Lecture 1

Chemical process Industries II

1. Cement 13. Formaldehyde
2. Sugar 14. Styrene
3. Vegetable oil 15. Phenols
4. Pulp & paper 16. Phthalic anhydride
5. Olefins 17. Alkyl benzenes
6. Ethylene 18. Amines
7. Propylene 19. Ketones,
8. Acetylene 20. Carboxylic acid
9. Butadiene 21. Esters
10. Methanol 22. Ethylene oxide
11. Benzene 23. Terephthalic acid.
12. Vinyl chloride
• Minor 1 (20 Marks)
• Presentation (5 Marks)
Cement
 Cement is the glue that holds the concrete together.
therefore critical for meeting society's needs of housing
and basic infrastructure such as bridges, roads, water
treatment facilities, schools and hospitals. Concrete is the
second most consumed material after water.
Applications of Cement
 Housing is the major sector of cement consumption
about 67% of the total consumption. Being one of the
basic elements for setting up strong and healthy
infrastructure, Cement plays a crucial role in economic
development of any country. Having more than a hundred
and fifty years history, it has been used extensively in
construction of anything, from a small building to a
mammoth multi purpose project.
Production Regions
 India is very vast and this makes cement industry to
divide in five regions. North, East, West, South and Central
region, so that transport and logging can be easy for
cement dealers and consumers. The south region has the
highest installed capacity of cement from other regions.
One third of total capacity is produced by southern
region. At present Lafarge, Ultratech and Wonder cement
have installed high capacitive plants.

4
History
 The first cement produced was Portland cement in
Calcutta, In1889, directory of George watts wrote
“Economic products of India” stated Portland cement but
it was an unorganised procedure for manufacturing
cement.
 In 1914, Porbandar plant showed direction to others and
got succeeded in organised cement process and produced
cement. Its capacity was only 1000 tonnes per annum.
Current Status
 Now India is the second largest producer of cement
in whole world. India is having more than 139 large
cement plants and over 365 small cement plants.
Cont…
 India is producing 350 million tonnes per year and it
is expected to grow to 550 million tonnes by financial
year 2020.
 It is expected that in the coming years cement
industry will have high market share because of the
upcoming housing projects and infrastructure
development programs in India.
 Ultratech cement, Ambuja cement, J.K. cement, Shree
cement and ACC cement are the top players of
cement industry in India.
 Cement
Cement is a mixture of finely ground silicates , aluminates, ferrites of calcium in varying
proportions which hydrates with water to form a rigid continuous structures or mass
with good compressive strength . Mixture is commonly called PORTLAND CEMENT

Basic Chemical Components of Portland Cement:

– Calcium (Ca)
– Silicon (Si)
– Aluminum (Al)
– Iron (Fe)

• Typical Raw Materials:

– Limestone (CaCO3)
– Sand (SiO2)
–Clay (SiO2, Al2O3, Fe2O3)
– Iron Ore (Fe2O3 )
--MgO,
8
CaO
functions and effects of various chemical ingredients of cement

Lime
Lime is the major ingredient of cement. It makes the cement sound and also provides
strength to the cement. Lime in excess makes the cement unsound and causes the cement
to expand and disintegrate. The deficiency of lime will decrease the strength and cause the
cement to set quickly.
Silica
Silica provides strength to the cement. Silica in excess causes the cement to set slowly.
Alumina
Alumina lowers the clinkering temperature. It provides quick setting property to the
cement. Alumina in excess weakens the strength of the cement.
Iron Oxide
Iron oxide provides colour, hardness and strength to the cement. It helps the fusion of
material at lower temperature during the manufacturing of cement.
Magnesium Oxide
Magnesium oxide provides colour and hardness to the cement. Excess magnesium oxide
remains in free state and makes the cement unsound.
Sulphur Trioxide
Sulphur trioxide makes the cement sound if present in very small quantity. Excess sulphur
trioxide makes the cement unsound.
9
Cement : Properties and
Types of Cement
Physical Properties of Cement

• SettingTime
• Soundness
• Fineness
• Strength
 Setting Time
• Cement paste setting time is affected by a number of items
including: cement fineness, water-cement ratio and chemical
content (especially gypsum content).
• For construction purposes, the initial set must not be too soon
and the final set must not be too late. Normally, two setting times
are defined:
• Initial set. Occurs when the paste begins to stiffen
considerably.
• Final set. Occurs when the cement has hardened to the
point at which it can sustain some load.
• Setting is mainly caused by C3A(Tricalcium Aluminate) and
C3S(Tricalcium Silicate ) and results in temperature rise in the
cement paste.
Vicat apparatus for Setting Time
Setting Time : Consistency
• The consistency is measured by the Vicat
apparatus using a 10mm diameter plunger.
• A trial paste of cement and water is mixed and
placed in the mould having an inside diameter of
70mm at the base and 60mm at the top, and a height
of 40mm.
• The plunger is then brought into contact with the
top surface of the paste and released. Under the
action of its weight the plunger will penetrate the
paste.The depth depending on the consistency.
Setting Time : Consistency
Setting Time : Consistency

• When the plunger penetrates the paste to a point 5

to 7mm from the bottom of the mould.The paste is
considered to be at “normal consistency”.
• The water content of the paste is expressed as a
percentage by weight of dry cement.The usual range of
values being between 26% and 33%.
 Setting Time : Setting time

• Initial setting time is regarded as the time elapsed

between the moment that the water is added to the
cement, to the time that the paste starts losing its
plasticity.

• The final setting time is the time elapsed between the

moment the water is added to the cement, and the time
when the paste has completely lost its plasticity and has
attained sufficient firmness to resist certain definite
pressure.
Setting Time : Setting time
• The setting time test is conducted by using the same Vicat
apparatus, except that a 1mm diameter needle is used for
penetration.
• The test is started about 15 minutes after placing the
cement paste (which has normal consistency) into the
mould.Trials for penetration of the needle are made.
• The final setting time is defined as the length of time
between the penetration of the paste and the time when the
needle(with annular ring) no longer sinks visibly into the
paste.
• The initial setting time is defined as the length of time
between the penetration of the paste and the time when the
needle penetrates 25mm into the cement paste.
Soundness
• When referring to Portland cement, "soundness"
refers to the ability of a hardened cement paste to
retain its volume after setting without delayed
expansion. This expansion is caused by excessive
amounts of free lime (CaO) or magnesia (MgO). Most
Portland cement specifications limit magnesia content
and expansion.
• The cement paste should not undergo large changes in
volume after it has set. However, when excessive
amounts of free CaO or MgO are present in the cement,
these oxides can slowly hydrate and cause expansion of
the hardened cement paste.
• Soundness is defined as the volume stability of the
cement paste.
 Soundness: Le Chatelier Test
• IS prescribe a Soundness Test conducted by using the
Le Chatelier apparatus.The apparatus consists of a
small brass cylinder split along its generatrix.Two
indicators with pointed ends are attached to the
cylinder on either side of the split.
 Soundness: Le Chatelier Test
• The cylinder (which is open on both ends) is placed on
a glass plate filled with cement paste of normal
consistency, and covered with another glass plate.
• The whole assembly is then immersed in water at 20 ±
1oC for 24 hours. At the end of that period the distance
between the indicator points is measured.The mould is
then immersed in water again and brought to a boil.
After boiling for one hour the mould is removed from
the water, after cooling, the distance between the
indicator points is measured again.
• This increase represents the expansion of the cement
paste for Portland cements, expansion is limited to
10mm.
Soundness: Le Chatelier Test
Fineness
• Fineness, or particle size of Portland cement affects
Hydration rate and thus the rate of strength gain.The
smaller the particle size, the greater the surface area-to-
volume ratio, and thus, the more area available for water-
cement interaction per unit volume.The effects of greater
fineness on strength are generally seen during the first
seven days.
• When the cement particles are coarser, hydration
starts on the surface of the particles. So the coarser
particles may not be completely hydrated.This
causeslow strength and low durability.
• For a rapid development of strength a high fineness is
necessary.
Fineness Test

• Fineness of Cement is measured by sieving cement

on standard sieve. The proportion of cement of
which the cement particle sizes are greater than
the 90 micron is determined.

• A good cement should retain

10% wt of cement when
it is sieved with 90 µm sieve.
Strength

• Cement paste strength is typically defined in three

ways: compressive, tensile and flexural.These
strengths can be affected by a number of items
including: water cement ratio, cement-fine aggregate
ratio, type and grading of fine aggregate, curing
conditions, size and shape of specimen, loading
conditions and age.
Strength of Cement
• The cement paste (consisting of 1 part cement+3
parts standard sand+ water, by weight) is placed
in 7cm moulds.

• The mortar specimens taken out of the mould are

subjected to compression to determine the
strength.
Strength : Compressive Strength

• The compressive strength test is conducted on mortar cubes.

After finding the breaking load in compression, Pmax ,
Compressive Strength is calculated by the = Pmax /A,
where A=50cm2 .
• The average of the results found by testing six specimen is
the compressive strength of the mortar cubes.
Properties of cements
 BROAD CLASSIFICATION OF CEMENT

1. Ordinary Portland Cement

2. Rapid Hardening Cement
3. Quick Setting Cement
4. Low Heat Cement
5. Blast Furnace Slag Cement
6. Portland Pozzolana Cement
7. Coloured Cement
8. White Cement
9. Sulphate Resisting Cement
10. Air Entraining Cement
11. Hydrophobic Cement
12. Oil Well Cement
13. High Alumina Cement
Ordinary Portland Cement

• Ordinary/Normal Portland cement is one of the

most widely used type of Portland Cement. The
name Portland cement was given by Joseph Aspdin
in 1824 due to its similarity in colour and its quality
when it hardens like Portland stone. Portland stone
is white grey limestone in island of Portland, Dorset.

• It is known as OPC cement in short and also

known as grey cement in India. It consists of 95%
clinker and only 5% gypsum and a few percentages
of other materials. It accounts 69 percent of total
consumption.
Uses Ordinary Portland Cement
• It is used for general construction
purposes where special properties are
not required.
• It is normally used for the reinforced
concrete buildings, bridges,
pavements, and where soil conditions
are normal.
• It is also used for most of concrete
masonry units and for all uses where the
concrete is not subject to special sulfate
hazard or where the heat generated by
the hydration of cement is not
objectionable.
• It has great resistance to cracking and
shrinkage but has less resistance to
chemical attacks.
Production
 Today, Ordinary Portland cement is the most widely
used building material in the world with about 1.56
billion tones produced each year. Annual global
production of Portland cement concrete is around
3.8 million cubic meters per year.
Rapid Hardening Cement

 It is also known as High-Early-Strength cement. It is

manufactured with such adjustments in the
proportion of raw materials so that the cement
produced attains maximum strength with-in 24-72
hours.
Properties & uses

• Two essential properties of Rapid Hardening Cement are

following.
(i) It contains relatively more tri-calcium silicate. This is done
by adding a greater proportion of limestone in the raw
materials compared to that required for ordinary cement.
(ii) It is more fine-grained ( Air permeability 3250 cm2/gm )
than the ordinary cement. This factors helps in quicker and
complete hydration of cement particles during setting and
helps in gaining early strength.
 Generally used for Road Pavement Works,
making of Beams and Colum's etc.
 Quick Setting Cement
 These Types of Cement are quite different than rapid
hardening cement.
 This type of cement is manufactured by reducing the amount
of gypsum and adding small amount of aluminium sulphate to
accelerate setting time of cement around 30 min.
 This property, of setting as quickly as possible is achieved
by following controls in the manufacturing process:
(i) The quantity of retarding agents like gypsum is reduced
to bare minimum.
(ii) The quantity of alumina-rich compound is reduced.
(iii) The clinker is ground to extreme fineness.
 Generally used for
 In Underwater Constructions
 In Cold and Rainy weather Conditions
Low Heat Cement

• This type cement is produced by lowereing the amount of

tri-calcium aluminate (C3A) & di-calcium silicate (C2S)
• Composition:
(i) The proportion of di-calcium silicate (C2S) is almost
double than ordinary cement.
(iii) The proportion of tricalcium silicate (C3S) and tri-calcium
aluminate (C3Al) are reduced by about 50 percent.
Uses
 It is mostly used in mega projects construction like DAMS. If
we use ordinary Portland cement instead of low heat cement
in such structures, Cracks will develop in such structures due
to the great amount of heat liberated during setting and
hardening.
 HIGH ALUMINA CEMENT
 This cement produced by grinding clinkers formed by
bauxite and lime. The bauxite is an aluminum
Oxide(Al2O3).
 In this cement alumina content should not less then
32%.
 Ratio of weight of alumina to the lime should not be
between 0.85 to 1.30.
 It can stand high temperature.

 It sets quickly and attainshigher ultimate strength in short

period.
 It is not suitable for mass construction as it evolves
great heat.
Properties & uses
 Blast Furnace Cement
 This cement made by Slag obtained from blast
furnace.
 The slag is waste product in the manufacturing
process of iron.
 It contains alumina, lime and silica.

 This cement more or less same as OPC.

 Its strength in early days is less and hence is

requires longer curing period.
 The slag cement offers better workability,
cohesiveness, and plasticity.
 Uses
 Slag Cement consists of 50 % blast furnace slag, 45% clinker
and 10% of gypsum. It accounts 10% of total consumption. It is
generally used for massive construction with high cohesiveness.
 It is used in construction of dams. It can be used for works
economic considerations is predominant.
Pozzolana Cement

 In this cement type, clinker and pozzolanic material

such as (volcanic ash, fly ash etc) are mixed in a
definite proportion with Portland cement.
 The pozzolanic materials do not have any cementing
qualities when used alone, but when mixed with
Portland cement, they react with cement
components and form compounds with cementing
properties.
Properties & uses

These qualities make it more useful for construction

near or along the coast and also in sulfate soil. It can
also be used in sewage works and for underwater
construction.
 COLOURED CEMENT
 Coloured cement will be obtained by mixing of
pigments with ordinary Portland cement.
 The amount of coloring material may vary from
5 to 10 %.
 If this percentage exceeds
10 % the strength of cement is
affected.
SI .No Pigment Colour
1 Chromium Oxide Green
2 Cobalt Imparts Blue
3 Iron Oxide in different Brown, Red, Yellow
proportion
4 Manganese Dioxide Black or Brown
Uses
 Coloured cement are widely used Finishing Interior
exterior, Flooring and artificial marble.
White Cement

 White cement are manufactured from pure

limestone (chalk) and clay that are totally free from
iron oxides and any other pigments like manganese
and chromium.
 The kiln is fired by oil rather than by coal to avoid
any contamination.
 The strength and setting time is similar to ordinary
Portland cement.
 WC used in white washing purpose
 Uses
 White cement are the most favored material for use in making
highways curbs and for a variety of ornamental work. They are
also used widely for making cast stones of appealing
appearance.
 White cement are comparatively a costly cement type and is,
therefore, used only selectively.
 HYDROPHOBIC CEMENT
 This type of cement contains admixtures which
decrease the wetting ability of cement grains.
 The usual hydrophobic admixtures are acidol,
naphthenesoap, oxidized petrolatum, Oletic acid
and Stearic acid.
 Above substance formed water repellent film
around each cement grains.
 This film protects them form the bad effect of
moisture during storage and transportation.
The film is broken out when the cement and
aggregate are mixed together.
USES

 Such cement types are used especially in cold, frost-

forming conditions.
Super Sulfate Cements

 These types of cement are manufactured by adding

additional quantities of calcium sulfate and blast
furnace slag in the Portland cement.
 It is especially useful for mass concrete work
especially in sulfate-rich environment and marine
conditions. Besides, it is comparatively economical
than other types of cement.
 Air Entraining Cement

 Air entraining cement is produced by adding indigenous

air entraining agents such as resins, glues, sodium salts
of sulphates etc. during the grinding of clinker.

 This type of cement is specially suited to improve the

workability with smaller water cement ratio and to
improve frost resistance of concrete because the voids
will reduces durability of concrete.
Manufacturing Process

Cement is usually manufactured by two processes:

• Wet process
• Dry process

There are five stages in manufacturing of cement by wet process:

1. Crushing and grinding of raw material

2. Mixing the material in proportion
3. Heating the prepared mixture in rotary kiln
4. Grinding the heated product known as clinker
5. Mixing and grinding of cement clinker with gypsum
 Crushing And Grinding:
In this phase, soft raw materials are first crushed into suitable size.
This is done usually in cylindrical balls or tube mills
containing the charge of steel balls.
 Mixing the material:
In this part, the powdered limestone is mixed with the clay paste in
proper proportion (75%=limestone; clay=25%)
The mixture is then grounded and made homogeneous by mean of
compressed gas.
The resulting material is known as “Slurry” having 35-40% water.
 Heating the slurry in rotary kiln:
Slurry is then introduced in rotary kiln with the help of conveyor.
The rotary kiln consists of large cylinders 8 to 15 feet in
diameter & height of 300-500 feet.
Kiln rotates at the rate of 1-2 revolution per minute. In rotary kiln,
slurry passed through different zones of temperature. This
whole process in kiln usually covers 2 to 3 hours.
Different temperature zones are as under:
i. Preheating Zone : Temperature is kept upto 500 degree
celsius.
ii. Decomposition Zone : Temperature is raised upto 800 degree
celsius.
iii. Burning Zone : Temperature is maintained upto 1500 degree
celsius.
iv. Cooling Zone : This is last stage where the whole assembly is
cooled upto 150 to 200 degree celsius.
 Clinker Formation:
The product which is obtained from the rotary kiln is known as the
“Cement Clinker”. Clinker is usually in the form of greenish
black or grey colored balls.
 Grinding the clinker with gypsum:
The cement clinker is then air cooled. The required amount of
gypsum (5%) is ground to fine powder and then mixed with
clinker.

 Finally, Cement is packed in bags and then transported to the

required site.
Dry Process

The powdered material behaves like a fluid when

exposed to compressed air in a chamber and mixing
becomes possible
This is the most widely used method in the recent
years
It reduces the fuel consumption as the slurry is
already dry unlike wet process.
2. Raw materials are ground to powder and blended.

or Source: PCA, 2003

2. Raw materials are ground, mixed with water to form slurry,

and blended.