INTENDED LEARNING OUTCOMES

1. Describe the fundamental operations and processes involved in the different

chemical and manufacturing industries.
2. Explain the processing of raw materials into usable and profitable products.
3. Relate chemical engineering concepts in the solution of real industrial problems.

PORTLAND CEMENTS

INTRODUCTION

Ever since the beginning of time, mans quest had always been focused on
developing ways that will satisfy their needs. Because of the boundless capacity of such
species, many remarkable discoveries were made that carved its way into the history of
humankind. One of such discovery is the cement.
Cement is a fine, grey powder, that when reacted with water, hardens, forming a
rigid chemical mineral structure. Because of this characteristic property, it binds itself as
the main ingredient in concrete, along with water, acting as a super glue that binds the
concrete together, giving it its strength. Moreover, because of the extreme versatility of
concrete due to its property of being moulded into any shape, reinforced with steel or
glass fibers, setting under water, among others; cement is the key material to all
infrastructures today. The credit for such discovery is given to the Romans who was the
first to formulate the idea of mixing limestone (CaCO3) with volcanic ash to produce
cement mortar. The success of such discovery is manifested through their
infrastructures that are still standing today such as the Colosseum.

BRIEF HISTORY

A cement was used by the Egyptians in constructing the Pyramids. The Greeks
and Romans used volcanic tuff mixed with lime for cement and a number of these
structures are still standing. In 1824, an Englishman, Joseph Aspdin, patented an
artificial cement made by calcination of an argillaceous limestone. He called this
portland because concrete made from it resembled a famous building stone obtained
from the Isle of Portland near England. This was the start of the Portland cement
industry of today. The hard clinker resulting from burning a mixture of clay and
limestone or similar materials is known by the term portland cement to distinguish at
from natural or pozzolan and other cements.

TYPES OF 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. Hydraulic calcium silicates possess
the ability to harden without drying or by reaction with atmospheric carbon dioxide, thus
differentiating them from other inorganic binders such as plaster of paris. The reactions
involved in the hardening of cement are hydration and hydrolysis. The types of portland
cements are the following:

Type I Regular portland cements are the usual products for general construction.

Type II Moderate-heat-of-hardening and sulfate-resisting portland cements are for use

where moderate heat of hydration is required or for general concrete
construction exposed to moderate sulfate action.

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Type III High-early-strength (HES) cements are made from raw materials with a lime
-to-silica ratio higher than that of Type I cement and are ground finer than Type I
cements. They contain a higher proportion of C3S than regular portland
cements.

Type IV Low-heat Portland cements contain a lower percentage of C3S and C3A, thus
lowering the heat evolution. Consequently, the percentage of C4AF is increased
because of the addition of Fe2O3 to reduce the amount of C3A.

Type V Sulfate-resisting portland cements are those which by their composition or

processing resist sulfates better than the other four types. It is used when high
sulfate resistance is required. These cements are lower in C3A than regular
cements. In consequence of this, the C4AF content is higher.

MANUFACTURING PROCEDURES
Two types of materials are necessary for the production of portland cement: one
rich in calcium (calcareous), such as limestone, chalk, etc., and one is rich in silica
(argillaceous) such as clay.

The cement industry uses the following abbreviations for these clinker compounds:

CaO = C Fe2O3 = F Na2O = N H2O = H

SiO2 = S MgO = M K2O = K

Al2O3 = A SO3 = S CO2 = C

Cement clinker is manufactured by both wet and dry processes. In the wet
process, the solid material, after dry crushing, is reduced to a fine state of division in wet
tube or ball mills and passes as slurry through bowl classifiers or screens. The slurry is
pumped to correcting tanks, where rotating arms make the mixture homogeneous and
allow the final adjustment in composition to be made. The dry process is especially
applicable to natural cement rock and to mixtures of limestone and clay, shale, or slate.
In this process, the materials may be roughly crushed, passed through gyratory and
hammer mills, dried, sized, and more finely ground in tube mills, followed by air
separators. This dry, powdered material is fed directly to rotary kilns, where the
chemical reactions take place.

OTHER CEMENTS

Pozzolans made by grinding 2 to 4 parts of a pozzolan with one part of

hydrated lime
- a material which is not cementations in itself but which becomes so upon
admixture with lime.
- advantage: it resists corrosive action of saline solutions and seawater
much better than does Portland cement.
High Alumina Cements (HAC) - sometimes known as calcium
aluminate cement (CAC) or aluminous cement
- composed of calcium aluminates, unlike Portland cement which is
composed of calcium silicates. It is manufactured from limestone or chalk
and bauxite.
Silicate Cements silica-filled, chemically setting silicate cements withstand all
concentrations of inorganic acids except hydrofluoric. They are not

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 suitable at pH values above 7 or in the presence of crystal-forming
systems.
Sulfur cements are resistant to nonoxidizing acids and salts but should not be
used in the presence of alkalies, oils, greases, or solvents.
Polymers concrete polymer-bonded concrete and usually contain no Portland
cement.
Magnesium oxychloride cement discovered by chemist Sorel; sometimes called
Sorels cement, is produced by the exothermic action of a 20% solution
of magnesium chloride on a blend of magnesia obtained by calcining
magnesite and magnesia obtained from brines.
- application : flooring cement

CALCIUM COMPOUNDS
LIME
Lime is a general term for calcium-containing inorganic materials (carbonates, oxide
and hydroxide predominate)

Limestone
- sedimentary rock which is relatively inert, except in the presence of a strong
acid.
- With the proper purity the rock deposit can be used to produce lime, a
manmade chemical.

Quicklime (Burnt lime)

- Calcium oxide (CaO)
- It is a white, caustic, alkaline crystalline solid at room temperature.
- Dangerous form of lime

Slaked Lime (Hydrated lime)

- Calcium hydroxide, Ca(OH)2
- It is a colorless crystal or white powder and is obtained when calcium oxide
(quicklime) is mixed, or slaked with water.
- Used in many applications, including food preparation.

Hydraulic Lime
- Slaked lime, used to make lime mortar (paste used to bind construction
blocks together and fill the gaps between them)
- Obtained from burning of limestone containing clay and other impurities
- Hydraulicity is the ability of lime to set under water or wet conditions

GYPSUM
- very soft sulfate mineral composed of calcium sulfate, CaSO 42H2O
- component of Portland cement used to prevent the flash settling of concrete
- added about 4- 5% during the final grinding

MISCELLANEOUS CALCIUM COMPOUNDS

Calcium carbonate it is sold for the neutralization of acids, for artificial stone,
and for chicken grit. Crude, pulverized limestone is used in agriculture to
sweeten soils in large tonnage.

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 Calcium sulfide made by reducing calcium sulfate with coke. Its main use is in
cosmetics.
Halide salts calcium chloride
- Application: lay dust on highways, to melt ice and snow on highways
on winter, to thaw coal, in oil, and gas well fluids, and as an antifreeze
for concrete.
Calcium Arsenate produced by the reaction of calcium chloride, calcium
hydroxide, and sodium arsenate or lime and arsenic acid.

MAGNESIUM COMPOUNDS
Magnesium is one of the most widely distributed elements. Important domestic
sources of magnesium salts are seawater, certain salt wells, bitterns from sea brine,
salines, dolomite, and magnesite (MgCO3).

Magnesium carbonates - Most of these of employed as fillers in inks, paints and

varnishes
Oxides and Hydroxides of Magnesium - On heating magnesium carbonate or
hydroxide, magnesium oxide (MgO) is formed. It is used in vulcanization
of rubber, insulating material, refractory material, for making other
magnesium compounds and as an abrasive
Magnesium sulfate prepared by the action of sulphuric acid on magnesium
carbonate or hydroxide.
Magnesium chloride made from hydrochloric acid and magnesium hydroxide.
- Application: in ceramics, in the sizing of paper, and in the manufacture
of oxychloride cement.
- Used in making of metallic magnesium
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, non-combustible
mineral and is used in the manufacture of many fireproof and insulating
materials. Talc is rather pure magnesium silicate in the form of
3MgO4SiO2H2O, found naturally in soapstone.

REFERENCES:
Book
Austin G. T. (1984) Shreves Chemical Process Industries: 5th edition. New York:
McGraw-Hill Book Company

Online Sources

Portland Cements, Calcium and Magnesium Compounds

Retrieved from https://www.slideshare.net/zhunneyworks/portland-
cements-calcium-and-magnesium-compounds

High Alumina Cements

Retrieved from
https://www.designingbuildings.co.uk/wiki/High_alumina_cement

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