CaO-
SiO2 and the CaO-Al2O3-SiO2 systems.

Portland cement clinker is a "phase assemblage" in which the main mineral crystalline species
are:
 Alite - roughly Ca3SiO5
 Belite - roughly Ca2SiO4
 Tricalcium Aluminate - roughly Ca3Al2O6
 Tetracalcium Aluminoferrite - roughly Ca2(Al,Fe)2O5

All these chemical formulae are "rough" because the phases are actually solid solutions, and the
atoms of the formula are substituted to a small but significant extent by other elements.

Independent of the raw meal used, the different clinker phases were formed in three stages:
 C2S, C3A and C4AF formation at ~900-1350 °C;

56
  Clinker melt formation at ~1350-1400 °C
 C3S formation at >1350 °C.

Phase diagrams represent the phase behavior of mixtures containing three components, liquid,
vapor, and solid phases, in a triangular diagram. An eutectic system (from the Greek "ευ" eu =
easy and "Τήξις" teksis = melting) describes a homogeneous solid mix of atomic and/or
chemical species, forming a joint super-lattice, by striking a unique atomic percentage ratio
between the components as each pure component has its own distinct bulk lattice
arrangement. It is only in this atomic/molecular ratio that the eutectic system melts as a
whole, at a specific temperature (the eutectic temperature) the super-lattice releasing at once
all its components into a liquid mixture. The eutectic temperature is the lowest possible
melting temperature over all of the mixing ratios for the involved component species.

Upon heating any other mixture ratio, and reaching the eutectic temperature one component's
lattice will melt first, while the temperature of the mixture has to further increase for the other
component lattices to melt. Conversely, as a non-eutectic mixture cools down, each mixture's
component will solidify form its lattice at a distinct temperature, until all material is solid.

The chemistry of clinker formation is still under study. Depending on the reaction conditions
as temperature, pressure, reaction time, composition, a significant variety of phases can be
formed from the four major reactants CaO, SiO2, Al2O3 and Fe2O3 of the raw material for
Portland cement clinker, which are also dominating under industrial conditions (Figure 20).
High CaO concentrations, of ~70 wt.%, are used to produce cement clinker.

57
 Figure 20: Ternary Systems of CaO-Al2O3-SiO

The CaO-SiO2 and CaO-Al2O3-SiO2 binary and ternary systems for clinker are given in Figure
21 respectively. The ternary system shows the temperature and compositional information of the
binary system (CaO-SiO2) but with the third component (Al2O3). The curved lines represent
temperature ‘valleys’ as on a map. Compositional information at a fixed temperature can be
derived from an isothermal section. The 1500oC section of the CaO-Al2O3-SiO2 system allows
some consideration of phase equilibria in cement making.
Figure 21: Binary and Ternary Systems of CaO-Al2O3-SiO2

58
At low CaO fraction (~20 wt.%), SiO2 phases like tridymite or cristobalite (important in glass
and ceramic chemistry) occur, while increasing CaO- concentration leads to the appearance of
the clinker phases C3S and C2S at > 57 wt.% CaO. This shows the importance of high cement
raw meal homogeneity. An insufficient high homogeneity, caused for example by poor mixing or
too coarse raw material particles could lead to local areas of different chemical composition than
the overall composition, potentially causing the formation of product phases other than the
typical clinker phases. This is illustrated in the ternary phase diagram (Figure 22) of the CaO-
SiO2-Al2O3-system. At a constant Al2O3 concentration shown with dotted line about 20 wt.%,
SiO2 phases like tridymite or cristobalite occur, while increasing CaO concentration leads to the
appearance of the clinker phases C3S and C2S at > 57 wt.% CaO. This shows the importance of
high cement raw meal homogeneity. An insufficient high homogeneity, caused by poor mixing
or too coarse raw material particles could lead to local areas of different chemical composition

59
than the overall composition, potentially causing the formation of product phases other than the
typical clinker phases.

Figure 22: Ternary Phase Diagram SiO2–Al2O3–CaO (Rankin Diagram) and Solid Model

In the Figure 22, the typical Portland cement clinker composition is given in circle. The area
marked by the square denotes the typical composition of these three reactants in Portland cement

60
clinker. Compositions due to inhomogeneities in Portland cement clinker, as denoted by the
circle, could result in the formation of a melt phase at lower temperatures, e.g. 1170o C.

Controlled clinker cooling is very important for clinker quality and for the energy efficiency of
the overall production process, since it allows heat recovery. It is essential, that the hot clinker is
cooled down quickly to below 1200-12500C, as fast cooling causes the re-crystallisation of the
finely grained aluminate phase which results in a desirable slow, controllable hydration reaction
during the setting process of cement.

Conversely, a coarsely grained aluminate phase formed due to low cooling rates, causes overly
rapid setting of cement. More important is the effect of rapid cooling on the important alite
clinker phase, which is thermodynamically stable only at temperatures above 1250 oC.
Below 1250oC, alite decomposes into belite and calcium oxide. Fast cooling to temperatures
below this critical temperature results in metastable alite.

The quality of clinker is often referred to the amount of free (non-reacted) CaO in the raw
meal, which reduces the strength of concrete. Up to now many theoretically and empirical
derived equations have been developed to calculate the so called “Lime Saturation Factor
(LSF)”. It is used to quantify the amount of CaO in the raw material that can be combined with
SiO2, Al2O3 and Fe2O3 to form the main clinker phases C3S, C2S, C3A and C4AF.

TURKISH CEMENT INDUSTRY

Turkey has 50 active integrated cement plants and 84.6Mt/yr of production capacity and with the
grinding plants as total 87 according to the Global Cement Directory 2015. A further three
integrated plants are under construction, one grinding plant is having its first clinker line
installed to become an integrated cement plant and another plant is being relocated in Afyon.
Turkey also has 17 active grinding plants (excluding the soon-to-be integrated cement plant) and
>8.56Mt/yr of grinding capacity. The production capacities of some of the grinding plants is
unavailable. The installed capacity utilization is given in Table 8.

The majority of cement producers in Turkey are Turkish companies. Akçansa Çimento, Oyak
Group, Çimsa Çimento, Limak Batı Çimento, Aşkale Çimento and Limak Çimento are the
country's major Turkish cement producers. There are also many companies that have one or two
cement plants each. Multinational producers like Votorantim Çimento, Lafarge, Cementir
Holding and Vicat are also active in Turkey's cement market.

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 Table 8: Cement production in Turkey in 2000 - 2014.

Year Cement production (Mt)

2008 48.0

2009 54.0

2010 60.0

2011 63.4

2012 60.0

2013 71.3

2014 75.0

Turkey's largest cement producers in 2015 by installed active integrated cement production
capacity are given in Table 8 below.

Table 8: Turkey's Largest Cement Producers

Rank Company Plants Production capacity (Mt/yr)

1 Oyak Group 6 15.3

2 Akçansa Çimento 5 8.63

3 Çimsa Çimento 5 8.12

4 Nuh Çimento 1 5.70

5 Limak Batı Çimento 5 5.41

6 Cementir Holding 5 5.37

7 AS Çimento 1 4.30

8 Limak Çimento 3 3.81

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 9 Vicat 2 3.40

10 Votorantim Çimento 4 3.30

11 Bursa Çimento Fabrikası 1 3.00

12 KÇS Kahramanmaraş Çimento 1 2.80

13 Göltaş Göller Bölgesi Çimento 1 2.00

14 Batıçim Batı Anadolu Çimento 1 2.00

15 Aşkale Çimento 2 1.96

Oyak Group is Turkey's largest cement producer by installed integrated cement production
capacity. In 2015 it has 15.3Mt/yr of production capacity from six plants. It also has two active
grinding plants. A third grinding plant run by its Bolu Çimento subsidiary in Caydurt, Bolu is
having a clinker line installed to convert it to an integrated plant.

Turkey's cement producers are well-prepared for growing cement demand amid a strong
construction sector

Figure 23: Location of Cement Plants in Turkey

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