Topic 5: CEMENT

A short series of lectures prepared for the Third year of

Geology, Tanta University
2013- 2014

by
Hassan Z. Harraz
hharraz2006@yahoo.com

13 March 2014

Prof. Dr. H.Z. Harraz Presentation Cement

OUTLINE OF TOPIC 5:
CEMENT
TYPES OF CEMENTS
PORTLAND CEMENT
TYPES OF PORTLAND CEMENT
GENERAL FEATURES OF THE MAIN TYPES OF PORTLAND CEMENT

ORDINARY PORTLAND CEMENT (OPC)

RAPID HARDENING PORTLAND CEMENT
SPECIAL TYPES OF RAPID HARDENING PORTLAND CEMENT
MANUFACTURE OF PORTLAND CEMENT:1) Raw Materials
2) Crushing & Grinding of Raw Materials
3)Type of cement processes:
a) Wet Process
b) B) Dry process
4) Burning Process
5) Grinding
6) storage, packing, dispatch
CEMENT CHEMISTRY
Chemical Compositions
Bogues Equations
Fineness of cement

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Prof. Dr. H.Z. Harraz Presentation Cement

CEMENT
DEFINATION:
Cement is the mixture of calcareous, siliceous, argillaceous and other substances.
Cement is a hydraulic binder and is defined as a finely ground inorganic material
which, when mixed with water, forms a paste which sets and hardens by means of
hydration reactions and processes which, after hardening retains it's strength and
stability even under water.
Cement used in construction is characterized as hydraulic or non-hydraulic.
1) Hydraulic cements (e.g., Portland cement) harden because of hydration, chemical
reactions that occur independently of the mixture's water content; they can harden even
underwater or when constantly exposed to wet weather. The chemical reaction that results
when the anhydrous cement powder is mixed with water produces hydrates that are not
water-soluble.
2) Non-hydraulic cements (e.g. Gypsum plaster) must be kept dry in order to retain their
strength.

TYPES OF CEMENTS:
1)Portland cements
2)Natural cements
3)Expansive cements
4)High-alumina cements
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Prof. Dr. H.Z. Harraz Presentation Cement

PORTLAND CEMENT
Portland Cement
is a hydraulic cement that hardens in water to form a waterresistant compound.
The hydration products act as binder to hold the aggregates
together to form concrete.
A hydraulic cement made by finely pulverizing the clinker
produced by calcining to incipient fusion a mixture of
argillaceous and calcareous materials
Portland cement is the fine gray powder that is the active
ingredient in concrete
Limestone + Shale/Clay + Heat = Clinker +CKD + Exit Gas
Material Temperatures Exceed 2700 oF
Pulverized Clinker + Gypsum = Portland Cement
Cement is powder so fine that one pound contains 150 billion
grains
The name Portland Cement comes from the fact that the colour
and quality of the resulting concrete are similar to Portland
stone, a kind of limestone found in England.

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Prof. Dr. H.Z. Harraz Presentation Cement

TYPES OF PORTLAND CEMENT

According to the ASTM standard, there are five basic types of Portland Cement:.
Regular cement, general use, called Ordinary Portland cement (OPC) Type
Moderate sulphate resistance, moderate heat of hydration, C3A < 7% , Modified cement Type
Rapid-hardening Portland cement , With increased amount of C3S, High early strength Type

Low heat Portland cement Type V

High Sulfate-resisting Portland cement Type V
It is possible to add some additive to Portland cement to produce the following types:
Portland blastfurnace cement Type S
Pozzolanic cement - Type P
Air-entrained cement - Type A
White Portland Cement (WPC)
Colored Portland Cement

Note:
sulphates can react with C4ASH18 to from an expansive product. By reducing the C3A

content, there will be less C4ASH18 formed in the hardened paste.

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
types are listed in Table 2.
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2014general characteristics of these
Prof. Dr. H.Z. Harraz Presentation

Cement

The oxide and mineral compositions of a typical Type I Portland cement were given in Tables.

GENERAL FEATURES OF THE MAIN TYPES OF PORTLAND CEMENT

ASTM
Type
Type I

Classification
General purpose

Type V

Moderate sulfate
resistance (Modified
cement)
High early strength
(Rapid-hardening)
Low heat of hydration
(slow reacting)
High sulfate
resistance

White

White color

Type II
Type III
Type IV

Characteristics
Fairly high C3S content for
good early strength
development
Low C3A content (<8%)
Ground more finely, may have
slightly more C3S
Low content of C3S (<50%)
and C3A
Very low C3A content (<5%)
No C4AF, low MgO

Applications
General construction (most
buildings, bridges,
pavements, precast units,
etc)
Structures exposed to soil or
water containing sulfate ions
Rapid construction, cold
weather concreting
Massive structures such as
dams. Now rare.
Structures exposed to high
levels of sulfate ions
Decorative (otherwise has
properties similar to Type I)

Chemical composition of
the main types of
Portland cement

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Prof. Dr. H.Z. Harraz Presentation Cement

ORDINARY PORTLAND CEMENT (OPC)

This type of cement use in constructions when there is no exposure to sulfates in the soil or
groundwater.
The chemical composition requirements are listed as shown below:

Lime Saturation Factor (L.S.F.) =

{CaO-0.7(SO3)}/ {2.8(SiO2)+1.2(Al2 O3)+0.65(Fe2O3)}
L.S.F. is limited between 0.66-1.02
Where each term in brackets denotes the percentage by mass of cement composition.
This factor is limited to assure that the lime in the raw materials, used in the cement
manufacturing is not so high, so as it cause the presence of free lime after the
occurrence of chemical equilibrium. While too low a L.S.F. would make the burning in
the kiln difficult and the proportion of C3S in the clinker would be too low.
Free lime cause the cement to be unsound.
Percentage of (Al2O3/Fe2O3) : is not less than 0.66
Insoluble residue: not more than 1.5%
Percentage of SO3 : limited by 2.5% when C3A7%, and not more than 3% when
C3A>7%
Loss of ignition L.O.I. : 4% (max.)
Percentage of MgO : 5% (max.)
Fineness : not less than 2250 cm2/gm

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Prof. Dr. H.Z. Harraz Presentation Cement

Typical compound composition of Ordinary Portland Cement (OPC)

Chemical Name

Oxide Formula

Cement
Notation

Mineral
Name

Weight
(%)

Tricalcium Silicate

3CaO.SiO2

C3S

Alite

50

Dicalcium Silicate

2CaO.SiO2

C2S

Belite

25

Tricalcium Aluminate

3CaO.Al2O3

C3A

Aluminate

12

C4AF

Ferrite

CSH2

Gypsum

3.5

Tetracalcium Aluminoferrite 4CaO.Al2O3.Fe2O3

Calcium sulfate dihydrate

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CaO.SO3.2H2O

Prof. Dr. H.Z. Harraz Presentation Cement

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.
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 a Type I and Type II cement, and it is common to see cements meeting both designations labeled as
Type I/II. The phenomenon of sulfate attack will be discussed in much more detail in Sections 5.3 and 12.3, but 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
WPC 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 because the
lack of iron improves the resolution of nuclear magnetic resonance (NMR) measurements.

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Prof. Dr. H.Z. Harraz Presentation Cement

RAPID HARDENING PORTLAND CEMENT

This type develops strength more rapidly than ordinary Portland cement. The initial strength is
higher , but they equalize at 2-3 months
Setting time for this type is similar for that of ordinary Portland cement
The rate of strength gain occur due to increase of C3S compound, and due to finer grinding of
the cement clinker ( the min. fineness is 3250 cm2/gm (according to IQS 5)
Rate of heat evolution is higher than in ordinary Portland cement due to the increase in C3S
and C3A, and due to its higher fineness
Chemical composition and soundness requirements are similar to that of ordinary Portland
cement

Uses
a)The uses of this cement is indicated where a rapid strength development is desired (to develop
high early strength, i.e. its 3 days strength equal that of 7 days ordinary Portland cement), for
example:
i) When formwork is to be removed for re-use
ii) Where sufficient strength for further construction is wanted as quickly as practicable, such
as concrete blocks manufacturing, sidewalks and the places that can not be closed for a
long time, and repair works needed to construct quickly.
b) For construction at low temperatures, to prevent the frost damage of the capillary water.
c) This type of cement does not use at mass concrete constructions.

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Prof. Dr. H.Z. Harraz Presentation Cement

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SPECIAL TYPES OF RAPID HARDENING PORTLAND CEMENT

A) Ultra High Early Strength Cement
The rapid strength development of this type of cement is achieved by grinding the cement to a very high
fineness: 7000 to 9000 cm2/g. Because of this, the gypsum content has to be higher (4 percent expressed as
SO3). Because of its high fineness, it has a low bulk density. High fineness leads to rapid hydration, and
therefore to a high rate of heat generation at early ages and to a rapid strength development ( 7 days strength of
rapid hardening Portland cement can be reached at 24 hours when using this type of cement). There is little
gain in strength beyond 28 days.
It is used in structures where early prestressing or putting in service is of importance.
This type of cement contains no integral admixtures.

B) Extra Rapid Hardening Portland Cement

This type prepare by grinding CaCl2 with rapid hardening Portland cement. The percentage of CaCl2 should not
be more than 2% by weight of the rapid hardening Portland cement.
By using CaCl2:
The rate of setting and hardening increase (the mixture is preferred to be casted within 20 minutes).
The rate of heat evolution increase in comparison with rapid hardening Portland cement, so it is more
convenient to be use at cold weather.
The early strength is higher than for rapid hardening Portland cement, but their strength is equal at 90 days.
Because CaCl2 is a material that takes the moisture from the atmosphere, care should be taken to store this
cement at dry place and for a storage period not more than one month so as it does not deteriorate.

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Prof. Dr. H.Z. Harraz Presentation Cement

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MANUFACTURING OF CEMENT

1) Quarry
2) Raw Material
3) Mixing and crushing of raw

materials:
a) Dry process
b) Wet process
4) Burning
5) Grinding
6) Storage
7) Packing
8) Dispatch

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Step in the Manufacture of Portland Cement

quarry
dumper
loader

Quarry face
1. BLASTING

2. TRANSPORT

storage at
the plant

crushing
conveyor

3. CRUSHING & TRANSPORTATION

Typical Quarry operation:

Typically shale provides the argillaceous components: Silica (SiO2, Aluminum (Al2O3) & Iron (Fe2O3)
Limestone provides the calcareous component: Calcium Carbonate (CaCO3 )
Raw materials may vary in both composition and morphology.
1. BLASTING : The raw materials that are used to manufacture cement (mainly limestone and clay) are blasted from the quarry.
2. TRANSPORT : The raw materials are loaded into a dumper.

THE CEMENT MANUFACTURING PROCESS

Raw grinding and burning

storage at
the plant

Raw mill
conveyor

preheating

Raw mix

1. RAW GRINDING

kiln
cooling
clinker
2. BURNING
1. RAW GRINDING : The raw materials are very finely ground in order to produce the raw mix.
2. BURNING : The raw mix is preheated before it goes into the kiln, which is heated by a flame that can
be as hot as 2000 C. The raw mix burns at 1500 C producing clinker which, when it leaves the kiln, is
rapidly cooled with air fans. So, the raw mix is burnt to produce clinker : the basic material needed to
make cement.

THE CEMENT MANUFACTURING PROCESS

Grinding, storage, packing, dispatch
Gypsum and the secondary additives are added
to the clinker.
clinker
storage

Finish grinding

1. GRINDING

silos

dispatch
bags

2. STORAGE, PACKING, DISPATCH

1.GRINDING : The clinker and the gypsum are very finely ground giving a pure cement. Other secondary
additives and cementitious materials can also be added to make a blended cement.
2. STORAGE, PACKING, DISPATCH :The cement is stored in silos before being dispatched either in
bulk or in bags to its final destination.

MANUFACTURE OF ORDINARY PORTLAND CEMENT

Ordinary Portland Cement (OPC) is one of several types of cement being manufactured throughout the
world.
OPC consists mainly of lime (CaO), silica (SiO2) , alumina (Al2O3) , iron (Fe2O3) and sulphur trioxide
(SO3). Magnesium (MgO) and other Oxide elements are present in small quantities as an impurity
associated with raw materials.
When cement raw materials containing the proper proportions of the essential oxides are ground to a
suitable fineness and then burnt to incipient fusion in a kiln, chemical combination takes place, largely
in the solid state resulting in a product named clinker.
This clinker, when ground to a suitable fineness, together with a small quantity of gypsum (SO3) is
Portland Cement. SO3 is added at the grinding stage to retard the setting time of the finished cement.
Basic Chemical Components of Portland Cement:
Calcium (Ca)
Silicon (Si)
Aluminum (Al)
Iron (Fe)
2/3 calcareous materials (lime bearing) - limestone

1/3 argillaceous materials (silica, alumina, iron)- clay

Typical Raw Materials:

Limestone (CaCO3)
Sand (SiO2)
Shale, Clay (SiO2, Al2O3, Fe2O3)
Iron Ore/Mill Scale (Fe2O3)

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2) Raw Materials for Cement Manufacture

The first step in the manufacture of Portland Cement is to combine a variety of raw ingredients so that
the resulting cement will have the desired chemical composition.
These ingredients are ground into small particles to make them more reactive, blended together, and
then the resulting raw mix is fed into a cement kiln which heats them to extremely high temperatures.
Since the final composition and properties of Portland Cement are specified within rather strict bounds,
it might be supposed that the requirements for the raw mix would be similarly strict. As it turns out,
this is not the case. 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 1 lists just some of the many possible raw ingredients that can be used to provide each of the
main cement elements.
Table 1: Examples of raw materials for Portland Cement manufacture
Calcium
Silicon
Aluminum
Iron
Limestone
Clay
Clay
Clay
Marl
Marl
Shale
Iron ore
Calcite
Sand
Fly ash
Mill scale
Gypsum
Shale
Aluminum ore
Shale
refuse
Fly ash
Phyllite
Blast furnace
Marly limestone
dust
Sea Shells
Rice hull
slate
slag
ash
Cement kiln dust
Silica
Chalk
Sand

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Typical Composition of Raw Materials

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2) Raw Materials for Cement Manufacture (Cont.)

The ingredients listed above include both naturally occurring materials such as
limestone and clay, and industrial byproduct materials such as slag and fly ash. From
Table 1 it may seem as if just about any material that contains one of the main cement
elements can be tossed into the kiln, but this is not quite true.
The raw materials used in the manufacture of cement are limestone, shale, sand and
iron ore, typical chemical compositions of which are given in the table below.
Limestone makes up approximately 80% of the raw material requirements, composes
of mainly calcium carbonate with small intrusions of magnesium carbonate. Quarrying
operations are geared to minimizing the intrusions. MgO in the cement, if present in
sufficient quantities will cause expansion upon hydration thus resulting in unsoundness
in the concrete.
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 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.
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Raw Material Proportioning

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

As coal is used as a fuel the coal ash, a combustion product of the coal, has to
be treated as an individual raw material component and the appropriate
corrections made at the weigh-feeder stage.
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2) Crushing & Grinding of Raw Materials

Due to the variable nature of these components, they are pre-blended prior to their use.
It is crushed and stored in a pre-blending hall, utilizing the chevron pile stacking
method. In this method, stacking takes place at one end of the pile. At the other end of
the pile the material is reclaimed and then stored in a feeding hopper which is ready for
use.
The limestone is crushed to less than 25mm in size.
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 (the dry process). The
addition of water facilitates 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. When it is ready to enter the kiln, the dry raw mix has 85% of the particles
less than 90 m in size

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The raw materials used for manufacturing Portland Cement are limestone, clay and
Iron ore.
a) Limestone (CaCO3) is mainly providing calcium in the form of calcium oxide
(CaO)
CaCO3 (1000oC) CaO + CO2
b) Clay is mainly providing silicates (SiO2) together with small amounts of Al2O3 +
Fe2O3
Clay (1450oC) SiO2 + Al2O3 + Fe2O3 + H2O
c) Iron ore and Bauxite are providing additional aluminum and iron oxide (Fe2O3)
which help the formation of calcium silicates at low temperature. They are
incorporated into the raw mix.

d) The clinker is pulverized to small sizes (< 75 m). 3-5% of gypsum (calcium sulphate)
is added to control setting and hardening.
The majority particle size of cement is from 2 to 50 m.
(Note: Blaine refers to a test to measure particle size in terms of surface area/mass)
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Type of cement processes

a) Dry process:
In this process calcareous material such
as lime stone (calcium carbonate) and
argillaceous material such as clay are
ground separately to fine powder in the
absence of water and then are mixed
together in the desired proportions.
Water is then added to it for getting
thick paste and then its cakes are
formed, dried and burnt in kilns. This
process is usually used when raw
materials are very strong and hard.
In this process, the raw materials are
changed to powdered form in the
absence of water.
Dehydration zone requires a somewhat
shorter distance than wet process.
74% of cement produced.
kilns less fuel requirements

b) Wet process:
In this process, the raw materials are changed to powdered
form in the presence of water.
In this process, raw materials are pulverized by using a
Ball mill, which is a rotary steel cylinder with hardened
steel balls. When the mill rotates, steel balls pulverize the
raw materials which form slurry (liquid mixture). The
slurry is then passed into storage tanks, where correct
proportioning is done. Proper composition of raw
materials can be ensured by using wet process than dry
process. Corrected slurry is then fed into rotary kiln for
burning.
This process is generally used when raw materials are soft
because complete mixing is not possible unless water is
added.
Actually the purpose of both processes is to change the
raw materials to fine powder.
dehydration zone would require up to half the length of
the kiln
easiest to control chemistry & better for moist raw
materials
high fuel requirements - fuel needed to evaporate 30+%
slurry water
The kiln is a continuous stream process vessel in which
feed and fuel are held in dynamic balance

3) Burning in a Kiln Formation of Cement Clinker

The next step in the process is to heat the blended mixture of raw ingredients (the
raw mix) to convert it into a granular material called cement clinker.
This requires maximum temperatures that are high enough to partially melt the raw
mix. Because the raw ingredients are not completely melted, the mix must be
agitated to ensure that the clinker forms with a uniform composition.
This is accomplished by using a long cylindrical kiln that slopes downward and rotates
slowly.
To heat the kiln, a mixture of fuel and air is injected into the kiln and burned at the
bottom end. The hot gases travel up the kiln to the top, through a dust collector, and
out a smokestack. A variety of fuels can be used, including pulverized coal or coke,
natural gas, lignite, and fuel oil. These fuels create varying types and amounts of ash,
which tend to have compositions similar to some of the aluminosilicate ingredients in
the raw mix. Since the ash combines with the raw mix inside the kiln, this must be
taken into account in order to correctly predict the cement compassion. There is also
an increasing trend to use waste products as part of the fuel, for example old tires. In
the best-case scenario, this saves money on fuel, reduces CO2 emissions, and
provides a safe method of disposal.

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Kiln Feed Preparation

Proportioning of feed stock.

Size reduction to < 125.
Control of moisture.
Blending to reduce standard deviation.
Uniform delivery rate of feed to the Kiln.

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Manufacturing control criteria in the Kiln

Silica Modulus (SM) :
Rate of reactions
SiO2
SM = -------------------Al2O3 + Fe2O3
2.3 to 3.5 (desired at least 3.0),
slow reaction if SM is high
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Alumina Modulus (AM):

controls melt temperature
Al2O3
AM = -------------Fe2O3

AM ~2
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Lime Saturation factor (LSF):

Designed to insure against equilibrium free lime
CaO
LSF = ----------------------------SiO2 + Al2O3 + Fe2O3
LSF : 0.92-0.96
Or
CaO
LSF = --------------------Al2O3 + Fe2O3
C/(A+F) should be equal to 2

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CEMENT KILNS
the Largest Moving Equipment in any Manufacturing Operation

And the Hottest

High temperature
Long residence time
Natural alkaline environment
CKD is only by-product of the process
Thermal stability

Kiln Process

Kiln Process Thermochemical Reactions

Process
Drying

Temperature (oC)
20 - <100

Reactions

Chemical Transformation

Escape of free water (i.e., Free

Water evaporates)
Escape of adsorbed water (i.e.,
Crystallization water driven out)

100 - 300
400 - 750
Pre-heat
600 - 900

Calcining

600 - 1000

Sintering
Clinkering

800 1550 (1350

exothermic)

Chemical water driven out,

Decomposition of shale., with
formation of metakaolinite
Decomposition of metakaolinite and
other compounds, with formation of
reactive oxide mixture
Decomposition of limestone, CO2
Driven out, Formation of Free lime ,
with formation of CS (CaO.SiO2) and
CA (CaO.Al2O3)
Uptake of lime by CS and CA,
Formation of Liquid Phase,
Formation of: Belite (C2S),
Aluminates (C3A) and Ferrites (C4AF)

Al4Si4O10(OH)8
2(Al2O3.2SiO2) + 4H2O
Al2O3.2SiO2 Al2O3.+ 2SiO2

3CaCO3 3CaO + 3CO2

3CaO + 2SiO2 + Al2O3
2(CaO.SiO2) + CaO.Al2O3
CS + C C2S
2C + S C2S
CA + 2C C3A
CA + 3C + F C4AF

Cooling

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Clinker Burning

For the production of cement clinker, the raw meal which is known as kiln feed at this stage
has to be heated to a temperature of about 1550 oC in the long cylindrical rotating kiln.
The kiln feed enters the system at the top of the pre-heater and fall until the lower end of
the kiln.
The heat exchange occurs during this process when the hot gases from the kiln end rise up
to the top of the pre-heater.
The clinker formation process is divided into four parts: drying, calcining, sintering and
cooling.
As the kiln feed moves towards the lower end of the kiln it undergoes successive reactions
as shown in the table:
CLINKER

Clinker is what comes out of the kiln

3 to 25 mm in diameter
20 25 % Molten

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Clinker Microstructure
Dark, Rounded C2S

C3S crystals magnified 3000 times

Light, Angular C3S

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Burning Process
This description refers to a standard dry-process kiln. Such a kiln is typically about 180 m
long and 6 m in diameter, has a downward slope of 3-4%, and rotates at 1-2 revolutions
per minute.
The raw mix enters at the upper end of the kiln and slowly works its way downward to
the hottest area at the bottom over a period of 60-90 minutes, undergoing several
different reactions as the temperature increases. It is important that the mix move
slowly enough to allow each reaction to be completed at the appropriate temperature.
Because the initial reactions are endothermic (energy absorbing), it is difficult to heat the
mix up to a higher temperature until a given reaction is complete.
The general reaction zones are as follows:
1) Dehydration zone (up to ~ 450C)
2) Calcination zone (>450C 900C)
3) Solid-state reaction zone (>900 - 1300C)
4) Clinkering zone (>1300C 1550C)
5) Cooling zone

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Burning Process (Cont.)

Reaction Zone Temperature (oC)

Dehydration

up to ~ 450

Calcination

450C 900

Solid-state
reaction

>900 - 1300

Characteristics
This is simply the evaporation and removal of the free water
Even in the dry process there is some adsorbed moisture in the raw mix.
Although the temperatures required to do this are not high, this requires significant time and
energy.
In the wet process, the dehydration zone would require up to half the length of the kiln, while
the dry process requires a somewhat shorter distance.
The term calcination refers to the process of decomposing a solid material so that one of its
constituents is driven off as a gas.
At about 600C the bound water is driven out of the clays,
and by 900C the calcium carbonate is decomposed, releasing carbon dioxide.
By the end of the calcination zone, the mix consists of oxides of the four main elements which
are ready to undergo further reaction into cement minerals.
Because calcination does not involve melting, the mix is still a free-flowing powder at this
point.
This zone slightly overlaps, and is sometimes included with, the calcination zone.
As the temperature continues to increase above ~ 900C there is still no melting, but solidstate reactions begin to occur.
CaO and reactive silica combine to form small crystals of C2S (dicalcium silicate; Belite), one of
the four main cement minerals.
In addition, intermediate calcium aluminates (C3A) and calcium ferrite (C4AF) compounds form.
These play an important role in the clinkering process as fluxing agents, in that they melt at a
relatively low temperature of ~1300C, allowing a significant increase in the rate of reaction.
Without these fluxing agents, the formation of the calcium silicate cement minerals would be
slow and difficult.
In fact, the formation of fluxing agents is the primary reason that Portland (calcium silicate)
Cements contain aluminum and iron at all.
The final aluminum- and iron-containing cement minerals (C3A and C4AF) in a Portland Cement
contribute little to the final properties.
As the mix passes through solid-state reaction zone it becomes sticky due to the tendency

Reaction Zone Temperature (oC)

Clinkering

Cooling

>1300 1550

Characteristics
This is the hottest zone where the formation of the most important cement mineral, Alite
(C3S), occurs.
The zone begins as soon as the intermediate calcium aluminate (C3A) and ferrite (C4AF) phases
melt.
The presence of the melt phase causes the mix to agglomerate into relatively large nodules
about the size of marbles consisting of many small solid particles bound together by a thin
layer of liquid.
Inside the liquid phase, Alite (C3S) forms by reaction between Belite (C2S) crystals and CaO.
(C2S + C C3S)
Crystals of solid Alite (C3S) grow within the liquid, while crystals of Belite (C2S) formed earlier
decrease in number but grow in size.
The clinkering process is complete when all of silica is in the C3S and C2S crystals and the
amount of free lime (CaO) is reduced to a minimal level (<1%).
As the clinker moves past the bottom of the kiln the temperature drops rapidly and the liquid
phase solidifies, forming the other two cement minerals C3A (aluminate) and C4AF (ferrite).
In addition, alkalis (primarily K) and sulfate dissolved in the liquid combine to form K2SO4 and
Na2SO4.
The nodules formed in the clinkering zone are now hard, and the resulting product is called
cement clinker.
The rate of cooling from the maximum temperature down to about 1100C is important, with
rapid cooling giving a more reactive cement.
This occurs because in this temperature range the C3S can decompose back into C2S and CaO,
among other reasons.
It is thus typical to blow air or spray water onto the clinker to cool it more rapidly as it exits the
kiln.
Rapid cooling of the clinker is essential as this hampers the formation of crystals, causing
part of the liquid phase to solidify as glass.
The faster the clinker cooling the smaller the crystals will be when emerging from the liquid
phase.

Dual Line Preheater

Planetary Cooler

i) Generalized Diagram of a Long Dry Process Kiln

Reaction

Exhaust
Gases

Raw
Feed

The kiln exit gas

temperature will
depend on the
process

Zone

Gas
Temperature
Material
Temperature

Clinker Out

Suspension Preheaters and Calciners

The chemical reactions that occur in the dehydration and calcination zones are
endothermic, meaning that a continuous input of energy to each of the particles
of the raw mix is required to complete the reaction. When the raw mix is piled up
inside a standard rotary kiln, the rate of reaction is limited by the rate at which
heat can be transferred into a large mass of particles. To make this process more
efficient, suspension preheaters are used in modern cement plants to replace the
cooler upper end of the rotary kiln. Raw mix is fed in at the top, while hot gas
from the kiln heater enters at the bottom. As the hot gas moves upward it creates
circulating cyclones that separate the mix particles as they settle down from
above. This greatly increases the rate of heating, allowing individual particles of
raw mix to be dehydrated and partially calcined within a period of less than a
minute.
Alternatively, some of the fuel can be burned directly within the preheater to
provide even more heating to the suspended particles. The area of the preheater
where fuel is burned is called a precalciner. With a precalciner, the particles are
nearly completely calcined as they enter the rotary kiln. Preheaters and
precalciners save on fuel and increase the rate at which the mix can be moved
through the rotary kiln.

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ii) General Diagram of Preheater/Precalciner Reactions

Dry Process Preheater/Precalciner System

Preheater Precalciner Kiln

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Kiln Process Control

Critical Parameters: Fuel, Feed, Kiln Speed, Gas Flow
Kiln Temperatures - Burning Zone
Kiln Stability
Chemistry
Instrumentation

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4) Grinding and the Addition of Gypsum

Cement Grinding
Now the final process is applied which is grinding of clinker, it is first cooled down to atmospheric

temperature.
Grinding of clinker is done in large tube mills.
After proper grinding gypsum (Calcium sulphate CaSO4) in the ratio of 01-04 % is added for
controlling the setting time of cement.
Finally, fine ground cement is stored in storage tanks from where it is drawn for packing.
Once the nodules of cement clinker have cooled, they are ground back into a fine powder in a
large grinding mill. At the same time, a small amount of calcium sulfate such as gypsum (calcium
sulfate) is blended into the cement. The calcium sulfate is added to control the rate of early
reaction of the cement
Cement is produced by grinding clinker with gypsum (calcium sulfate) in the finish-grinding mill to
a required fineness.
A small quantity of gypsum, about 3 to 5 %, is needed to control the setting time of cement
produced.
The amount of gypsum being used is determined by the Sulphuric anhydride (SO3) contents in
cement.

 Clinker, gypsum, and optional additives are weighed to

proper proportions and ground in the cement mills.
Additives may include: Fly-ash, Limestone..
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Schematic of a
Grinding Mill

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Cement Storage & Distribution

At this point the manufacturing process is complete and the
cement is ready to be bagged or transported in bulk away
from the plant After the grinding process, cement is
pumped into the storage silos.
This silo is preventing the moisture to react with cement.
When needed cement from the silos is packed into bags or
loaded into road tankers and rail wagons for dispatch.
However, the cement is normally stored in large silos at the
cement plant for a while so that various batches of cement
can be blended together to even out small variations in
composition that occur over time.

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CEMENT CHEMISTRY

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CHEMICAL COMPOSITIONS
1) Cement chemistry notation based on oxides

The properties of cement

during hydration vary
according to:
Chemical composition
Degree of fineness
It is possible to manufacture
different types of cement by
changing the percentages of
their raw materials.

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Oxide
CaO
SiO2
Al2O3
Fe2O3
SO3

Notation
C
S
A
F

H2O
MgO
Na2
O

H
M
N

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Compound Composition of
Clinker / Cement
Chemical
Formula

Oxide Formula

Cement
Notation

Mineral Name

Ca3SiO5

3CaO.SiO2

C3S(40-60%)

Alite

Dicalcium Silicate

Ca2SiO4

2CaO.SiO2

C2S(16-30%)

Belite

Tricalcium Aluminate

Ca3Al2O6

3CaO.Al2O3

C3A(7-15%)

Aluminate

Tetracalcium
Aluminoferrite

Ca2AlFeO5

4CaO.Al2O3.Fe2O3

C4AF(7-12%)

Ferrite

Calcium hydroxide

Ca(OH)2

CaO.H2O

CH

Portlandite

Calcium sulfate
dihydrate

CaSO4.2H2O

CaO.SO3.2H2O

CSH2

Gypsum

Calcium oxide

CaO

CaO

Lime

Chemical Name
Tricalcium Silicate

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Phase Diagram
Tricalcium Silicate

Tricalcium Aluminate

CaO

CaO

SiO2

Al2O3

CaO

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CaO

CaO

CaO

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Bogues Equations Compound composition

To calculate the amounts of C3S, C2S, C3A, and C4AF in clinker (or the cement)
from its chemical analysis (from the mill certificate)
Assumptions in calculations:
Chemical equilibrium established at the clinkering temperature
Components maintained unchanged through the rapid cooling
period
Compounds are pure
A simple estimate of the phase composition of a Portland Cement can be obtained
from the oxide composition if one assumes that the four main cement minerals
occur in their pure form.
With this assumption, all of the Fe2O3 is assigned to C4AF and the remaining Al2O3
is assigned to C3A.
This leaves a set of two linear equations to be solved for the amounts of C2S and
C3S.
This method is named after the cement chemist R.H. Bogue. A standardized
version of this simple method is given in ASTM C 150. There are two sets of
equations, based on the ratio of A/F in the cement (both inputs and outputs are in
weight percent):

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Case 1 : If
A/F >=0.64
C3S = 4.071C - 7.6S - 6.718A - 1.43F - 2.852S
C2S = 2.867S - 0.7544C3S
C3A = 2.65A - 1.692F
C4AF = 3.043F

Case 2 : If

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A/F < 0.64

C3S = 4.071C - 7.6S - 4.479A 2.859F - 2.852S

C2S = 2.867S - 0.7544C3S
C3A = 0
C4AF = 2.10A + 1.702F

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Fineness of cement
Grinding is the last step in
processing
Measures of fineness
Specific surface
Particle size
distribution
Blaines fineness
Measure of air
permeability
Typical surface areas
350m2 / kg (Normal
cements)
~ 500 m2 / kg (High early
strength cements)

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Significance of fineness
Finer cement = Faster reaction
Finer cement = Higher heat of
hydration
Large particles do not react
with water completely
Higher fineness
Higher shrinkage
Reduced bleeding
Reduced durability
More gypsum needed

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