Pamantasan ng Lungsod ng Maynila

College of Engineering and Technology

Department of Chemical Engineering

INTRODUCTION

The industrial uses of limestone and cements have provided important

undertakings for chemists and engineers since the early years. Cement is the
key material in the Building and Construction Industry. In 2011 alone, world
production value exceeded 3.3 billion tons. Throughout history, Cementations
materials have played a vital role, and some might even say that cement has
helped to create the modern society as we know it. The convenience,
cheapness, adaptability, strength and durability of cement products have been
a foundation of these applications.

The growth of Global cement production has expected to continue

increasing. At the manufacturing it involves both high energy consumptions
and the emission of harmful gasses. About 5% of the annual global CO2
emission from human activity stemmed from the Cement Industry. As a result
the Cement Industry is constantly focused on developing more environmental
friendly technologies, while at the same time securing profitability in order to
embrace these challenges.

PORTLAND CEMENTS

Portland cement has been defined as the product obtained by

pulverizing clinker consisting essentially of hydraulic calcium silicates, usually
containing one or more forms of calcium sulfate as an interground addition.

HISTORY

Although the history of Portland Cement is comparatively short, the use

of the structural binding agent dates back thousands of years. One of the
earliest examples is that of the water tanks at Aden which were constructed
6000 B.C. and are still in use today. Analysis of the mortar used by the
Egyptians in the construction of the Pyramid of Cheops in about 3600 B.C.
show that they possessed a good practical knowledge of the subject at the time.

The Greeks, at a very early period of their civilization, used compositions

of lime as a base to cover walls. According to Plinius, the walls of the palace of
Croesus were also protected and ornamented in this manner.

In Italy, the first people to employ mortar in their buildings were the
Etruscans. It was from them that the Romans derived their knowledge of the
art. It says much for their ability as builders that the dome of the Pantheon of
Rome, constructed with a type of concrete, is still in an excellent state of
preservation today.
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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

With the fall of the Roman Empire, all knowledge of cement seemed to
have vanished and nothing more was heard of it until the early part of the
eighteenth century when its use could be traced to England, in almost exactly
the same form as that used by the Egyptians and Romans!

During the first part of the eighteenth century very little progress was
made with the evolution of cement. In 1756, an Engineer named John Smeaton
gave serious attention to the principle of setting lime under water.

After considerable research, Smeaton found that by mixing lime and

pozzolana, a substance was produced which, became hard and solid, with the
addition of water. Although this was not Portland Cement, it was a vast
improvement over lime mortars. The fact that Smeatons lighthouse, which he
built with his own product, stood for 120 years on the Eddystone Rock is
evidence of his success.

Very little notice was taken of Smeatons discovery at the time but 50
years later, the French Chemist, Vicat, went a step further by burning
pulverized chalk and clay together in the form of a paste. His product, like
Smeatons received very little attention. They even carefully picked out and
discarded the very portion of the burnt material which would have given them
Portland Cement! It was not until 1824, that Joseph Aspdin, a Leeds
bricklayer, discovered what is known as Portland Cement.

Aspdin found that by mixing finely pulverized clay in specified

proportions, burning them to a high temperature and then grinding the
resultant clinker, he was able to produce a hydraulic binding material far
superior to any product known at the time. It was Aspdin who named it
Portland Cement because when set it looked like Portland Stone.

CEMENT CHEMISTRY NOTATION AND MINERAL NAMES

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.

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Chemical
Chemical Name Oxide Formula Cement Notation Mineral Name
Formula

Tricalcium
Ca3SiO5 3CaO.SiO2 C3 S Alite
Silicate
Dicalcium
Ca2SiO4 2CaO.SiO2 C2 S Belite
Silicate
Tricalcium
Ca3Al2O6 3CaO.Al2O3 C3A Aluminate
Aluminate

Tetracalcium
Ca2AlFeO5 4CaO.Al2O3.Fe2O3 C4AF Ferrite
Aluminoferrite
Calcium
Ca(OH)2 CaO.H2O CH Portlandite
hydroxide
Calcium
sulfate CaSO4.2H2O CaO.SO3.2H2O C H2 Gypsum
dehydrate
Calcium oxide CaO CaO C Lime

TYPES OF PORTLAND CEMENT

Classification Characteristics Applications

General construction
Fairly high C3S content
Type (most buildings, bridges,
General purpose for good early strength
I pavements, precast units,
development
etc)
Structures exposed to soil
Type Moderate sulfate
Low C3A content (<8%) or water containing sulfate
II resistance
ions
Type Ground more finely, may Rapid construction, cold
High early strength
III have slightly more C3S weather concreting
Type Low heat of hydration Low content of C3S Massive structures such
IV (slow reacting) (<50%) and C3A as dams. Now rare.
Type High sulfate Very low C3A content Structures exposed to
V resistance (<5%) high levels of sulfate ions

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

General Use (GU) is a general-purpose cement suitable wherever the special

properties of other types are not required. Its uses in concrete include
pavements, floors, reinforced concrete buildings, bridges, tanks, reservoirs,
pipe, masonry units and various concrete products. The typical compound
compositions of this type are:

55% (C3S), 19% (C2S), 10% (C3A), 7% (C4AF), 2.8% MgO, 2.9% (SO3), 1.0%
Ignition loss, and 1.0% free CaO.

A limitation on the composition is that the (C3A) shall not exceed fifteen
percent.

Moderate Sulphate Resistant (MS) is used where precaution against

moderate sulphate attack is important. It is used in normal structures or parts
of structures that are exposed to soil or ground waters where sulphate
concentrations are higher than normal but not unusually severe. Its typical
compound composition is:

51% (C3S), 24% (C2S), 6% (C3A), 11% (C4AF), 2.9% MgO, 2.5% (SO3), 0.8%
Ignition loss, and 1.0% free CaO.

A limitation on the composition is that the (C3A) shall not exceed eight percent
which reduces its vulnerability to sulfates. When sulphates in moist soil or
water enter concrete, they cause chemical reactions that result in expansion,
scaling and cracking. Wetting and drying in a sulphate environment aggravates
the formation of sulphate salts or compounds that have sufficient
crystallization pressure to disrupt cement paste.

Concrete exposed to seawater is often made with Moderate Sulphate Resistant

cement. Seawater contains significant amounts of sulphates and chlorides.
Although sulphates in seawater are capable of attacking concrete, the presence
of chlorides reduces the expansive reaction that is characteristic of sulphate
attack.

Moderate Heat of Hydration Hydraulic Cement (MH) is specially

manufactured to generate less heat, at a slower rate than General Use
hydraulic cement. Heat of hydration is the heat generated by the chemical
reaction when cement is initially mixed with water. The requirement of
moderate heat of hydration can be specified at the option of the purchaser.
This type of cement can be used in structures of considerable mass, such as
large piers, foundations and thick retaining walls, in which temperature-related
cracking may be a problem, especially when concrete is placed in warm
weather.

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

High Early Strength Hydraulic Cement (HE) provides high strength relatively
quickly, usually in a week or less. It is chemically and physically similar to
General Use hydraulic cement, except that its particles are more finely ground.
It is used when forms need to be removed promptly or when the structure must
be put into service quickly. In cold weather, its use reduces the length of the
curing period. Its typical compound composition is:

57% (C3S), 19% (C2S), 10% (C3A), 7% (C4AF), 3.0% MgO, 3.1% (SO3), 0.9%
Ignition loss, and 1.3% free CaO.

Low Heat of Hydration Hydraulic Cement (LH) is used where the rate and
amount of heat from hydration must be minimized. It develops strength at a
slower rate than other cement types. This type of cement is intended for use in
massive concrete structures, such as large gravity dams, where the
temperature rise resulting from heat of hydration must be minimized. It is
generally only available by specific request for large projects. Its typical
compound composition is:

28% (C3S), 49% (C2S), 4% (C3A), 12% (C4AF), 1.8% MgO, 1.9% (SO3), 0.9%
Ignition loss, and 0.8% free CaO.

The percentages of (C2S) and (C4AF) are relatively high and (C3S) and (C3A) are
relatively low. A limitation on this type is that the maximum percentage of (C3A)
is seven, and the maximum percentage of (C3S) is thirty-five.

High Sulphate Resistant Hydraulic Cement (HS) is used in concrete exposed

to severe sulphate action, principally where soils or ground waters have high
sulphate content. It gains strength more slowly than General Use hydraulic
cement. Use of a low water-to-cementing-materials ratio and low permeability
are critical to the performance of any concrete exposed to severe sulphate
attacks. Like other portland cements, it is not resistant to acids and other
highly corrosive substances. Its typical compound composition is:

38% (C3S), 43% (C2S), 4% (C3A), 9% (C4AF), 1.9% MgO, 1.8% (SO3), 0.9%
Ignition loss, and 0.8% free CaO.

This cement has a very low (C3A) composition which accounts for its high
sulfate resistance

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

RAW MATERIALS
Typical constituents of Portland cement plus Gypsum
Clinker CCN Mass %
Tricalcium silicate C3S 45-75%
(CaO)3 SiO2
Dicalcium silicate C2S 7-32%
(CaO)2 SiO2
Tricalcium aluminate C3A 0-13%
(CaO)3 Al2O3
Tetracalcium C4AF 0-18%
aluminoferrite (CaO)4
Al2O3 Fe2O3
Gypsum CaSO4 2 H2O C H2 2-10%

Calcium Iron Silica Alumina Sulfate

Alkali Waste Blast-furnace Calcium Aluminum- Anhydrite
Argonite flue dust Silicate ore refuse Calcium,
Calcite Clay Cement Rock Bauxite Sulfate
Cement-kiln Iron ore Clay Cement Rock Gypsum
dust Mill Scale Fly ash Clay
Cement Rock Ore washings Fullers earth Copper Slag
Chalk Pyrite Loess Fly ash
Clay Shale Marl Fullers earth
Fullers Ore washings Grandiorite
Earth Quartzite Limestone
Limestone Rice-Hull ash Loess
Marble Sand Ore washings
Marl Sandstone Shale
Seashells Shale Slag
Shale Slag Staurolite
Slag Traprock

Function of Compounds

When portland cement is mixed with water its chemical compound

constituents undergo a series of chemical reactions that cause it to harden (or
set). These chemical reactions all involve the addition of water to the basic
chemical compounds. This chemical reaction with water is called "hydration".
Each one of these reactions occurs at a different time and rate. Together, the

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 Pamantasan ng Lungsod ng Maynila
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Department of Chemical Engineering

results of these reactions determine how portland cement hardens and gains
strength.

Compound Function
Tricalcium silicate (C3S) Hydrates and hardens rapidly and is
largely responsible for initial set and
early strength. Portland cements with
higher percentages of C3S will exhibit
higher early strength.
Dicalcium silicate (C2S) Hydrates and hardens slowly and is
largely responsible for strength
increases beyond one week.
Tricalcium aluminate (C3A) Hydrates and hardens the quickest.
Liberates a large amount of heat
almost immediately and contributes
somewhat to early strength. Gypsum
is added to portland cement to retard
C3A hydration. Without gypsum, C3A
hydration would cause portland
cement to set almost immediately after
adding water.
Tetracalcium aluminoferrite (C4AF) Hydrates rapidly but contributes very
little to strength. Its use allows lower
kiln temperatures in portland cement
manufacturing. Most portland cement
color effects are due to C4AF.

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

MANUFACTURING PROCESS

Part 1 - raw materials extraction

Part 2 - blending and clinkerization

Part 3 - grinding and distribution

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Manufacturing
Description Equipment
Process
Bulldozers

Involves blasting of Lime

stones and clay for rock
Quarrying
quarries by boring and
setting explosives

Crusher Machine

The quarried material is

then reduced in size by
compression and/or impact
Crushing in various mechanical
crushers. Crushed rock is
reduced in size from 120 cm
to between 1.2 and 8 cm.

Conveyor Belt

Raw material is then

transported from the
Transporting
crusher using conveyors,
and rail wagons.

Roller Mill
The raw materials are milled
and dried in a roller mill.
Heavy rollers are held over a
Raw Milling rotating table and the coarse
material is milled until it is
fine enough to be carried by
air to a homogenizing silo.

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Mixing Bed

The proportional mixing of

Homogenization the clay, lime stones and
other required material

Cyclone pre-heaters enable Pre-Heaters

the raw material of cement
production to be preheated
before entry into the kiln.
This increases the energy
Pre-Heating
efficiency of the kiln as the
material is 20-40% calcined
at the point of entry into the
kiln.

Rotary Kiln
Where the raw materials
react at very high
temperatures to form
Clinkerization 3CaOSiO2, 2CaOSiO2,
3CaOAl2O3, and
4CaOAl2O3Fe2O3

Clinker Cooler

The molten cement clinker is

then cooled as rapidly as
possible. The ambient air
used to cool the clinker is
Cooling
then fed into the kiln as
combustion air - ensuring
high utilization of the heat
produced.

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Clinker Silos

Clinker may be either stored on

site in preparation for grinding
to form cement, or transported
Storing to other sites.

Cement Grinder

The crushing of the clinker

into smaller sizes and then
Grinding
the clinker is mixed with
Gypsum

Cement Mill
Finish milling is the grinding
together of cement clinker,
with around 5% of natural
or synthetic gypsum. Other
Raw Milling cementitious materials such
as slag, fly ash or other
pozzolans may also be
incorporated into the final
cement powder.
Cement Silos

The cement is housed in

Storing Cement Silos from where it
is extracted

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Automated Packing Machine

Cement extracted from silos

is conveyed to the automatic
Packaging electronic packers where it is
packed in 50 kg bags and
dispatched in trucks.

LIME
The word "lime" refers to products derived from
burnt (calcined) limestone, such as quicklime and
hydrated lime. Limestone is a naturally occurring and
abundant sedimentary rock consisting of high levels of
calcium and/or magnesium carbonate, and/or dolomite
(calcium and magnesium carbonate), along with small
amounts of other minerals. It is extracted from quarries
and underground mines all over the world.

Lime Cycle

Quicklime
When limestone/chalk (calcium carbonate) is burnt in the kiln and
releases carbon dioxide.
Hydrated Lime
When water can be added to quicklime/burnt lime.
Recarbonation
Over the lifetime of lime products, carbon dioxide is gradually re-
absorbed by lime from the air, which is known as recarbonation.
Chemically, this begins to turn the lime back into calcium carbonate.
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Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

MANUFACTURING PROCESS

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College of Engineering and Technology
Department of Chemical Engineering

Manufacturing
Description Equipment
Process
Bulldozers

Extraction of limestone or
Quarrying chalk rock from quarries
and mines.

Crusher Machine
The Limestone enters a
primary crusher to break the
rock. Depending on the size
of the feedstone required,
Crushing
limestone may go through a
secondary or tertiary
crusher to further reduce its
size.

Screener

Sorting and separating of

Screening rock pieces into different
sizes

Kiln

The rock is heated to 800C

in the preheater and then
Calcination
1200C to 2000C to make
lime.

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Cooling Tower

Quicklime leaving the

calcining zone is cooled by
Cooling
direct contact with cooling
air.

Lime Hydrators
Quicklime can be processed
into hydrated lime by
crushing the quicklime,
adding water to the crushed
lime (water accounts for
Hydration approximately 1% of raw
hydrate), and then
classifying the hydrated lime
to ensure it meets customer
specifications before it is
transported.

Lime Silos

The Lime is housed in Lime

Storing Silos from where it is
extracted

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

GYPSUM

Gypsum is calcium sulfate dihydrate (CaSO4

2H2O), a white or gray naturally occurring mineral.
Raw gypsum ore is processed into a variety of
products such as a portland cement additive, soil
conditioner, industrial and building plasters, and
gypsum wallboard. To produce plasters or wallboard,
gypsum must be partially dehydrated or calcined to
produce calcium sulfate hemihydrate(CaSO4 H2O),
commonly called stucco.

Raw Material

Gypsum rock (calcium sulphate dihydrate CaSO4.2H2O)

Was formed in geological time through the evaporation of seawater. It is
often laid down in beds, ranging in thickness from a few centimeters to several
tens of meters.

Because gypsum rock is slightly soluble in water it is not usually found

above ground in wet or damp areas, but may be found underground, where it
is not affected by the water table. In dry regions it may also be found on the
surface, sometimes in the form of gypsum sand. The presence of gypsum on or
just below the surface of the ground is often indicated by changes in
vegetation; some plants thrive on gypsum-rich (alkaline) soil whereas others
are not at all tolerant of those conditions.

Gypsum rock is usually white or colorless, although it may sometimes

have grey, yellow, pink, or brown hues. Gypsum is much softer than minerals
of similar color, such as calcite or quartz, and is the only one that can be
scratched with a fingernail. If a piece of gypsum rock is held over a flame it will
turn cloudy and opaque and give off water.

When heated slightly, the following occurs,

CaSO42H2O CaSO2 H2O + 1H2O
If the heating is at a higher temperature, gypsum loses all its water and
becomes anhydrous calcium sulfate, anhydrite

Calcined gypsum (the half water salt) can be made into wall plaster by
addition of a filler material (eg. asbestos, wood pulp or sand)

Plaster of paris (without addition) can be used for making sculptures and craft
projects
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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

MANUFACTURING PROCESS

Manufacturing
Description Equipment
Process
Bulldozer

Gypsum ore, from quarries

Quarrying and underground mines is
extracted

Crusher Machine

The Gypsum ore is further

crushed and screened to
Crushing about 50 millimeters (2
inches) in
diameter.

Raymond Mill

The ore is then ground into

Grinding
smaller pieces.

Rotary Dryer

The ground ore is then

Drying heated to 350F

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

Kettle Calciners

A chemical reaction that

happens when the ground
Calcination ore is then heated to 350F
and 75% water is driven off
as steam.

Gypsum Silos

The Gypsum is then stored

Storage
to Gypsum Silos

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

MISCELLANEOUS CALCIUM COMPOUNDS

Calcium
Description Application Image
Compound
A very widely used
industrial chemical , in
both its pure state
Whiting
A pure, finely
divided CaCO3 Paint, Rubber,
Calcium
prepared by wet Pharmaceutical,
Carbonate
grinding and and Paper
levigating natural Industries
chalk.
Putty Produced
when whiting is
mixed with 18%
boiled linseed oil.

Depilatory in
Made by reducing tanning industry
Calcium
calcium sulfate with and in
Sulfide
coke cosmetics.
Fungicides

Calcium Chloride
Obtained
commercially as a
by-product of
To lay dust on
chemical
highway, and
manufacture and
as an
from natural brines
antifreeze for
Halide Salts which contain more
concrete
or less magnesium
chloride.
Medicine and
Calcium Bromide
Photography
And Iodide
Have properties
similar to Chloride.
Prepared by the

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 Pamantasan ng Lungsod ng Maynila
College of Engineering and Technology
Department of Chemical Engineering

action of the halogen

acids on calcium
oxide or calcium
carbonate

Produced by the Used extensively

Calcium reaction of CaCl2, as an insecticide
Arsenate Ca(OH)2, NaH2AsO4 and as a
H2O (lime) , H3AsO4 fungicide

Calcium acetate and employed

lactate largely in
Prepared by the dying of
reaction of calcium textiles
carbonate with acetic
acid. used in
Calcium
Calcium soaps medicines and
Organic
Made by the action of in foods as
Compounds
the sodium salts of source of
acids on a calcium calcium
salt such as chloride.
These are insoluble in used as
water but soluble In waterproofing
hydrocarbons. agents

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