Pamantasan ng Lungsod ng Maynila

College of Engineering and Technology

Department of Chemical Engineering

Chemical Process Industries

Portland Cement and
Miscellaneous Calcium and
Magnesium Compounds

Fulugan, Ceazar Justine L.

Raguini, Jasmin Fatima D.
Redublo, Anne Paulinne P.
BS ChE 3-1

Engr. Milagros R. Cabangon

Portland Cement and Miscellaneous Calcium and Magnesium Compounds 1

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

TABLE OF CONTENTS

Introduction 4

History of Cement 5

Chemical Composition of Portland cement 7

Properties of Portland cement 8

Types of cement 9

Types of Portland cement 11

Uses of Portland cement 13

Raw materials 14

Companies in the Philippines 17

Manufacturing process

Wet Process and Dry Process 20

Portland cement (Dry Process) 21

Process Layout 26

Gypsum 27

Miscellaneous Calcium Compound 28

Miscellaneous Magnesium Compound 29

Conclusion 32

References 34

Portland Cement and Miscellaneous Calcium and Magnesium Compounds 2

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

OBJECTIVES

General Objective:

To identify and enumerate the raw materials, unit operations, and equipment involved

in the Manufacturing Process of Portland Cement

Specific Objectives:

 To present the history of Cement, uses and the cement companies in the Philippines

 To identify the types of Cement and Portland Cement

 To identify the chemical composition and properties of Portland Cement

 To enumerate the major and minor raw materials in the production of Portland Cement

 To enumerate and evaluate the step by step process of manufacturing Portland Cement

 To present the manufacturing process of gypsum

 To specify and discuss the miscellaneous calcium and magnesium compounds

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

INTRODUCTION

Cement is a binder, a substance that sets and hardens independently, and can bind
other materials together. Cement is a very important material used in the construction industry.
Cement has replaced all other binding materials, for example, clay and lime. Cement is the
strongest binding material.
Cement is a fine, soft, powdery-type substance made
from a mixture of elements that are found in natural materials
such as limestone, clay, sand and/or shale. When cement is
mixed with water, it can bind sand and gravel into a hard, solid
mass called concrete. Cement mixed with water and sand,
forms cement plaster. Cement mixed with water, lime and
sand, forms mortar.
Cement is used as one of the materials in making concrete buildings, roads, bridges and
other structures. It is one of the ingredients of concrete, the others being gravel and sand.
Cement has been used as a binder of materiel for millenia. No one knows for sure who
first came up with the idea to use a cement substance to bind materials together to make
concrete, bricks, and other building materials. The process can be traced back to Ancient
Macedonia, but was more widely popularized during the Roman Empire. Early forms of cement
used things like lime and pozzolana, a type of volcanic ash. The Romans were able to produce
massive structures like the Pantheon and the Roman aqueducts using this formula.
Currently, cement comes in two forms: Hydraulic and Non-Hydraulic. Hydraulic cement
refers to any cement that uses water to begin a chemical reaction that hardens the mixture and,
when fully formed, creates a water resistant product. This reaction is independent of the water
content of the mixture so allows for the material to harden even underwater. This makes it a
very versatile construction material. Most all cements used today are hydraulic cements. Non-
hydraulic cement uses materials that do not harden when exposed to water. While this type is
much cheaper than hydraulic cement, the problems of long drying times, combined with the
inability to use it in wet environments makes it a poor choice in most applications.

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

The most common type of modern cement is portland cement (sometimes referred to
as OPC for “Ordinary Portland Cement”). This type of cement is typically made by grinding small
rock-like bits of sintered limestone and aluminosilicate minerals into a very fine powder. Its fast
drying times combined with its higher compression strength compared to other cements, makes
it a great choice for use in concrete, mortar, grout, and stucco.
Concrete and cement are not synonymous terms. Concrete is artificial stone made from
a carefully controlled mixture of cement, water, and fine and coarse aggregate (usually sand and
coarse rock).

HISTORY OF CEMENT

Time Events/Discoveries
3,000 BC The Egyptians used gypsum mortars and lime mortars to
build the pyramids.

800 BC Greeks and Cretans used lime mortars, which later became
the base of the famous Roman Mortar.
300 AD - The Romans used lime and cementing pozzolan from
476 AD Pozzuoli, Italy, to build the Apian Way, the Roman baths,
the Coliseum, and the Pantheon in Rome. They used
animal milk and blood as additives when preparing the
mixture of two parts of pozzolan and one part of lime.
These structures still exist nowadays.

1779 Bry Higgins promoted a patent for hydraulic cement

(stucco) to be used in exterior plasters.

1793 John Smeaton found that calcining limestone-containing

clay formed a lime that gets hardened under the water
(hydraulic lime).
1796 Joseph Parker patented in England a natural hydraulic
cement produced by the calcination of coarse limestone
nodules containing clay which was called Parker Cement or
Roman Cement.

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

1812 - 1813 The Frenchman Louis J. Vicat prepared an artificial

hydraulic lime by the calcination of a mixture of limestone
and clay.
1822 James Frost prepared a hydraulic lime similar to that
prepared by Vicat and called it British Cement.
1824 Joseph Aspdin, a bricklayer and mason in Leeds, England,
invented the Portland cement by the calcination of a
mixture of chalk and clay finely divided. The senterized
product was milled and denominated Portland cement, for
its similarity in high quality for construction to that found
in the stones quarried on the isle of Portland, England. His
Portland cement was called ‘proto-Portland Cement’
1853 William Aspdin made what could be called 'meso-Portland
cement' (a mix of Portland cement and hydraulic lime).

1854 Isaac Charles Johnson further refined the production of

‘meso-Portland cement’ (middle stage of development)
and claimed to be the real father of Portland cement.

1858 The next development with the manufacture of Portland

cement was the introduction of the rotary kiln patented by
German Friedrich Hoffmann called a Hoffmann kiln for
brick making.

1860 The Hoffman “endless” kiln which gave “perfect control

over combustion” was tested and showed the process
produced a better grade of cement.
1875 The first Portland cement was produced by Coplay Cement
Company under the direction of David O. Saylor in Coplay,
Pennsylvania.

1878 The Association of German Cement Manufacturers issued

a standard on Portland cement.
20th American made Portland cement had displaced most of
century the imported Portland cement.

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

CHEMICAL COMPOSITION OF PORTLAND CEMENT

Portland cements are composed of four basic chemical compounds, shown with their
names, chemical formulas, and abbreviations:

1. Tricalcium silicate: 3CaO · SiO2 = C3S

2. Dicalcium silicate: 2CaO ·SiO2 = C2S
3. Tricalcium aluminate: 3CaO · Al2O3 = C3A
4. Tetracalcium aluminoferrite: 4CaO · Al2O3FeO3 = C4AFe

Tricalcium silicate hardens rapidly and is largely responsible for initial set and early
strength. In general, the early strength of Portland cement concretes will be higher with
increased percentage of C3S. Dicalcium silicate hardens slowly, and its effect on strength
increases occurs at ages beyond one week. Tricalcium aluminate contributes to strength
development in the first few days because it is the first compound to hydrate. It is, however, the
least desirable component because of its high heat generation and its reactiveness with soils
and water containing moderate-to-high sulfate concentrations. Cements made with low C3A
contents usually generate less heat, develop higher strengths, and show greater resistance to
sulfate attacks. Tetracalcium aluminoferrite assists in the manufacture of Portland cement by
allowing lower clinkering temperature. C4AFe contributes very little to the strength of concrete
even though it hydrates very rapidly.

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

PROPERTIES OF PORTLAND CEMENT

1. Fineness
One factor which affects the
hydration of cement, regardless of its
chemical composition, is its fineness. The
finer a cement is ground, the higher the heat
of hydration and resulting accelerated
strength gain.

2. Soundness
Soundness is the ability of a cement
to maintain a stable volume after setting. An
unsound cement will exhibit cracking,
disruption, and eventual disintegration of the
material mass. This delayed-destruction
expansion is caused by excessive amounts of
free lime or magnesium.
Le Chatelier Test
3. Setting Time
Cement used in concrete must not set too fast, for then it would be
unworkable, that is, it would stiffen and
become hard before it could be placed or
finished. When it sets too slowly, valuable
construction time is lost. Most Portland
cements exhibit initial set in about 3 hours and
final set in about 7 hours. If gypsum were not
added during final grinding of normal Portland
cement, the set would be very rapid. Vicat Apparatus
4. Compressive Strength
The ability of cement to develop
compressive strength in a concrete is an
important property. Compressive strength is
the ability of the cement to resist squeezing
(compressive) load without fracture.

Compressive Strength Test

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

TYPES OF CEMENT

1. Portland Cements
It is the product obtained by pulverizing
clinker consisting essentially of hydraulic calcium
silicates, to which no additions have been made
before calcinations other than water or untreated
calcium sulfate, provided the addition will not
exceed 1.0%. it is the main raw material in the
production of concrete.

2. Pozzolans
Since the beginning of the Christian era,
the Italians have successfully employed pozzolan
cement, made by grinding 2 to 4 parts of a
pozzolan with 1 part of hydrated lime. A pozzolan is
a material which is not cementitious in itself but
which becomes so upon admixture with lime. The
early strength of such a cement is lower than that
of Portland cement, but within a year the strengths
are equal. The advantage of this cement is that it
resists the corrosive action of saline solutions and
seawater much better than does Portland cement.

3. Rapid Hardening Cement

As the name implies, it develops strength
rapidly and therefore can be called as highearly
strength cement. The rate of setting is same as that
of ordinary Portlandcement.The increased rate of
gain of strength of RHC is achieved by a higher C3S
Content and by finer grinding of clinker. The rapid
gain of strength is accomplished by a high rate of
heat development and hence it should not be used
in mass concrete constructions like concrete
gravity dam, concrete retaining walls.The Use of
RHC is recommended in the following situations: In pre-fabricated concrete
construction, for road repair works, place where form-work is required to be removed
early for re-use elsewhere, in Cold weather concreting and in wall sealing.

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

4. High Alumina Cements

High-alumina cement, essentially a calcium
aluminate cement is manufactured by fusing a mixture
of limestone and bauxite, the latter usually containing
iron oxide, silica, magnesia, and other impurities. It is
characterized by a very rapid rate of development of
strength and superior resistance to seawater and
sulfate-bearing water.

5. Silicate Cements
Silica-filled, chemically setting silicate
cements withstand all concentrations of inorganic
acids except hydrofluoric. They are not suitable at
pH values above 7 or in the presence of crystal-
forming systems. Usually 2 parts by weight of finely
divided silica powder is used to 1 part of sodium
silicate. Two typical applications are the joining of
bricks in chromic acid reaction tanks and in alum
tanks.

6. Quick setting Cement

This cement sets very early but does not
gain strength early. The early setting property is
brought out by reducing the gypsum content at
the time clinker grinding. Sometimes aluminum
sulphate is added to accelerate the setting
process. It contains higher percentage of C3A. It
is required to be mixed, placed and compacted
very early. The use of quick setting cement is
recommended under water construction and
grouting operations.

7. White Cement
It is more costly and is used in architectural
purposes such as facing panels and terrazzo surface.
The Grayish color of Portland is due to the presence of
Iron Oxide. The Process of manufacturing of white
cement is the same as that of Portland cement but the
amount of iron oxide is limited to less than 1 %. The

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

raw material used are high purity lime stone (96 % CaCO3 and less than 0.07 % iron
oxide)

8. Colored Cement
It is widely used for decorative works in
floors. For manufacturing of various colored
cements either Grey Portland Cement or White
Cement is used as a Base. With the use of Grey
cement only red or brown cement can be
produced. Colored cement consists of Portland
Cement with 5 -10 % of pigment. For proper
mixing of pigment, it is usual to grind pigment
and cement clinkers together.

TYPES OF PORTLAND CEMENT

1. ASTM Type I
This type is a general concrete construction cement utilized when the special
properties of the other types are not required. It is used where the concrete will not be
subjected to sulfate attack from soil or water or be exposed to severe weathering
conditions. It is generally not used in large masses because of heat generated due to
hydration. Its uses include pavements and sidewalks, reinforced concrete buildings,
bridges, railway structures, tanks, reservoirs, culverts, water pipes, masonry units.

2. ASTM type II (Moderate heat or Modified)

Type II cement is used where resistance to moderate sulfate attack is important,
as in areas where sulfate concentration in groundwater is higher than normal but not
severe. Type II cements produce less heat hydration than Type I, hence their use in
structures of mass such as piers, abutments, and retaining walls. They are used in warm-
weather concreting because of their low temperature rise than Type I. The use of type II
for highway pavements will give the contractor more time to saw control joints because
of the lower heat generation and resulting slower setting and hardening.

3. ASTM Type III (High-Early-Strength)

Type III cements are used where an early strength gain is important and heat
generation is not a critical factor. When forms have to be removed for reuse as soon as
possible, Type III supplies the strength required in shorter periods of time than the other
types. In cold-weather concreting, Type III allows a reduction in the heated curing time
with no loss in strength.

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

4. ASTM Type IV (Low Heat)

Type IV cement is used where the rate and amount of heat generated must be
minimized. The strength development for Type IV is at a lower rate than Type I. it is
primarily used in large mass placements such as gravity dams where the amount of
concrete at any given time is so large that the temperature rise resulting from heat
generation during hardening becomes a critical factor.

5. ASTM Type V (Sulfate-Resisting)

Type V is primarily used where the soil or groundwater contains high sulfate
concentrations and the structure would be exposed to severe sulfate attack.

6. Air – Entraining Portland Cements

ASTM C175 governs the air-entraining cements, Types IA, IIA and IIIA. The three
cements correspond to Types I, II, and III, with the addition of small quantities of air-
entraining materials integrated with the clinker during the manufacturing process.
These cements provide the concrete with improved resistance to freeze-thaw
action and to scaling caused by chemicals and salts used for ice and snow removal.
Concrete made with these cements contains microscopic air bubbles, separated,
uniformly distributed, and do small that there are many billions in a cubic foot.

7. White Portland Cement

White Portland cement is a true Portland cement, its color being the principal
difference between it and normal Portland cement. The cement is manufactured to
meet ASTM C150 and C175 specifications. The selected raw materials used in the
manufacture of white cement have negligible amounts of iron and manganese oxide,
and the process of manufacture is controlled to produce the white color. Its primary use
is for architectural concrete products, cement paints, tile grouts and decorative
concrete.

8. Portland Blast-Furnace Slag Cements

In these cements, granulated blast-furnace slag of selected quality is
interground with Portland cement. The slag is obtained by rapidly chilling or quenching
molten slag in water, steam, or air. Portland blast-furnace slag cements include two
types; Type IS and Type IS-A, conforming to ASTM C595. These cements can be used in
general concrete construction when the specific properties of other types are not
required. However, moderate heat of hydration (MH), moderate sulfate resistance
(MS), or both are optional provisions. Type IS has about the same rate of strength
development as Type I cement, and both have the same strength requirements.

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

9. Portland-Pozzolan Cements
IP, IP-A, and P-A designate the Portland-pozzolan cements with the A denoting
air-entraining additives as specified in C595. They are used principally for large hydraulic
structures such as bridge piers and dams. These cements are manufactured by
intergrinding Portland cement clinker with a suitable pozzolan such as volcanic ash, fly
ash from power plants, or diatomaceous earth, or by blending the Portland cement or
Portland blast-furnace slag cement and a pozzolan.

10. Masonry Cements

Type I and type II masonry cements are manufactured to conform to ASTM C91
and contain Portland cement, air-entraining additives, and materials selected for their
ability to impart workability, plasticity, and water-retention properties to the masonry
mortars.

11. Special Portland cements

a. Oil well cement

Oil well cement is used for sealing oil wells. It is usually slow setting and
resistant to high pressures and temperatures. The American Petroleum Institute
Specifications for Oil Well Cements (API standard 10A) cover requirements for six
classes of cements. Each class is applicable for use at a certain range of well depths.

b. Waterproof Portland cement

Waterproof Portland cement is manufactured by the addition of a small amount
of calcium, aluminum, or other stearate to the clinker during final grinding. It is
manufactured in either white or gray color and is used to reduce water penetration
through the concrete.

USES OF PORTLAND CEMENT

Portland Cement is used widely for the construction of various structures. Some of
them are listed below:
a. Used for filling cracks in concrete structures.
b. Used for masonry work, plastering and pointing.
c. Used for the construction of various structures like buildings, bridges. water tanks,
tunnels, docks, harhours etc.
d. Used to manufacture lamp posts, telephone posts, railway sleepers, piles etc.
e. For manufacturing cement pipes, garden seats, dust bins, flower pots etc. It is
useful for the construction of roads, footpaths, courts for various sports etc.

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

RAW MATERIALS

The main raw materials used in the cement manufacturing process are
limestone, sand, shale, clay, and iron ore.

Calcareous
 Limestone (includes aragonite, marble, chalk)
 Cement rock (include marl)
 Oyster shell

Argillaceous
 Clay
 Shale
 Others (includes Staurolite, bauxite, aluminum dross, pumice and volcanic
materials)

Siliceous
 Sand
 Sandstone and Quartz

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

Ferrous
 Iron Ore
 Pyrites
 mill-scale and other iron-bearing materials

Other
 Gypsum and anhydrite
 Blast furnace Slag
 Fly ash

Percentage of Raw Materials used in

Manufacturing Cements

Calcareous
9%
Argillaceous

18%
Siliceous
60% Ferrous
Gypsum
5%
5% Slag
3%

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

According to Bayquen (2007), cement uses minerals, containing the four essential
elements for its creation: calcium, silicon, aluminum and iron.

1. Volcanic Tuff

- Rock composed of the finer or

volcanic detritus usually fused
together through heat.

2. Limestone

- Rock that is formed chiefly by

accumulation of organic
remains (such as shells or
corals); consists mainly of
calcium carbonate. It yields lime
when burned.

3. Pyrite

- A common mineral that consists

of iron disulfide, FeS2 and has a
pale brass-yellow color and
metallic luster. It is being
burned to make sulfur dioxide
and sulfuric acid.

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

4. Silica sand

- Impure silicon dioxide SiO2.

5. Gypsum

- A widely distributed mineral

CaSO4 ∙ 2H2O consisting of
hydrated calcium sulfate.

COMPANIES IN THE PHILIPPINES

1. Holcim Philippines

Mailing Address: 7th Floor Two World

Square McKinley Hill, Fort Bonifacio, Taguig
City, 1634 Philippines Telephone No.: + (632)
459 3333
Website: www.holcim.ph
Plant Locations:
 Holcim Philippines - La Union Plant
Quirino, Bacnotan, La Union (Region I)
 Holcim Philippines - Bulacan Plant
Barangay Matictic, Norzagaray, Bulacan (Region III)
 Holcim Philippines - Lugait Plant
Lugait, Misamis Oriental (Region X)

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

 Holcim Philippines - Davao Plant

Bo. Ilang, Davao (Region XI)

2. Northern Cement Corporation

Mailing Address: 151 Epifanio Delos Santos (EDSA),
Brgy.Wack-Wack, Mandaluyong City, Philippines
Telephone Number: +(63 2) 667-5676
Fax Number: +(63 2) 320-3155
Website: www.ncc.com.ph
Plant Location: Bo. Labayug, Sison, Pangasinan (Region I)

3. Eagle Cement Corporation

Office Address: 153 EDSA, Mandaluyong City,
Philippines
Telephone No.: +(63 2) 727-4913 Fax No.: +(63 2) 723-
9283
Website: www.eaglecement.com.ph
Plant Location: Brgy. Akle, San Idelfonso, Bulacan

4. Solid Cement Corporation (CEMEX Philippines Group of Companies)

Office Address: 8th Floor, Petron Megaplaza, 358 Sen.

Gil J. Puyat Avenue, Makati City, 1200 Philippines
Telephone Number: +(63 2) 849-3585
Website: www.cemexphilippines.com
Plant Location: SitioTagbac, Brgy. San Jose, Antipolo
City, Rizal (Region IV-A)

5. Apo Cement Corporation (CEMEX Philippines Group of Companies)

Offices: 8th Floor Petron Megaplaza, 358 Sen. Gil J.

Puyat Avenue, Makati City, 1200 Philippines
Telephone Nos.: +(63 2) 489-3300
Website: www.cemexphilippines.com
Plant Location: APO Cement Plant Compound, Tina-an,
Naga City, Cebu (Region VII)

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

6. Lafarge Republic Incorporated

Office Address: 20th Floor, Salcedo Tower, 169 H.

V. Dela Costa Street, Salcedo Village, Makati City,
Philippines
Telephone No.: +(63 2) 885-4599
Fax No.: +(63 2) 815-2668
Website: www.lafarge.com.ph
Plant Locations:
 Lafarge Republic Bulacan Plant
Barrio Minuyan, Norzagaray, Bulacan (Region III)
 Lafarge Republic Norzagaray Plant
Barrio Bige, Norzagaray, Bulacan (Region III)
 Lafarge Republic Teresa Plant
Brgy.Dulumbayan, Teresa, Rizal (Region IVA)
 Lafarge Republic Batangas Plant
Brgy.Mapulo, Taysan, Batangas (Region IVA)
 Lafarge Republic Danao Plant
Brgy.Dungo-an, Danao City, Cebu
 Lafarge Iligan Plant
Brgy.Kiwalan, Iligan City

7. Taiheiyo Cement Philippines, Inc.

Office Address: 11th Floor, Insular Life Cebu Business Centre,

Cebu Business Park Cebu City, 6000 Philippines
Plant Location: South Poblacion, San Fernando, Cebu
Telephone No.: +(63 32) 230-7333
Fax No.: +(63 32) 230-7300
Website: www.taiheiyo-cement.com.ph

8. Goodfound Cement Philippines, Inc.

Office Address: Palanog, Camalig, Albay (Region v)

Plant Location: Palanog, Camalig, Albay
Telephone Nos.: +(63 52) 484-1322

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

MANUFACTURING PROCESS

A. TWO PROCESSS INVOLVED IN THE MANUFACTRUE OF PORTLAND CEMENT

1. Wet Process
The original rotary cement kilns were called
'wet process' kilns. In their basic form they were
relatively simple compared with modern
developments. The raw meal was supplied at
ambient temperature in the form of slurry. A wet
process kiln may be up to 200m long and 6m in
diameter. It has to be long because a lot of water has
to be evaporated and the process of heat transfer is
not very efficient. The slurry may contain about 40%
water. This takes a lot of energy to evaporate and
various developments of the wet process were
Basic principle of a wet-process kiln.
aimed at reducing the water content of the raw
meal. An example of this is the 'filter press' (imagine a musical accordion 10-20 metres long and
several metres across) - such adaptions were described as 'semi-wet' processes.

The wet process has survived for over a century because many raw materials are suited
to blending as a slurry. Also, for many years, it was technically difficult to get dry powders to
blend adequately. Quite a few wet process kilns are still in operation, usually now with higher-
tech bits bolted on. However, new cement kilns are of the 'dry process' type.

2. Dry process
In a modern works, the blended raw material
enters the kiln via the pre-heater tower. Here, hot
gases from the kiln, and probably the cooled clinker at
the far end of the kiln, are used to heat the raw meal.
As a result, the raw meal is already hot before it
enters the kiln.
The dry process is much more thermally efficient than
the wet process.
Firstly, and most obviously, this is because the
meal is a dry powder and there is little or no water
that has to be evaporated. Secondly, and less
Basic principle of a precalciner cement
obviously, the process of transferring heat is much
more efficient in a dry process kiln. kiln.

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

An integral part of the process is a heat exchanger called a 'suspension preheater'. This
is a tower with a series of cyclones in which fast-moving hot gases keep the meal powder
suspended in air. All the time, the meal gets hotter and the gas gets cooler until the meal is at
almost the same temperature as the gas.
The basic dry process system consists of the kiln and a suspension preheater. The raw
materials, limestone and shale for example, are ground finely and blended to produce the raw
meal. The raw meal is fed in at the top of the preheater tower and passes through the series of
cyclones in the tower. Hot gas from the kiln and, often, hot air from the clinker cooler are blown
through the cyclones. Heat is transferred efficiently from the hot gases to the raw meal.
The heating process is efficient because the meal particles have a very high surface area in
relation to their size and because of the large difference in temperature between the hot gas
and the cooler meal. Typically, 30%-40% of the meal is decarbonated before entering the kiln.

B. MANUFACTURING PROCESS OF PORTLAND CEMENT (DRY PROCESS)

EQUIPMENT UNIT OPERATIONS AND PROCESSES

Excavator QUARRYING

Limestone and shale are extracted from the quarry

by open pit method, through drilling and blasting
techniques. For safety, the workers must maintain
a distance of at least 50 meters from the area
they’ll blast. Sand, waste bauxite, and iron ore are
sometimes consumed in small amounts to adjust
the composition of the mix.

Dump Truck TRANSPORTING THE RAW MATERIALS

Raw materials extracted from the quarry are

delivered to the plant by the use of dump trucks.

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

Gyratory Mill CRUSHING

The bulk of limestone and shale would be reduced

into smaller pieces approximately 3.8 in size by
gyratory mill. There is a constant spray of water to
keep dust from billowing up.

Hammer Mill PRE-HOMOGENIZATION

Reduces the crushed limestone and shale or clay

to a finer powder; allows limestone and shale to
mix better.

Vertical roller mill RAW MATERIAL MILLING

The pre-homogenized materials (limestone and

shale/clay) and two other raw materials (silica
sand and pyrite) are proportioned, milled and
dried, producing raw meal.

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

Blending Silos HOMOGENIZATION

The raw meal ground in the raw mill is thoroughly

blended in vertically tall blending silos of capacity
upto 10,000-15,000 tonnes or more. The blending
is performed pneumatically by introducing the
compressed air in the bed of fine raw meal fed to
the blending silo or mechanically by distributing
the raw meal at different cross section of the silo
with the help of airslides.

Preheating tower PREHEATING

The raw meal enters the pre-heater at a

temperature from 900⁰C to 1000⁰C. Within 40
seconds, this begins the process of bonding the
minerals together, so they’ll later harden when
hydrated with water. In about 5 seconds, it
removes about 95% of the carbon dioxide of
powder through a chemical reaction, which
isolates the lime – the most important component
of cement. The preheating of material before
calcination helps save energy.
𝐶𝑎𝐶𝑂3 → 𝐶𝑎𝑂 + 𝐶𝑂2(𝑔)

Rotary kilns CALCINATION

 Lime reacts with silica in stages and clinker

minerals are finally formed at 1450°C.
 The final product formed consists of hard
granular masses from 3 to
20 mm in size called clinker.
 The kiln is slightly inclined so that the
materials fed in the upper end travel
slowly to the lower firing end.
 Portland cement clinker mainly consists of
CaO, 𝑆𝑖𝑂2 , 𝐴𝑙2 𝑂3 and 𝐹𝑒2 𝑂3 ; are

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

accounting for more than 95%. The minor

Length: 45m components in total less than 3% are
Internal diameter: 2.5 to 6 m MgO, 𝑇𝑖𝑂2 , 𝑃2 𝑂5 and alkalis.
Rotational speed: 0.5 to 2 rpm  The clinker formation is exothermic with a
Rotation period: 1 to 3 h probable value of 200 B.t.u. per lb. of
Heat sources: mined coal, fuel oil, natural gas clinker.
and alternative fuel resources (like rice husk)
Clinker Formation:

CaO = C; 𝑆𝑖𝑂2 = S; 𝐴𝑙2 𝑂3 = A; 𝐹𝑒2 𝑂3 = F

Composition of Portland Cement:

1. Belite (𝐶2 𝑆) constitutes 15-30%. It is dicalcium
silicate (𝐶𝑎2 𝑆𝑖𝑂4).
2. Alite (𝐶3 𝑆) is the most important constituent,
50-70%. It is tricalcium silicate (𝐶𝑎3 𝑆𝑖𝑂5).
3. Aluminate ( 𝐶3 𝐴 ) constitutes 5-10%. It is
Tricalcium aluminate (𝐶𝑎3 𝐴𝑙2 𝑂6 ).
4. Ferrite ( 𝐶4 AF) makes up 5-15%. It is a
tetrcalcium aluminoferrite (𝐶𝑎4 𝐴𝑙𝐹𝑒𝑂5 ).

Clinker cooler COOLING

Clinker is discharged from rotary kiln into the air-

quenching coolers, which quickly bring its
temperature down to approximately 100 to 200⁰C.
The sudden cooling of material results to gray-
colored nodules which is called clinker.

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

Steel silos STORING

After the molten clinker is quickly air- cooled, it is

transported by bucket conveyors to the shaded
storage to avoid weathering effects.

Cement Mill CEMENT MILLING

Clinker, together with about 4-5% gypsum (help

regulate the setting time when the cement is
mixed with other materials and become concrete),
is finely ground at the cement mill. The powder
product is now called cement.

Packaging machine PACKAGING AND SHIPPING

Closed circuit grinding is preferred rather than

open-circuit grinding because The final product is
shipped either in bulk (ships, barges, tanker trucks,
railroad cars, etc.) or in strong paper bags which
are filled by machine.

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

Dusting Bag Filter

The entire process of cement making creates a lot of dust, so a Continuous Emission Monitoring
System (CEMS) is applied. This way, we can be sure there is no pollution in the air. So,
everything is environment-friendly.

PROCESS LAYOUT

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

C. MANUFACTURING PROCESS OF GYPSUM

1 1
CaSO4 ∙ 2H2O(c) CaSO2 ∙ H2O(c) +1 H2O(g)
2 2
A mineral occurs in large deposits throughout the world. It is the second softest
mineral following after talc in Mohr’s Hardest Scale. It is hydrated calcium sulfate, the
formula CaSO4.(2H2O).
If heating is at a higher temperature, gypsum loses all its water and becomes
anhydrous sulfate or anhydrite. It is hydraulic and hardens under water, but is also
slightly soluble in water.

EQUIPMENT UNIT OPERATIONS AND PROCESSES

Calciners CALCINATION OF GYPSUM

The usual method of calcination of gypsum consists

of grinding the mineral and placing it in large
calciners holding 9 to 22 tons. The temperature is
raised to about 120 -150 ℃, with constant agitation
to maintain a uniform temperature. The material in
the kettle known to the public as plaster of paris and
to the manufacturer as first-kettle plaster, may be
withdrawn and sold at this point, or it may be heated
further to 190℃ to give a material known as second–
settle plaster.

Calcining kettle HARDENING OF PLASTER

1 1
CaSO4 ∙ 2H2O +12H2O CaSO4 ∙ 2H2O
This equation is the reverse of that for the
dehydration of gypsum. The plaster sets and hardens
because the liquid water reacts to form a solid,
crystalline hydrate. Hydration with liquid water takes
place at temperatures below 99℃ and thus gypsum
must be heated above 99℃ for practical dehydration.
Commercial plaster usually contains some glue in the
water used or a material such as hair or tankage from
the stockyards to retard the setting time in order to
give the plasterer opportunity to apply the material.

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

MISCELLANEOUS CALCIUM COMPOUNDS

CALCIUM CARBONATE
Calcium carbonate is a very widely used
industrial chemical, in both its pure and its impure
state. As marble chips, it is sold in many sizes as a filler
for artificial stone, for the neutralization of acids, and
for chicken grit. Marble dust is employed in abrasives
and in soaps. Crude, pulverized limestone is used in
agriculture to “sweeten” soils in large tonnage. Some
pulverized and levigated limestone, to replace imported
chalk and whiting, is manufactured quite carefully from
very pure raw material and is finding acceptance.
Whiting is pure, finely divided calcium carbonate
prepared by wet grinding and levigating natural chalk. Whiting mixed with 18% boiled linseed oil
yields putty, which sets by oxidation and by formation of the calcium salt. Much whiting also is
consumed in the ceramic industry. Precipitated, or artificial, whiting arises through
precipitation, e.g., from reacting a boiling solution of calcium chloride with a boiling solution of
sodium carbonate or passing carbon dioxide into a milk-of-lime suspension. Most of the latter
form is used in the paint, rubber, pharmaceutical, and paper industries.

CALCIUM SULFIDE
Calcium sulfide is made by reducing calcium
sulfate with coke. Its main use is as a depilatory in the
tanning industry and in cosmetics. In a finely divided
form it is employed in luminous paints. Polysulfides,
such as CaS2 and CaS5, made by heating sulfur and
calcium hydroxide, are consumed as fungicides.

HALIDE SALTS
Calcium chloride is obtained commercially as a by-
product of chemical manufacture and from natural brines
which contain more or less magnesium chloride. In 1980,
730,000 t was sold. Its main applications are to lay dust on
highways in winter, to thaw coal, in oil and gas well fluids,
and as antifreeze for concrete.
Calcium bromide and iodide have properties similar to
those of the chloride. They are prepared by the action of
the halogen acids on calcium oxide or calcium carbonate.

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

They are sold as hexahydrates for yse in medicine and photography. Calcium fluoride occurs
naturally as a fluorspar. Calcium hypochlorite [Ca(OCl)2] is prepared by the action of chlorine on
calcium hydroxide. Its primary use is for swimming pool sanitation.

CALCIUM ARSENATE
Calcium arsenate is produced by the reaction of
calcium chloride, calcium hydroxide, and sodium arsenate or
lime and arsenic acid. Some free lime is usually present.
Calcium arsenate is used extensively as an insecticide and as a
fungicide.

CALCIUM ORGANIC COMPOUNDS

Calcium acetate and lactate are prepared by the
reaction of calcium carbonate or hydroxide with acetic or lactic
acid. The acetate was formerly pyrolyzed in large amounts to
produce acetone, but now it is employed largely in the dyeing
of textiles. The lactate is sold for use in medicines and in foods
as a source of calcium; it is an intermediate in the purification
of fermentation lactic acid. Calcium soaps such as stearate,
palmitate, and the abietate are made by the action of the
sodium salts of the acids on a soluble calcium salt such as the
chloride. These soaps are insoluble in water but are soluble in
hydrocarbons. Many of them form jellylike masses, which are constituents of greases. These
soaps are used mainly as waterproofing agents.

MISCELLANEOUS MAGNESIUM COMPOUNDS

Magnesium is one of the most widely distributed

elements, occupying 1.9 percent of the earth’s crust. It
occurs usually in the chloride, silicate, hydrated oxide,
sulfate or carbonate in either a complex or in simple salts.
Magnesium metal first became available commercially
shortly before 1914, when the Germans initiated
production using magnesium chloride from the Stassfurt
deposits as the raw material.

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

MAGNESIUM CARBONATES
These vary from dense MgCO3 used in magnesite bricks
to the very low density 4MgCO3·Mg(OH)2·5H2O and
3MGCO3·MG(OH)2·3H2O once employed for insulation. There are
also other basic carbonates on the market with variations in
adsorptive index and apparent density. Many of these are
employed as fillers in inks, paints, and varnishes.

OXIDES AND HYDROXIDE OF MAGNESIUM

On heating magnesium carbonate or
hydroxide, magnesium oxide (MgO) is formed. This
oxide has many uses, e.g., in the vulcanization of
rubber, as a material for making other magnesium
compounds, as an insulating material, as a refractory
material, and as an abrasive. The magnesium
hydroxide is principally made directly from seawater.
The seawater is screened and pumped to a battery of
three 38-m diameter concrete hydrotreaters. Here
enough calcined dolomite is added to pretreat or
soften the seawater by precipitating carbonates,
which are removed by rakes. The softened seawater
flows to two primary reactors 25 m in diameter into
which is fed the main addition of calcined dolomite to precipitate the Mg(OH)2, which in a fine
suspension overflows into three parallel-flow 76-m-diameter thickeners, the overflow being
returned to the sea. The underflow of the two primary reactors is fed first into an 18-diameter
secondary reactor and then into the tertiary reactor, from which the three-times-reacted
residue, now largely silicious material and unreacted dolomite, is wasted. The thickened
Mg(OH)2 slurry from the three 76-m thickeners is united and washed with calcined-dolomite-
softened fresh water in two 76-m thickeners in series. The Mg(OH)2 underflow is conducted
through storage to a 4- by 5.5-m rotary filter operating at about 26.7-kPa vacuum and delivering
about 50% Mg(OH)2. This is removed from the rotary filter and conveyed either to sale or to one
of three rotary kilns operating up to 1800°C to give different grades of MgO. After purification
this is the well-known milk of magnesia used in medicine. Magnesium peroxide is available from
the reaction of magnesium sulfate and barium peroxide. It is employed as an antiseptic and a
bleaching agent.

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

MAGNESIUM SULFATE
Magnesium sulfate is prepared by the action of
sulfuric acid on magnesium carbonate or hydroxide. It is sold
in many forms, one of which is the hydrate MgSO4·7H2O,
long known as Epsom salts. The less pure material is used
extensively as sizing and as a fireproofing agent.

MAGNESIUM CHLORIDE
Magnesium chloride is made from hydrochloric acid and
magnesium hydroxide as described above. The compound itself
much resembles calcium chloride and has many of the same
uses. In addition, it finds application in ceramics, in the sizing of
paper, and in the manufacture of oxychloride cement. Its
principal use is in the making of metallic magnesium.

MAGNESIUM SILICATES
A consideration of magnesium silicates includes two widely used naturally occurring
compounds, asbestos and talc. Asbestos is a magnesium silicate mixed with varying quantities of
silicates of calcium and iron. It is a fibrous, noncombustible mineral and is used in the
manufacture of many fireproof and insulating materials. Because of the cancer-causing
characteristics of its fibers, government regulations have sharply reduced its use. Talc is a rather
pure magnesium silicate in the form of 3MgO·4SiO2·H2O, found naturally in soapstone. It is
employed as a filler in paper and plastics and in many cosmetic and toilet preparations.

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

CONCLUSION

Cement is a fine, soft, powdery-type substance made from a mixture of elements that
are found in natural materials such as limestone, clay, sand and/or shale. Cement is a binder, a
substance that sets and hardens independently, and can bind other materials together. Cement
is a very important material used in the construction industry. Cement has replaced all other
binding materials, for example, clay and lime. Cement is the strongest binding material.

There are eight different types of cement which are: Portland Cement, Pozzolans, Rapid
Hardening Cement, High Alumina Cement, Silicate Cement, Quick Setting Cement, White
Cement, and Colored Cement. The most common type of cement is Portland Cement. The
different types of Portland Cement are: ASTM Type I (General Use), ASTM Type II (Moderate
heat or Modified), ASTM Type III (High-Early-Strength), ASTM Type IV (Low Heat), ASTM Type V
(Sulfate-Resisting), Air – Entraining Portland Cements, White Portland Cement, Portland Blast-
Furnace Slag Cements, Masonry Cements, and Special Portland cements.

Portland cements are composed of four basic chemical compounds: Tricalcium silicate,
Dicalcium silicate, Tricalcium aluminate, and Tetracalcium aluminoferrite. Its physical properties
are fineness, soundness, tensile strength and compressive strength.

Portland Cement is used for filling cracks in concrete structures, for masonry work,
plastering and pointing, for the construction of various structures like buildings, bridges. water
tanks, tunnels, docks, used to manufacture lamp posts, telephone posts, railway sleepers, piles,
and it is also used to manufacturing cement pipes, garden seats, dust bins, flower pots etc. It is
useful for the construction of roads, footpaths, courts for various sports etc.

The raw materials in the production of Portland cement are calcareous (limestone,
cement rock), argillaceous (clay, shale), siliceous (sand, quartz), ferrous (iron ore), and others
such as gypsum. According to Bayquen (2007), cement uses minerals, containing the four
essential elements for its creation: calcium, silicon, aluminum and iron. And the specific raw
materials used are volcanic tuff, pyrite, limestone, silica sand, and gypsum.

There are two processes involved in the manufacture of Portland cement: wet process
and dry process. Dry process is more thermally efficient than wet process. In manufacturing of
Portland cement through Dry process, the first step is quarrying then transportation of raw
materials. Next it will undergo crushing, pre-homogenization, raw material milling,
homogenization, pre-heating, calcination, cooling, storing and then, cement milling. Finally it will
be packed and shipped.

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

Gypsum is a mineral occurs in large deposits throughout the world. It is the second
softest mineral following after talc in Mohr’s Hardest Scale. It is hydrated calcium sulfate, the
formula CaSO4.(2H2O). In manufacturing gypsum two process is done: calcination of gypsum
and hardening of plasters.
Magnesium is one of the most widely distributed elements, occupying 1.9 percent of the
earth’s crust. It occurs usually in the chloride, silicate, hydrated oxide, sulfate or carbonate in
either a complex or in simple salts. The miscellaneous magnesium compunds are: Marnesium
carbonates, oxides and hydroxides of Magnesium, Magnesium sulfate, Magnesium chloride, and
Magnesium silicates like absestos and talc.
Miscellaneous Calcium Compunds are: Calcium carbonate, Calcium sulfide, Halide salts,
Calcium arsenate, and Calsium organic compounds.

Portland Cement and Miscellaneous Calcium and Magnesium Compounds 33

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

REFERENCES

Austin, G. T. (1984). Shreve’s Chemical Process Industries 5th edition

Coffey, J.C., Lafeur, C.B., LaPlante,C., Marotta,T.W. (2011). Basic Construction materials
th
8 edition
Cement. Retrieved from http://iti.northwestern.edu/cement/monograph/Mono
graph3_8.html on November 18, 2015
Uses of Cement. Retrieved fromhttp://www.civilengineeringx.com/traditional-
materials/uses-of-cement/ on November 18, 2015

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