CEMENT INDUSTRY

CHEMICAL PROCESS TECHNOLOGY-I

CE-400
DEPARTMENT OF CHEMICAL ENGINEERING
UNIVERSITY OF KARACHI
 IMNRODUCTION
• A cement is a binder, a substance used for
construction that sets, hardens, and adheres
to other materials to bind them together.
• Cement is seldom used on its own, but rather
to bind sand and gravel (aggregate) together.
• Cement mixed with fine aggregate
produces mortar for masonry, or
with sand and gravel, produces concrete.
 INTRODUCTION
• Cements used in construction are
usually inorganic, often lime or calcium
silicate based.
• They can be characterized as either
1. hydraulic or
2. non-hydraulic
depending on the ability of the cement to set in
the presence of water.
 INTRODUCTION
• Non-hydraulic cement does not set in wet
conditions or under water. Rather, it sets as it
dries and reacts with carbon dioxide in the air.
It is resistant to attack by chemicals after
setting.
• Non-hydraulic cement should be kept dry to
attain strength, and be able to maintain its
structure.
 INTRODUCTION
• It takes a substantially longer time to dry off
and gain strength after being set.
Example is lime.
• Here hardening takes place by carbonation-
reaction of hydrated lime with carbon dioxide
in the atmosphere.
• Other examples are gypsum and magnesium
cement.
 INTRODUCTION
• Hydraulic cements (e.g., Portland cement) set
and become adhesive due to a chemical
reaction between the dry ingredients and
water.
• The chemical reaction results in
mineral hydrates that are not very water-
soluble and so are quite durable in water and
safe from chemical attack.
 INTRODUCTION
• This allows setting in wet conditions or under
water and further protects the hardened
material from chemical attack.
• The chemical process for hydraulic cement
found by ancient Romans used volcanic
ash (pozzolana) with added lime (calcium
oxide).
 HISTORY
Cementing materials have played a vital role and
were used widely in the ancient world.
• The Egyptians used calcined gypsum as a
cement
• The Greeks and Romans used lime made by
heating limestone and added sand to make
mortar, with coarser stones for concrete.
 HISTORY
• In places where volcanic ash was scarce, such
as Britain, crushed brick or tile was used
instead.
• The Romans were therefore probably the first
to manipulate systematically the properties of
cementitious materials for specific
applications and situations.
 HISTORY
• The Romans found that a cement could be
made which set under water and this was
used for the construction of harbours.
This cement was made by adding crushed
volcanic ash to lime and was later called a
"pozzolanic" cement, named after the village of
Pozzuoli near Vesuvius.
 ROMAN’S CONTRIBUTION
• Marcus Vitruvius Pollio, a Roman architect and
engineer in the 1st century BCE wrote his "Ten
books of Architecture" - a revealing historical
insight into ancient technology. Writing about
concrete floors, for example:

"First I shall begin with the concrete flooring,

which is the most important of the polished
finishings, observing that great pains and the
utmost precaution must be taken to ensure its
durability".
 ROMAN’S CONTRIBUTION
• And on pozzolana:

"There is also a kind of powder from which

natural causes produces astonishing results. This
substance, when mixed with lime and rubble, not
only lends strength to buildings of other kinds, but
even when piers are constructed of it in the sea,
they set hard under water."

(Vitruvius, "The Ten Books of Architecture," Dover

Publications, 1960.)
 INDUSTRIAL REVOLUTION
• In eighteenth century Britain, the interests of
industry and empire coincided, with the need
to build lighthouses on exposed rocks to
prevent shipping losses.
• The constant loss of merchant ships and
warships drove cement technology forwards.
 INDUSTRIAL REVOLUTION
• Smeaton, building the third Eddystone
lighthouse (1759) off the coast of Cornwall in
Southwestern England, found that a mix of
lime, clay and crushed slag from iron-making
produced a mortar which hardened under
water.
 INDUSTRIAL REVOLUTION
• Joseph Aspdin took out a patent in 1824 for
"Portland Cement," a material he produced by
firing finely-ground clay and limestone until
the limestone was calcined.
• He called it Portland Cement because the
concrete made from it looked like Portland
stone, a widely-used building stone in
England.
 INDUSTRIAL REVOLUTION
• A few years later, in 1845, Isaac Johnson made
the first modern Portland Cement by firing a
mixture of chalk and clay at much higher
temperatures, similar to those used today.
• At these temperatures (1400ᵒC-1500ᵒC),
clinkering occurs and minerals form which are
very reactive and more strongly cementitious.
 INDUSTRIAL REVOLUTION
• While Johnson used the same materials to make
Portland cement as we use now, three important
developments in the manufacturing process lead to
modern Portland cement:

1. Development of rotary kilns

2. Addition of gypsum to control setting

3. Use of ball mills to grind clinker and raw materials

 INDUSTRIAL REVOLUTION

• From the turn of the 20th century, rotary

cement kilns gradually replaced the original vertical
shaft kilns, used originally for making lime.

• Rotary kilns heat the clinker mainly by radiative heat

transfer and this is more efficient at higher
temperatures, enabling higher burning temperatures
to be achieved.
 INDUSTRIAL REVOLUTION
• Also, because the clinker is constantly moving
within the kiln, a fairly uniform clinkering
temperature is achieved in the hottest part of the
kiln, the burning zone.

• The two other principal technical developments,

gypsum addition to control setting and the use of
ball mills to grind the clinker, were also
introduced at around the start of the 20th
century.
 MAJOR TYPES OF CEMENTS
The major types of cements are:
• Portland Cement
• Slag Cement
• High-alumina Cement
• Expanding and nonshirinking Cement
• Gypsum Plasters
• Polymer Cements
• Magnesium Oxychloride Cement
 CHEMISTRY OF CEMENT
• Non-hydraulic cement, such as slaked lime
(calcium oxide mixed with water), hardens
by carbonation in the presence of carbon
dioxide, which is naturally present in the air.
• First calcium oxide (lime) is produced
from calcium carbonate (limestone or chalk)
by calcination at temperatures above 825 °C
(1,517 °F) for about 10 hours at atmospheric
pressure:
 CaCO3 → CaO + CO2
• The calcium oxide is then spent (slaked) mixing it with
water to make slaked lime (calcium hydroxide):
CaO + H2O → Ca(OH)2
• Once the excess water is completely evaporated (this
process is technically called setting), the carbonation
starts:
Ca(OH)2 + CO2 → CaCO3 + H2O
• This reaction takes time, because the partial pressure
of carbon dioxide in the air is low. The carbonation
reaction requires that the dry cement be exposed to
air, so the slaked lime is a non-hydraulic cement and
cannot be used under water. This process is called
the lime cycle.
 CHEMISTRY OF CEMENT
• Conversely, hydraulic cement hardens by
hydration when water is added. Hydraulic
cements (such as Portland cement) are made of a
mixture of silicates and oxides, the main
components being:
– Tricalcium silicate, C3S
– Dicalcium silicate, C2S
– Tricalcium aluminate, C3A
– Tetracalcium aluminoferrite, C4AF
– Gypsum, CSH2
 CHEMICAL REACTIONS DURING
HYDRATION
When water is added to cement, the following series of
reactions occur:
• The tricalcium aluminate reacts with the gypsum in the
presence of water to produce ettringite and heat:

C3A + 3CSH2 + 26H → C6AS3H32, ∆H = -207 cal/g

Ettringite consists of long crystals that are only stable in a

solution with gypsum. The compound does not
contribute to the strength of the cement glue.
• The tricalcium silicate (alite) is hydrated to
produce calcium silicate hydrates, lime and
heat:

2C3S + 6H → C3S2H3 + 3CH, ∆H = -120 cal/g

The CSH has a short-networked fiber structure

which contributes greatly to the initial strength
of the cement glue.
• Once all the gypsum is used up as per reaction (i),
the ettringite becomes unstable and reacts with
any remaining tricalcium aluminate to form
monosulfate aluminate hydrate crystals:

2C3A + 3 C6AS3H32 + 22H → 3C4ASH18,

The monosulfate crystals are only stable in a sulfate

deficient solution.
In the presence of sulfates, the crystals resort back
into ettringite, whose crystals are two-and-a-half
times the size of the monosulfate.
It is this increase in size that causes cracking when
cement is subjected to sulfate attack.
• The belite (dicalcium silicate) also hydrates to
form calcium silicate hydrates and heat:

C2S + 4H → C3S2H3 + CH, ∆H = -62 cal/g

Like in reaction (ii), the calcium silicate hydrates

contribute to the strength of the cement paste.
This reaction generates less heat and proceeds at a
slower rate, meaning that the contribution of C2S to
the strength of the cement paste will be slow
initially.
This compound is however responsible for the long-
term strength of portland cement concrete.
• The ferrite undergoes two progressive reactions with the
gypsum:

– in the first of the reactions, the ettringite reacts with the

gypsum and water to form ettringite, lime and alumina
hydroxides, i.e.

C4AF + 3CSH2 + 3H → C6(A,F)S3H32 + (A,F)H3 + CH

– the ferrite further reacts with the ettringite formed above to

produce garnets, i.e.

C4AF + C6(A,F)S3H32 + 2CH +23H → 3C4(A,F)SH18 + (A,F)H3

The garnets only take up space and do not in any way

contribute to the strength of the cement paste.
 THE HARDENED CEMENT PASTE
Hardened paste consists of the following:

Ettringite 15 to 20%
Calcium silicate hydrates, CSH 50 to 60%
Calcium hydroxide (lime) 20 to 25%
Voids 05 to 06%
(in the form of capillary voids and entrapped
and entrained air)
PORTLAND CEMENT
 INTRODUCTION
• Portland cement is the most common type of cement in general use
around the world as a basic ingredient of:

Concrete: is a composite material composed of fine and

coarse aggregate bonded together with a fluid cement (cement paste) that
hardens over time

Mortar: is a workable paste used to bind building blocks such

as stones, bricks, and concrete masonry units together.

Stucco: is a material made of aggregates, a binder and water. It is used as a

decorative coating for walls and ceilings, and as a sculptural and artistic
material in architecture.

Non-specialty grout: is a dense fluid which is used to fill gaps or used as

reinforcement in existing structures. Mixture of water, cement and sand.
• The most common, called ordinary Portland
cement (OPC), is grey in colour, but white
Portland cement is also available.
• Its name is derived from its similarity
to Portland stone which was quarried on
the Isle of Portland in Dorset, England. It was
named by Joseph Aspdin who obtained a
patent for it in 1824.
• Portland cement is caustic, so it can cause chemical
burns.
• The powder can cause irritation or, with severe
exposure, lung cancer, and can contain some hazardous
components, such as crystalline silica and hexavalent
chromium.
• Environmental concerns are the high energy
consumption required to mine, manufacture, and
transport the cement, and the related air pollution,
including the release of greenhouse gases(e.g., carbon
dioxide), NOx, SO2, and particulates.
• Concrete produced from Portland cement is one of the
world's most versatile construction materials.
 CHEMICAL COMPOSITION
Made up of four main compounds:

• Tricalcium silicate (3CaO · SiO2),

• Dicalcium silicate (2CaO · SiO2),
• Tricalcium aluminate (3CaO · Al2O3), and
• Tetra-calcium aluminoferrite (4CaO · Al2O3Fe2O3).

In an abbreviated notation differing from the normal atomic

symbols, these compounds are designated as C3S, C2S, C3A,
and C4AF, where C stands for calcium oxide (lime), S for silica,
A for alumina, and F for iron oxide.

Small amounts of uncombined lime and magnesia also are

present, along with alkalies and minor amounts of other
elements.
 HYDRATION
• The most important hydraulic constituents are the calcium silicates,
C2S and C3S.

• Upon mixing with water, the calcium silicates react with water
molecules to form calcium silicate hydrate (3CaO · 2SiO2 · 3H2O)
and calcium hydroxide (Ca[OH]2).

• These compounds are given the shorthand notations C–S–H

(represented by the average formula C3S2H3) and CH, and the
hydration reaction can be crudely represented by the following
reactions:

2C3S + 6H = C3S2H3 + 3CH2C2S + 4H = C3S2H3 + CH

• During the initial stage of hydration, the parent compounds

dissolve, and the dissolution of their chemical bonds generates a
significant amount of heat.
 TYPES OF PORTLAND CEMENT
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 inter-ground addition.
• It can harden without drying or by reacting
with atmospheric carbondioxide.
TYPES OF PORTLAND CEMENT
 MANUFACTURING OF PORTLAND
CEMENT
• The next step in the process is to heat the
blended mixture of raw materials.
• Convert it into a granular material called cement
clinker.
• This requires maximum temperatures that are
high enough to partially melt the raw
mix. Because the raw ingredients are not
completely melted, the mix must be agitated to
ensure that the clinker forms with a uniform
composition.
• This is accomplished by using a long cylindrical
kiln that slopes downward and rotates slowly.
MANUFACTURING OF CEMENT BY DRY
PROCESS
ROTARY KILN FOR DRY PROCESS
TEMPERATURE ZONES IN ROTARY KILN FOR DRY PROCESS
TEMPERATURE ZONES IN ROTAY KILN FOR WET PROCESS
 DESCRIPTION OF THE PROCESS
• The raw mix enters at the upper end of the kiln
and slowly works its way downward to the
hottest area at the bottom over a period of 60-90
minutes, undergoing several different reactions
as the temperature increases.
• It is important that the mix move slowly enough
to allow each reaction to be completed at the
appropriate temperature.
• Because the initial reactions are endothermic
(energy absorbing), it is difficult to heat the mix
up to a higher temperature until a given reaction
is complete.
 DESCRIPTION OF THE PROCESS
• Dehydration zone (up to ~ 450˚C): This is
simply the evaporation and removal of the
free water. Even in the “dry process” there is
some adsorbed moisture in the raw
mix. Although the temperatures required to
do this are not high, this requires significant
time and energy. In the wet process, the
dehydration zone would require up to half the
length of the kiln, while the dry process
requires a somewhat shorter distance.
 DESCRIPTION OF THE PROCESS
• Calcination zone (450˚C – 900˚C): The term calcination
refers to the process of decomposing a solid material
so that one of its constituents is driven off as a gas.
• At about 600˚C the bound water is driven out of the
clays, and by 900˚C the calcium carbonate is
decomposed, releasing carbon dioxide.
• By the end of the calcination zone, the mix consists of
oxides of the four main elements which are ready to
undergo further reaction into cement minerals.
• Because calcination does not involve melting, the mix
is still a free-flowing powder at this point.
 DESCRIPTION OF THE PROCESS
• Solid-state reaction zone (900˚ - 1300˚C): This zone slightly overlaps, and
is sometimes included with, the calcination zone. As the temperature
continues to increase above ~ 900˚C there is still no melting, but solid-
state reactions begin to occur.
• CaO and reactive silica combine to form small crystals of C2S (dicalcium
silicate), one of the four main cement minerals. In addition, intermediate
calcium aluminates and calcium ferrite compounds form.
• These play an important role in the clinkering process as fluxing agents, in
that they melt at a relatively low temperature of ~ 1300˚C, allowing a
significant increase in the rate of reaction.
• Without these fluxing agents, the formation of the calcium silicate cement
minerals would be slow and difficult. In fact, the formation of fluxing
agents is the primary reason that portland (calcium silicate) cements
contain aluminum and iron at all.
• The final aluminum- and iron-containing cement minerals (C3A and C4AF)
in a portland cement contribute little to the final properties. As the mix
passes through solid-state reaction zone it becomes “sticky” due to the
tendency for adjacent particles to fuse together.
 DESCRIPTION OF THE PROCESS
• Clinkering zone (1300˚C – 1550˚C): This is the hottest zone where
the formation of the most important cement mineral, C3S (alite),
occurs. The zone begins as soon as the intermediate calcium
aluminate and ferrite phases melt.

• The presence of the melt phase causes the mix to agglomerate into
relatively large nodules about the size of marbles consisting of
many small solid particles bound together by a thin layer of liquid.
• Inside the liquid phase, C3S forms by reaction between C2S crystals
and CaO. Crystals of solid C3S grow within the liquid, while crystals
of belite formed earlier decrease in number but grow in size.
• The clinkering process is complete when all of silica is in the C3S and
C2S crystals and the amount of free lime (CaO) is reduced to a
minimal level (<1%).
 DESCRIPTION OF THE PROCESS
• Cooling zone: As the clinker moves past the bottom of the kiln the
temperature drops rapidly and the liquid phase solidifies, forming
the other two cement minerals C3A (aluminate) and C4AF (ferrite).
• In addition, alkalis (primarily K) and sulfate dissolved in the liquid
combine to form K2SO4 and Na2SO4. The nodules formed in the
clinkering zone are now hard, and the resulting product is called
cement clinker.
• The rate of cooling from the maximum temperature down to about
1100˚C is important, with rapid cooling giving a more reactive
cement.
• This occurs because in this temperature range the C3S can
decompose back into C2S and CaO, among other reasons. It is thus
typical to blow air or spray water onto the clinker to cool it more
rapidly as it exits the kiln.
DIFFERENCE BETWEEN THE TWO
PROCESSES
TYPES OF CEMENT
 POZZOLAN CEMENT
• Lime cements are mixtures of
ground pozzolan and lime.
• These are the cements the Romans used, and are
present in surviving Roman structures like
the Pantheon in Rome.
• They develop strength slowly, but their ultimate
strength can be very high.
• The hydration products that produce strength are
essentially the same as those in Portland cement.
 SLAG-LIME CEMENTS
• Ground granulated blast-furnace slag is not
hydraulic on its own, but is "activated" by
addition of alkalis, most economically using
lime.
• They are similar to pozzolan lime cements in
their properties.
• Only granulated slag (i.e., water-quenched,
glassy slag) is effective as a cement
component.
 MAGNESIUM OXYCHLORIDE CEMENT
• A high performance cement binder that has a
multitude of beneficial properties when
compared to Ordinary Portland Cement (OPC)
binder systems. The binder is formed through an
acid-base reaction.
• Also known as Sorel’s Cement.
• Produced by exothermic action of 20% solution of
MgCl2 on a blend of magnesia obtained by
calcining magnesite.
• Reaction is as follows:
3MgO + MgCl2 + 11H2O → 3MgO.MgCl2.11H2O
• The material does not need wet curing, has
high fire resistance, excellent mold resistance,
low thermal conductivity, low shrinkage and
excellent abrasion resistance.
• In the right proportions it can provide high
compressive and flexural strength.
• Compressive strength can reach 7,000 to
10,000 psi when fully cured even in the
presence of 40-50% filler.
 POLYMER CEMENTS
• Made from organic chemicals that polymerize.
• Producers often use thermoset materials.
• While they are often significantly more
expensive, they can give a water proof material
that has useful tensile strength.
• Also composed of aggregates that
include silica, quartz, granite, limestone, and
other high quality material. The aggregate must
be of good quality, free of dust and other debris,
and dry.
 SUPER SULPHATED CEMENTS
• contain about 80% ground granulated blast
furnace slag, 15% gypsum and a little
Portland clinker or lime as an activator.
• They produce strength by formation
of ettringite, with strength growth similar to a
slow Portland cement.
• They exhibit good resistance to aggressive
agents, including sulfate.
 CALCIUM ALUMINATE CEMENTS
• Calcium aluminate cements are hydraulic cements
made primarily from limestone and bauxite.
• The active ingredients are monocalcium aluminate
CaAl2O4 (CaO · Al2O3 or CA in Cement chemist notation,
CCN) and mayenite Ca12Al14O33 (12 CaO · 7 Al2O3, or
C12A7 in CCN).
• Strength forms by hydration to calcium aluminate
hydrates.
• They are well-adapted for use in refractory (high-
temperature resistant) concretes, e.g., for furnace
linings.
 CALCIUM SULPHO-ALUMINATE
CEMENTS
• Made from clinkers that
include ye'elimite (Ca4(AlO2)6SO4 or C4A3S in Cement
chemist's notation) as a primary phase.
• They are used in expansive cements, in ultra-high early
strength cements, and in "low-energy" cements.
• Hydration produces specialized physical properties (such as
expansion or rapid reaction) are obtained by adjustment of
the availability of calcium and sulfate ions.
• The lower limestone content and lower fuel consumption
leads to a CO2 emission around half that associated with
Portland clinker. However, SO2 emissions are usually
significantly higher.
 HIGH ALUMINA CEMENTS
• The raw materials of HAC are limestone or
chalk and bauxite (a residual deposit formed
by weathering under tropical conditions of
rock containing Al2O3, Fe2O3, FeO)
• Interground and calcined at 1600ᵒC in the kiln.
• The solidified material is fragmented and
ground to a fineness of 2500-3000 cm2/gr. Its
color is dark grey.
• High resistance to the action of sulfate waters
(due to absence of Ca(OH)2).
• Extremely high early strength (suitable for
emergency repairs). 80% of the ultimate strength
is achieved in 24 hours or even at 6-8 hours.
• Initial set = 4 hrs.
• Final set = 5 hrs.
• Rapid hardening is not accompanied by rapid
setting.
• With special aggregates such as firebrick, it can
be used to make refractory concrete that can
stand high furnace temperature (T> 1300ᵒC).
• It is expensive.
• Never mix HAC with PC (gives low strength).
OXIDE COMPOSITION OF ORDINARY
PC
CHEMICAL ANALYSIS OF ORDINARY PC
MAIN CHEMICAL COMPOUNDS OF PC
TIME FOR 80% HYDRATION