Cement Industry

DIPLOMA IN CHEMICAL ENGINEERING - 5TH SEMESTER

Cement Industry, Unit-VII

Baishakhi Kayal
Lecturer in Chemical Engineering

Hooghly Institute of Technology, Hooghly

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CHEMICAL TECHNOLGY- I

CEMENT INDUSTRY, UNIT- VII

INTRODUCTION
Cement is broadly described as material having adhesive and cohesive property
with capacity to bond the material like stone, bricks, building blocks etc. Cement
is a binder, a substance that sets and hardens independently, and can bind other
materials together. Cements are inorganic material that shows the cementing
properties of setting and hardening when mixed with water. Cement is prepared
from calcareous (Ca) material and argillaceous (Al + Si) material.

Cement has property of setting and hardening under water by virtue of chemical
reaction of hydrolysis and hydration. Therefore, cements are generally divided
into two types hydraulic and non-hydraulic that is on the basis of their setting
and hardening pattern. Hydraulic cements 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. Non-hydraulic cements must
be kept dry in order to retain their strength. Portland cement is example of
hydraulic cement material while ordinary lime and gypsum plaster are consider
as example of non- hydraulic cement.

Cement is used for structural construction like buildings, roads, bridges, dam etc.
The most important use is the production of mortar and concrete the bonding of
natural or artificial aggregates to form a strong building material that is durable

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in the face of normal environmental effects.

Both cement and concrete are different, because the term cement refers to the
material used to bind the aggregate materials of concrete. Concrete is a
combination of a cement and aggregate.
CLASSIFICATION

Based on source of cement

1. Natural cement
2. Artificial cement

1. Natural cement
Natural cement is obtained by burning and crushing of 20-40% clay, carbonate
of lime and small amount of magnesium carbonate. It is brown in colour and best
variety known as Roman cement. The natural cement resembles very costly
element hydraulic lime and sets very quickly and strongly as compare to
artificial cement. It finds very limited application

2. Artificial cement
Artificial cement is obtained by burning of calcareous mixture at very high
temperature. Mixture of ingredients should be intimate and they should be in
correct proportion. Calcined product is known as Clinker. A small quantity of
gypsum added to clinker and pulverized to fine powder is known as cement or
ordinary cement or normal setting cement. After setting, this cement closely a
variety of sandstone which is found in abundance in Portland in UK. Therefore,
it is also known as Portland cement.

Other types of Cement

1. Puzzolana cement
It is the material which when mixed with lime without heating gives hydraulic
cement. They mainly contains silicates of aluminum, iron and calcium natural

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Puzzolana which is found in deposits of volcanic ash consist of glassy material

and simple mixing and grinding gives the cement. Similarly slaked lime also
gives Puzzolana cement but they are the cement of ancient time and at present
hardly used.
Puzzolana is a volcanic powder. It is found in Italy near Vesuvius. It resembles
surkhi which is prepared by burning bricks made from ordinary soils. It can also
be processed from shales and certain types of clays. Puzzolana material should
be used in between10 to 30%.

Advantage
➢ Evolves less heat during setting
➢ Possesses higher tensile strength
➢ Imparts higher degree of water tightness
➢ Attains comprehensive strength with age
➢ Can resist action of sulfates
➢ Imparts plasticity and workability to mortar and concrete prepared from it.
➢ Offers great resistance to expansion
➢ It is cheap

Disadvantages
➢ Compressive strength in early days is less
➢ Possesses less resistance to erosion and weathering action

This cement is used to prepare mass concrete of lean mix and for marine
structures. It is also used in sewage works and for laying concrete under water.

2. High alumina cement

It is produced by grinding clinkers formed by calcining bauxite (ore of
Aluminium) and lime. It is specified that total alumina content should not less
than 32% and the ratio by weight of alumina to lime should be between 0.85 and
1.30.

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Advantage
1. Can withstand high temperatures
2. Initial setting time is more than 3 hours. Final setting time is about 5
hours. Therefore, it allows more time for mixing and placing operations
3. Evolves great heat during setting, hence, not affected by frost
4. Resists the action of acids in a better way
5. Sets quickly and it attains compressive strength of about 400 kg/cm2
after 1 day and that after 3 days is about 500 kg/cm2
6. Its setting action mainly depends on the chemical reactions and hence, it
is not necessary to grind it to fine powder

Disadvantage
1. Extreme care is to be taken to see that it does not come in contact with
even traces of lime or ordinary cement.
2. It cannot be used in mass construction as it evolves great heat.
3. It is costly.

3. Slag cement
It is made by mixing blast furnace slag and hydrated lime. Furnace slag largely
contains silicates of calcium and aluminum which is granulated by pouring it
into cold water. Later it is dried and mixed with hydrated lime and the mixture is
finally powdered to increase the rate of setting. Accelerator like clay, salt or
caustic soda may be added.

4. Hydraulic Lime cement is used only for brick mortar composition , low price
and strength.

5. Magnesium oxychloride cement is lightly calcined MgO mixed with MgCl2

forms excellent high strength , spark proof , wear resistant flooring , high

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bonding strength to wood fibers so useful in forming indoor construction

material with only fair resistance to water.

6. Acid resistance cement

It is composed of

1. Acid resistant aggregates like quartz

2. Additives such as Na 2SiF6
3. Aqueous solution of sodium silicate or sodium glass

Sodium fluorosilicate accelerates the hardening process of soluble glass and

increase the resistance to acid.

Soluble glass (water solution of sodium or potassium silicate) is used as binding

material.

The cement has poor water resistance and fails when attacked by water or weak
acids. By adding 0.5% linseed oil or 2% ceresit, its resistance to water is
increased and cement is known as acid and water resistance cement.
It is used in acid resistant and heat resistant coatings or insulations in chemical
industry.

7. White cement
It is a variety of ordinary cement having white colour. It is prepared from
colourless oxides of iron, manganese or chromium. For burning of this cement,
oil fuel is used instead of coal. It should not set earlier than 30 minutes. It should
be carefully transported and stored in closed containers only. It is more costly
than ordinary cement because of specific requirements imposed upon the raw
materials and the manufacturing process.

It is used for floor finish, plaster work ornamental work etc.

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8. Rapid hardening cement

The cement is slightly costly than ordinary cement. Initial and final setting times
of it are the same as those of ordinary cement. But it attains high strength in early
days due to following facts

1. Very fine grinding

2. Burning at high temperatures.
3. Increased lime content in cement composition.

Advantage
1. As it sets rapidly, construction work may be carried out speedily.
2. Increased the frequency of use of formwork of concrete, due to possible
earlier removal
3. Structural members constructed with this cement may be loaded earlier.
4. Requires short period of cutting
5. It obtains strength in a short period. Compressive strength at the end of
one day is about 115 kg/cm2 and after 3 days is about 210 kg/cm2.
Similarly tensile strength at the end of one day is about 20 kg/cm 2 and
that after 3 days is about 30 kg/cm2
6. It is light in weight
7. Allows higher permissible stresses in the design. It therefore results in
economic design.

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Properties of Cement

Physical Properties of Cement

Different blends of cement used in construction are characterized by their physical

properties. Some key parameters control the quality of cement. The physical
properties of good cement are based on:

• Fineness of cement
• Soundness
• Consistency
• Strength

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• Setting time
• Heat of hydration
• Loss of ignition
• Bulk density
• Specific gravity (Relative density)

Fineness of Cement

The size of the particles of the cement is its fineness. The required fineness of good
cement is achieved through grinding the clinker in the last step of cement
production process. As hydration rate of cement is directly related to the cement
particle size, fineness of cement is very important.

Soundness of Cement

Soundness refers to the ability of cement to not shrink upon hardening. Good
quality cement retains its volume after setting without delayed expansion, which is
caused by excessive free lime and magnesia.

Consistency of Cement

The ability of cement paste of flow is consistency

Strength of Cement
Three types of strength of cement are measured- compressive, tensile and flexural.
Various factors affect the strength, such as water-cement ratio, cement –fine
aggregate ratio, curing conditions, size and shape of a specimen, the manner of
molding and mixing, loading conditions and age.

Setting Time of Cement

Cement sets and hardens when water is added. This setting time can vary
depending on multiple factors , such as fineness of cement, cement water ratio,
chemical content and admixtures. Two setting times are measured :

Initial set : When paste begins to stiffen ( occurs within 30-45 min)

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Final set : When the cement hardens , being able to sustain load ( occurs below 10
hours ).

Heat of Hydration :

When water is added to cement , the reaction that takes place is called hydration.
Hydration generates heat , which can affect the quality of the cement .The heat of
hydration is affected most by C3S and C3A present in cement, water -cement ratio
and fineness of cement.

Loss of cement : Heating of cement sample at 900 -10000C , causes weight loss.

Bulk Density :

Cement has a varying range of density depending on the cement composition

percentage. The density of cement may be anywhere from 62 to 78 pounds per
cubic foot.

Specific Gravity : Portland cement has a specific gravity of 3.15 , but other types
of cement may have a specific gravities of about 2.90.

Chemical properties of Cement

The raw materials for cement production are limestone ( calcium), sand or clay
(silicon), bauxite (aluminium) and iron ore , and iron ore, and may inclide shells ,
chalk , marl , shale , clay , blast furnace slag , slate. Chemical analysis of cement
raw materials provides insight into the chemical properties of cement.

1. Tri Calcium aluminate (C3A): Low content of cement C3A makes the cement
sulphate resistant.

2. Tri Calcium silicate (C3S): C3S causes rapid hydration as well as hardening
and is responsible for the cement’s early strength gain in initial setting.
3. Di Calcium silicate ( C2S) : Di Calcium silicate in cement helps the strength
gain after one week.
4. Ferrite (C4AF) : Ferite is a fluxing agent . It reduces the melting temperature
of the raw materials in the kiln from 30000F to 26000F . Though it hydrates
rapidly , it does not contribute much to the strength of the cement.

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5. Magnesia (MgO) : The manufacturing process of Portland cement uses

magnesia as a raw material in dry process plants. An excess amount of
magnesia may make the cement unsound and expansive , but a little amount
of it can add strength to the cement.
6. Sulphur Trioxide (SO3): Sulphur Trioxide in excess amount can make
cement unsound.
7. Iron oxide / Ferric Oxide ( Fe2O3) : Iron oxide or ferric oxide is mainly
responsible for the colour of the cement.
8. Alkalis [ (K2O) and ( Na2O)] : The amount of Potassium Oxide ( K2O) and
Sodium Oxide ( Na2O) determine the alkali content of cement. Cement
containing large amount of alkali can cause some difficulty in regulating the
setting time of cement. Low alkali content , when used with calcium chloride
in concrete , can cause discoloration.
9. Free Lime : Free lime , which is sometimes present in cement may cause
expansion.
10. Silica Fumes : Silica fume is added to cement in order to improve a variety of
properties especially compressive strength , abrasion resistance and bond
strength.
11.Alumina (Al2O3) : Cement containing high alumina has the ability to
withstand frigid temperature since alumina is chemical resistant. It also
quickens the setting but weakens the cement.

Constituents of Cement

Code Chemical formula Type %

(a) Portland C2S 2 CaO.SiO2 Silicate Major

C3S 3CaO.SiO2 Silicate Major

C3A 3CaO.Al2O3 Aluminate Major

C4AF 4CaO. Al2O3.Fe2O3 Aluminate Minor

__ MgO Minor

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__ CaO Minor

➢ Tricalcium Silicate (C3S): Hardens rapidly and is largely responsible for

initial set and early strength. In general, the early strength of Portland
cement concrete is higher with increased percentages of C3S
➢ Dicalcium Silicate (C2S): Hardens slowly and contributes largely to
strength increases at ages beyond 7 days.
➢ Tricalcium Aluminate (C3A): Liberates a large amount of heat during
the first few days of hardening and together with C3S and C2S may
somewhat increase the early strength of the hardening cement. It affects
setting time.
➢ Tetracalcium Aluminoferrite (C4AF): Contributes very slightly to
strength gain. However, acts as a flux during manufacturing. Contributes
to the colour effects that makes cement gray.

(b) High Alumina C3A 3CaO. Al2O3 Aluminate Major

C2S 2 CaO.SiO2 Silicate Minor

C4AS 4CaO. Al2O3.SiO2 Mixed Minor

(c) Hydraulic __ Ca(OH)2 Hydroxide Major

Hydrated lime
C2S 2CaO.SiO2 Silicate Minor

C3A 3CaO.Al2O3 Aluminate Minor

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Uses of Cement

1. Production of Concrete
2. Construction purpose i.e Buildings, Bridges, Dams, water pipes, drains,
canals , etc.
3. Transport i.e road ,pavements , crossing etc.
4. Agricultural field

Types of Portland Cement

Varying the percentage of constituents changes the rate of setting , heat evolution ,
strength characteristics , Portland cement can be classified as :

1. Type I – Regular : 40-60 % C3S , 10-30 % Ca2S , 7-13 % Ca3A, hardens to full
strength in 28 days.

2. Type II – Modified : Higher C2S/ C3S to resist sulfate attack

3. Type III – High Early strength : Attains strength of Type I in only 3 days ; high
heat rates , useless on massive structure , higher C3S and C3A percentage with finer
grinding to increase hydration rate.

4. Type IV – Low Heat : Designed for massive structure work ; low C3S and C3A
which are largest contributors to heat of hydration.

5. Type V – Sulphate Resistant : Good for sea water contact : C3A˂ 4 %.

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Method of Production :

Classification of processes :

1. Cement rock beneficiation

2. Portland cement production.

1. Cement rock beneficiation

Much of the locally available limestone has too high a silica and iron content for
direct use in cement manufacture. These undesirable constituents can be removed
by ore dressing or beneficiation methods.

Quantitative requirements: For 1 ton of low grade limestone

Water required: 2-3 tons

Reagents: 50-200 gm

Electricity: 2.5 KWH

Process Description:

The operations are grinding, classification, flotation and thickening.

The rock is wet ground, fed to a hydro separator where the overflow goes directly
to the final thickener, being of satisfactory composition. If not, it is subjected to
flotation separation as well as the course material which must be floated to remove
silica, mica and talc.

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Flotation is based on the ability of a collecting agent to wet certain minerals

causing these to be entrained in an air froth which rises to the surface and
overflows the flotation cell into the thickener cascade. In these latter units the
flotation liquor is recycled and the beneficiated cement rock slurry is fed directly to
cement kilns.

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Portland cement Production Process

Raw materials
Basis: 1000kg of cement
Clay = 100-300kg
Limestone = 1200-1300kg
Gypsum = 30-50kg
Coal = 250-400kg
Water = 3000kg
Electricity = 80kWH

The most commonly used composition on % basis by mass for the Portland
cement manufacturing is given below

Component % range
by mass
Lime ( CaO) 60-69
Silica (SiO2) 17-25
Alumina (Al 2O3) 3-8
Iron oxide (Fe 2O 3) 2-4
Magnesium oxide (MgO) 1-5
Sulfur trioxide (SO3) 1-3
Alkali Oxide (Na 2O + K 2O) 0.3-1.5
Gypsum 2-4

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Significance of constituents

Lime

Lime is also defined as non-hydraulic cement mainly consisting of calcium oxide

and small amount of magnesium oxide. It is prepared by calcining the lime stone
(CaCO3) at temperature that it will slake, when brought in contact with water. It
is principal constituent of cement. Proper amount of lime is important as excess
of it reduces the strength as well as lesser amount also reduces the strength and
makes its quick setting. Lime is mainly used for white washing of mortar for
joining bricks, metallurgy and glass industries.

Silica

It imparts strength to cement.

Alumina

It works as an accelerator and makes the cement quick settling. However excess
of alumina makes the cement unsound.

Gypsum (Calcium sulfate)

It retards the setting action of cement but enhances the initial setting time.

Iron oxide

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It provides colour, strength and hardness of cement.

Magnesia

If present in small amount impart hardness and colour to cement

Sulfur trioxide

If present in small amount it imparts soundness to cement but excess of it is

undesirable

Alkalis

Most of the alkalis present in raw materials are carried away by the flue gases
during heating and cement contains only a small amount of alkalis. If present in
excess causes the efflorescent to cement.

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Process Description:

It involves the following steps

1. Mixing of raw material

2. Burning
3. Grinding
4. Storage and packaging

1. Mixing of raw material

Mixing can be done by any one of the following two processes

a) Dry process

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b) Wet process

Mixing in Dry process

Lime stone or chalk and clay are crushed into gyratory crusher to get 2-5 cm size
pieces. Crushed material is ground to get fine particle into ball mill or tube mill.
Each material after screening stored in a separate hopper. The powder is mixed
in require proportions to get dry raw mix which is stored in silos (storage tank)
and kept ready to be fed into the rotary kiln. Raw materials are mixed in required
proportions so that average composition of the final product is maintained
properly.

Mixing in Wet process

Raw materials are crushed, powdered and stored in silos. The clay is washed
with water in wash mills to remove adhering organic matter. The washed clay is
stored separately. Powdered lime stone and wet clay are allowed to flow in
channel and transfer to grinding mills where they are intimately mixed and paste
is formed known as slurry. Grinding may be done either in ball mill or tube mill
or both. Then slurry is led to correcting basin where chemical composition may
be adjusted. The slurry contains 38-40% water stored in storage tank and kept
ready for feeding to a rotary kiln.

Burning
Burning is carried out in rotary kiln which rotating at 1-2 rpm at its longitudinal
axis. Rotary kiln is steel tubes having diameter in between 2.5-3.0meter and
length varies from 90-120 meter. The inner side of kiln is lined with refractory

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bricks. The kiln is rested on roller bearing and supported columns of masonry or
concrete in slightly inclined position at gradient of 1 in 25 to 1 in 30. The raw
mix or corrected slurry is injected into the kiln from its upper end. Burning fuel
like powdered coal or oil or hot gases are forced through the lower end of the
kiln so long hot flame is produced.

Due to inclined position and slow rotation of the kiln, the material charged from
upper end is moving towards lower end (hottest zone) at a speed of
15meter/hour. As gradually descends the temperature is rises. In the upper part,
water or moisture in the material is evaporated at 4000C temperature, so it is
known as drying zone.

In the central part (calcination zone), temperature is around 1000 0C, where
decomposition of lime stone takes place. After escapes of CO2, the remaining
material in the forms small lumps called nodules.

CaCO3 CaO + CO2

The lower part (clinkering zone) have temperature in between 1500-17000C

where lime and clay are reacts to yielding calcium aluminates and calcium
silicates. This aluminates and silicates of calcium fuse to gather to form small
and hard stones are known as clinkers. The size of the clinker is varies from 5-
10mm.

2CaO + SiO2 Ca 2SiO4 (dicalcium silicate (C 2S))

3CaO + SiO2 Ca 3SiO 5 (tricalcium silicate(C 3S)

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3CaO + Al 2O 3 Ca 3Al 2O 6 (dicalcium aluminate (C 2A))

4CaO + Al 2O 3 + Fe 2O 3 Ca 4Al 2Fe 2O10 (tetracalcium
Alumino ferrite (C 4AF))

As clinkers are coming from burning zone, they are very hot. The clinkers are
cooled down by air admitting counter current direction at the base of rotary kiln.
Resulting hot air is used for burning powdered coal or oil and cooled clinkers are
collected in small trolleys or in small rotary kiln.

2. Grinding

Cooled clinkers are ground to fine powder in ball mill or tube mill. 2-3%
powdered gypsum is added as retarding agent during final grinding. So that,
resulting cement does not settle quickly, when comes in contact with water.
After initial set, cement - water paste becomes stiff, but gypsum retards the
dissolution of tri-calcium aluminates by forming tricalcium sulfoaluminate
which is insoluble and prevents too early further reactions of setting and
hardening.

3CaO.Al 2O 3 + xCaSO 4.7H 2O 3CaO.Al 2O 3.xCaSO4.7H 2O

3. Storage and packaging

The ground cement is stored in silos, from which it is marketed either in

container load or 50kg bags.

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Comparison of dry process and wet process

Criteria Dry process Wet process

Hardness of raw material Quite hard Any type of raw material
Fuel consumption Low High
Time of process Lesser Higher
Quality Inferior quality Superior quality
Cost of production High Low
Overall cost Costly Cheaper
Physical state Raw mix (solid) Slurry (liquid)

Composition of Portland cement clinker

Components Content in clinker

Wt. %
CaO 63.8-70.1
SiO2 19.7-24.3
Al 2O3 3.8-6.8
Fe 2O3 1.3-1.6
MgO 0.0-4.5
SO3 0.2-2.1
K 2O 0.3-1.8
Na 2O 0.0-0.3
Mn 2O3 0.0-0.7

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TiO2 0.2-0.5
P 2O 5 0.0-0.3
CO2 0.0-0.8
H 2O 0.0-1.1

Gypsum addition in the cement

In the manufacture process of cement, clinkers are formed. These cement
clinkers are cooled down and added with small amount of gypsum. The mixture
then sent to final grinding process. For ordinary Portland cement it remains
between 3 to 4% and in case of Quick setting cement it can be reduced up to
2.5%.

Role of Gypsum in Cement

Gypsum is a mineral and is hydrated calcium sulphate in chemical form.
Gypsum plays a very important role in controlling the rate of hardening of the
cement, so it is generally termed as retarding agent of cement. It is mainly used
for regulating the setting time of cement and is an indispensable component.
The main purpose of adding gypsum in the cement is to slow down the hydration
process of cement once it is mixed with water.

The process involved in hydration of cement is that, when the water is added into
cement, it starts reacting with the C 3A and hardens. The time taken in this
process is very less, which doesn’t allow time for transporting, mixing and
placing.

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A retarder or a negative catalyst is required for controlling the setting. Gypsum

acts as setting retarder. The amount of gypsum required to produce the most
favorable ‘time of set’ has been found to depend on the alumina. It is known
that compounds of alumina, i.e. tricalcium aluminate ( C3A) and tetracalcium
alumino-ferrite ( C4AF) react quickly with water and are the first to hydrate.
With the addition of gypsum , alumina reacts with calcium sulphate to form
calcium sulpho – aluminate which is insoluble and does not hydrate. This has a
general retarding action on the starting of the initial setting after the water is
added and also retards the hydration of tricalcium silicate.

Effects of Gypsum on Cement

1. Gypsum prevents Flash Setting of cement during manufacturing.

2. It retards the setting time of cement.
3. Allows a longer working time for mixing, transporting and placing.
4. When water is mixed to cement Aluminates and sulfates get react and
evolve some heat but gypsum acts as coolant and brings down the heat
of hydration.
5. Gypsum cements possess considerably greater strength and hardness
when compared to non gypsum cement.
6. Water required in gypsum based cement for hydration process is less.

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References :

1. Chemical Process Industries by Shreve , McGraw-Hill Book Co. Ltd., New Yorkand
Kogakusha Co. Ltd., Tokyo.

2. Outlines of Chemical Technology by Dryden , Affiliated East-West Press Pvt. Ltd., New
Delhi

3. Introduction to Chemical Engineering by Ghosal, Sanyal, Dutta , Tata McGraw-Hill Pub.

Co. Ltd., New Delhi

4. Study material of NTPEL online courses.

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