• MANUFACTURING PROCEDURE of PORTLAND

CEMENT

• Two types of materials are necessary for the production of

portland cements.

• - Materials rich in calcium , such as limestone, chalk

• - Materials rich in silica , such as clay

• Some raw materials used in portland cement production

• Calcerous: Limestone, cement rock

• Argillaceous: Clay, Shale
• Siliceous: Sand, Sandstone and quarz
• Ferrous : Iron ore, pyrites
• Other: Gypsum, Fly ash
• These raw materials are finely ground, mixed and heated in a
rotary kiln to form cement clinker.

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 PORTLAND CEMENT

The phase compositions in portland

cement are denoted by ASTM as
tricalcium silicate (C3S), dicalcium silicate
(C2S), tricalcium aluminate (C3A), and
tetracalcium aluminoferrite (C4AF).

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 RAW MATERIALS OF CEMENT

There are four main raw materials of

cements. These are;
Limestone
Clay
Sand
Additives

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 LIMESTONE

Limestone is calcareous
sedimentary rocks formed at
the bottom of lakes and
seas with the accumulation
of shells, bones and other
calcium rich goods. It is
composed of calcite
(CaCO3). The rock which
contains more than 95% of
calcium carbonate is known
as high-calcium limestone.

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 CLAY
Clay is the second
important raw material
for cement. The main
component of clay is
aluminum silicates. Clays
are plastic sediments.
They consist mainly of
the remains of
preexisting rocks which
have been broken down
by weathering and
erosion.

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 SAND
Sand is source
of SiO2. Sand is
used because the
ratio of SiO2 in the
clay is not enough.
So, sand is used as
a raw material for
producing cement.

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 ADDITIVES
TRASS
Trass is the
pozzalonic material.
Trass can be found as
volcanic tuff containing
silica. Trass is a
powerful hydraulic
connector. It increases
the resistance of
cement. Trass contains
50-60 % silica (SiO2).
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 ADDITIVES

SLAG
Slag is the product
of iron-steel industry.
When it is mixed
with lime it shows
connecting property.

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 ADDITIVES
GYPSUM
Gypsum is known as
calcium sulphate
(CaSO4.2H2O). Gypsum
is added to clinker when
grinding is started.
Gypsum prevents early
freezing.

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12/08/21 Ballice, 2010 10
 PRODUCTION
Raw Material Preparation

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 Raw Grinding & Burning

12/08/21 Ballice, 2010 12

Cement Grinding & Shipping

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12/08/21 Ballice, 2010 14
 • Cement technology is very traditional
and the basic principles have
remained unchanged for a long time.

• However, very profound changes in

the production techniques were
introduced leading to the diminishing
of energy consumption and decrease
in employment as well as fundamental
pollution limitations.

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 • Significant progress has been
achieved in pollution control.
• The dust emission decreased to
about 0.2-0.3 g/kg of cement.
• NOx, SO2 and CO are of the
order 1200, 400 and 500 ppm,
respectively, per cubic metre of
kiln gases. For the special pre-
calciner NOx can be as low as
400 ppm.

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 • The problem is CO2 emission,
which originates mainly from
CaCO3 decomposition during
clinker burning.

• A partial solution to this problem is

the increasing production of cement
with additives, chiefly slag, fly ash
and limestone.

12/08/21 Ballice, 2010 17

 • Raw material preparation

• Clinker produced in the

properties of Portland cement is
determined by the mineralogical
composition of clinker.

• The classic Portland clinker has

the following mineralogical
composition:

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 • 3CaO .SiO2 alite 55-65%

• 2CaO. SiO2 belite 15-25%

• 3CaO. AI2O3 aluminate 8-14%

• 4CaO .Al2O3 .Fe2O3

brownmillerite 8-12 %

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 • The entire content of minor
components such as MgO, K2O,
TiO2, Mn2O, and SO3 is normally
under 5 per cent.

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 • Raw material crushing

• There have been no major changes in

the technology of primary crushing of
raw materials in recent years.

• As a rule, mainly the single- and twin-

rotor hammer crushers and impact
crushers are used for the primary size
reduction. Jaw crushers, also in
combination with roll crushers and
gyratory crushers, are applied,
especially for hard as well as for
softer materials.

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 CRUSHERS
The raw materials
which are taken from
their mines are big
pieces. But the raw
materials must be
broken before use.
The machine which
breaks the big raw
materials is called
crusher.
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 RAW MILLS

The next step in the

process is to grind the
above particles to a size
of 90 microns or less
which is done in a raw
mill, a closed circuit ball
mill equipped with high
efficiency separator.
The main part of
grinding operation is
done by balls.

12/08/21 Ballice, 2010 23

 • Raw material grinding

• For wet and dry grinding of the

raw materials, ball mills are used
which operate either as open
circuit mills or in closed circuit,
in case of the dry process with
an air classifier. By wet grinding
the process is closed through
the vibrating screen or arc-
screen.
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 • The quick elimination of the fine
fraction in closed circuit
increases the grinding efficiency
by about 20 per cent.

• The granulometric composition

of the feed greatly influences the
energy consumption.

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 • The energy consumption in ball mills
is also heavily influenced by the
grinding media filling ratio, by the
design of the mill liners and by
grinding media classification in the
last chamber.

• For the solution of the grinding media

classification the so-called
autoclassifying liners are used.

• Because of the predominance of the

dry method of clinker production, in
the dry grinding technology more new
achievements have been introduced.
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 • Classifiers

• A classifier exerts significant

influence on mill efficiency and
consequently on energy
consumption.

• For the product containing 90 per

cent of the fraction under 30 μm,the
energy consumption of the ball mill is
65 kWh/t when the classifier
efficiency is 25 per cent, but falls to
35 kWh/t for 100 per cent classifier
efficiency.

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 • Homogenization

• Raw material homogenization is

a very important technological
operation because the kiln feed
should have a very stable
chemical composition.

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 • The variations of chemical
composition of raw mix influence
unfavourably the kiln exploitation
and clinker quality.

• For a stable kiln operation, the LSF

factor (lime saturation factor)
fluctuations should be lower than
one point. Each technological
operation should increase the
stability of raw materials.
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12/08/21 Ballice, 2010 31
 • The effect of homogenization can
be calculated using the following
equation:

• H= Sα/Sβ
• where Sα is the standard
deviation of input variations
• and Sβ is the standard deviation
of output variations.

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 • There are several methods of raw
meal homogenization

• Significant progress in
pneumatic homogenization of
raw meal has been made with
continuous blending systems.

• There are two major types of

blending silo designs: turbulence
and controlled flow.

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 • In a turbulence silo, the material
is tumbled about by the injection
of high volume air through air-
pads on the silo floor.

• In the controlled flow system, the

silo is divided into a large
number of flow streams which
run parallel at different flow
rates, and the meal is finally
blended in a tank.
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12/08/21 Ballice, 2010 38
 BURNING
Burning is same for all kiln systems. Clinker
leaves the rotary kiln at 1400-1500°C. But
before to reach that temperature there must be
some processes. Also after the real burning in
kiln there must be other processes to reach cold
clinker. So burning process arises some
common processes. They are;

Preheating (Cyclone preheaters)

Precalcination (Precalciner)
Rotary Kiln
Clinker Cooling

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 BURNING
CYCLONE PREHEATERS
Cyclone preheater kilns can
have any number of stages
between 1 and 6, with increasing
fuel efficiency with more cyclone
preheater stages. The most
common is the 4-stage
suspension preheater, where
gases typically leave the
preheater system at around
350°C.

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 BURNING
PRECALCINER

In precalciner kilns, the combustion air for burning

fuel in the preheater no longer passes through the kiln,
but it is taken from the cooler region by a special tertiary
air duct to a specially designed combustion vessel in the
preheater tower. the calcination operates at
temperatures around the calcination temperature of raw
meal (800°C-900°C), there may not be a flame as such.
The advantages of precalciner are increasing the
capacity, decreasing the energy consumption.

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 BURNING
ROTARY KILNS

The real chemical

reactions take place in
rotary kilns. The rotary kilns
are important for cement
production. The main
chemical reactions to
produce the calcium
silicates that later give
cement its bonding strength
occur in the kiln system.
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 BURNING
ROTARY KILNS
Reactions:
Dehydration of clay minerals:
Al4 [(OH)8 Si 4 O10 ]  2( Al2 O3 2SiO 2 )  4H 2 O
Al2O3 .SiO2  Al2O3  SiO2

Decomposition of Carbonates:
CaCO3  CaO  CO2
3CaO  2SiO2  Al 2 O3  2(CaO.SiO2 )  CaO. Al 2 O3

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 BURNING
ROTARY KILNS
Reactions:
Solid Reactions (reactions below clinkering):

CaO. Al 2 O3  2CaO  3CaO. Al 2 O3

CaO. Al 2 O3  3CaO  Fe2 O3  4CaO. Al 2 O3 .Fe2 O3
CaO.SiO2  CaO  CaO.SiO2

Reactions in the presence of liquid phase (clinkering):

CaO  2CaO.SiO2  3CaO.SiO2

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 BURNING
CLINKER COOLERS
Planetary Coolers: In this
type of cooler the flow of clinker
from the kiln is divided over 10
individual cooling tubes
disposed around the kiln tube.
Grate Coolers: In majority of
the existing plants, conventional
grate coolers are used. These
coolers have lower recuperation
efficiency, occupy more space
and need more cooling air.

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 • Clinker burning

• The dry method became

predominant in the cement
industry because of the much
lower heat consumption, a
typical value being 3000 kJ/kg of
clinker for dry and 5500 kJ/kg for
wet method.

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 • The latest aehievement in
burning technology is
constituted by very short kilns
with L/D ratio of about 10 .
• These kilns ensure a very rapid
clinker formation, which gives a
very quick reactions run without
recrystallization phenomena and,
as a result, a higher hydraulic
activity of the clinker is obtained.

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 • High volumetric loading of these
kilns causes the drop in heat
consumption due to a reduction
of the heat losses from radiation
from the kiln shell and preheater,
but the main problem remains
the heat losses with the exit
gases.

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 • Cement grinding

• For cement grinding, ball mills

are more frequently used. They
have a rather high-energy
consumption, typically 34 kWh/t
for cement having a specific
surface of 300 m2/kg.

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 CEMENT MILLS
The clinker is cooled and ground into a
fine gray powder. A small amount of
gypsum is also added during the final
grinding. It is now the finished product -
Portland cement
During milling, the clinker, gypsum and
other additives are broken down to
particles less than 0.2mm in size.

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 • Ball mills have low efficiency, the
majority of energy being
transformed into heat.

• Significant progress in grinding

technology has been due to the
application of roller press for pre-
grinding or finish grinding.

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• The specific energy consumption for a complete
cement grinding plant shown on Figure is between 26
and 29 kWh/t for a finished product.

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 • Automation

• The process technology and

mechanical equipment for
cement production has became
increasingly complex in recent
years.

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 • Product quality and diversity,
environmental protection,
secondary fuels, and energy
management require more
sensitive plant management.

• These are the main reasons for

the introduction of computers for
process control and for
information systems.

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• The classical structure of the process control and
information systems is distinguished by a relatively
clear pyramid hierarchy.

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 • Environmental protection

• The manufacture of cement

necessarily involves interference
with the environment, although
the cement industry is doing its
best to minimize the negative
effects of this.

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 • The problem comprises the water
discharge, solid waste, noise and air
pollution.

• Solid waste practically concerns kiln

bricks. When chromium bricks are
eliminated, the alumina bricks can be
added to the raw material and
magnesium bricks sent to the landfill.

• Air pollution has been the main

problem for the cement industry.
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 • For twenty years, a significant
progress has been made within
the cement industry in the field
of air pollution protection.

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 • The dust emission problem is
now practically solved and the
new construction of electrostatic
precipitators and fabric filters,
operating with a compressed air
(reverse-pulse) cleaning system,
have ensured a very low
emission level, typically under 50
mg/m3 of gases.

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 • Portland cements is the product
obtained by pulvarizing clinker
consisting essentially of hydraulic
calcium silicates, usually containing
one or more forms of calcium sulfate
as an interground addition.

• Hydraulic calcium silicates poses the

ability to harden without drying or by
reaction with atmospheric carbon
dioxide.

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 • Five types of portland cements are recognized

• Type I : Regular portland cements are the usual

products for general construction such as white
(less ferric oxide), oil-well cement, quick-setting
cement.

• Type II: Moderate heat of hardening and sulphate

resisting portland cements are for use where
moderate heat of hydration is required or for general
concrete construction exposed to moderate sulphate
action.

• Type III: High early strength (HES) cements are made

from raw materials with lime to silica ratio higher that
of Type I cements. They contain a higher proportion
of tricalcium silicate (C3S) than regular portland
cements. This kind of cements can be put on service
road constructions insteaed of regular cements.

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 • Type IV: Low heat portland cements
contain a lower percentage of C3S
and tricalcium aluminate (C3A). The
percentage of tetracalcium
aluminoferrite (C4AF) is increased
because of the addition of the Fe2O3
to reduce the amount of C3A.

• Type V: Sulphate resisting portland

cements are resist sulfate better than
other four types. These cements are
lower in C3A than regular cements. In
consequence of this, the C4AF
contents is higher.
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 • SETTING AND HARDENING OF CEMENT

• The reaction of the setting and hardening of cement

involves hydration and hydrolysis.

• The hydration products have very low solubility in

water. (It is clear that the concrete is not attacted by
water.)

• The heat of hardening for some compounds

• C3A > C3S > C4AF > C2S

• low heat of hardening cements are made low in C3A

and C3S but high C2S

• This accomplished by adding more Fe2O3, which

takes Al2O3 out of circulation as C4AF, thereby
diminishing the amount of C3A. and by decreasing
CaO/SiO2 ratio.

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 • Low heat of setting cements is used in the
construction of all large dams to avoid
cracking the structure from heat stresses
during setting and cooling.

• Additives increases some properties of

cements:

• For example; superplasticizer naphtelene

derivatives

• Calcium nitrite ( to inhibit the corrosion of

steel reinforcing bars in concrete)

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 • OTHER CEMENTS

• For many corrosive conditions,

portland cements is not suitable.
For that reasons, many special
cements have been developed.

• The types of special cements

based on organic plastic, known
as adhesives .

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 • POZZOLANS:

• A pozzolans is a material which is not

cementitious in itself but which becomes
so upon admixture with lime.

• The early strengthof such a cement is lower

than that of portland cement but within a
years the strength are equal.

• The advantages: It resist the corrosive

action of saline solution and seawater

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 • HIGH ALUMINA CEMENTS:

• It is manufactured by fusing a mixture

of limestone and bauxite ( includes
also iron oxide, silica, magnesia and
other impurities) and is called as
calcium aluminate cements.

• The advantages: The very rapid

development of strength, superior
resistance to seawater and sulphate-
bearing water.
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 • SILICATE CEMENTS:

• This type of cements is

withstand all concentration of
inorganic acids except
hydrofluoric.

• Using area: Joining of bricks in

chromic acid reaction tanks and
in alum tanks.

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 • SULFUR CEMENTS

• Sulfur cements are resistanst to

nonoxiding acids and salts but should
not be used in the presence alkalies ,
oils, greases, or solvents.

• Using area: Thiokol -plasticized silica

- filled sulphur cements have been
accepted as a standart materials for
joining bricks, and cast iron pipes.

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 • POLYMER CONCRETE:

• These products consist of resins

such as epoxy methyl methacrylate,
or polyester.

• Advantages: rapid curing, corrosion

resistance and high compressive
strength

• These concretes are much higher in

price than regular portland cement
concrete
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 • MAGNESIUM OXYCHLORIDE CEMENT:

• This cement is produced by the following

reaction:
• 3MgO + MgCl2 + 11H2O 
3MgO.MgCl2.11H2O

• The product is hard and strong but is

attacked by water,which leaches out the
magnesium chloride.

• Using area: Flooring cements with an inert

filler and a coloring pignent, and as a base
for such as flooring as tile and terrazzo. It is
strongly corrosive to iron pipes in contact
with it. Sand and wood pulp may be added
as fillers.
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 • The magnesia used may contain small
amount of calcium oxide, calcium
hydroxide, or calcium silicates , which
during the setting process increase
the volume changes, thus decreasing
strength and durability.

• As an additive, copper powder is also

added to increases water resistance ,
adhesion and dry and wet strenght
over that of ordinary magnesium
oxychloride cements.

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 • LIME

• Lime itself may be used for:

• - medical purposes
• - insecticides
• - plant and animal food
• - gas adsorption
• - precipitation
• - causticizing

• It is employed as a reagent in the sulfite process for

papermaking , dehairing hides, the manufacture of
highgrade steel and cement , water softening,
recovery of by-product ammonia , and manufacture
of soap, rubber, varnish, refractories, and sand lime
brick.

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 • The suitability of lime for any
particular use depends on its
composition and physical
properties all of which can be
controlled by the selection of the
limestone and the detail of the
manufacturing process.

• Much lime must be finely ground

before use.

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 • Depending of composition,

• There are several distinct types of

limes.

• - Hydraulic limes (obtained from the

burning of limestone containing clay)

• - High-calcium-content limes (harden

only with the adsorption of carbon
dioxide from the air)- it is used
especially for chemical purposes
except for the sulfite paper process.
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 • Magnesian limes (or dolomite) - it
is used for refractory material in
furnaces

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 HOW LIME IS PRODUCED ?

 Quarrying or mining
Limestone is extracted in both
underground and surface mines. Lime-
quality limestone must be carefully
identified and extracted to maintain its
purity.
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 HOW LIME IS PRODUCED ?

 Stone preparation

This step includes crushing and

screening, and in many cases, washing to
remove impurities.

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 HOW LIME IS PRODUCED?
 Calcining
Limestone, which is primarily composed of calcium
carbonate, is heated to convert the calcium carbonate
into calcium oxide. This process is generally carried
out in either large rotary kilns or vertical shaft kilns.
Because of the high temperatures. The product of the
calcining process is quicklime, which can be used as
"pebble lime," or may be crushed or pulverized,
depending on its intended use.

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 HOW LIME IS PRODUCED?

 Hydrating

Hydrated (or slaked) lime is

produced by reacting quicklime with
water in continuous hydrators. The end
product is a fine dry powder, or, with
additional water, pumpable milk of lime. 
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 Manufacturing Process of Lime

There are two main reactions when lime is produced

from limestone.

Calcination
CaCO3(s) → CaO(s) + CO2(g)

Hydration
CaO(s) + H2O(l) → Ca(OH)2(s)

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12/08/21 Ballice, 2010 101
 Vertical Kilns

The main characteristic that all vertical kilns have in

common four sections:
• Storage
• Preheating
• Calcining
• Cooling

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 Vertical Kilns

The limestone is charge into the top of the kiln and

cooled lime is discharged at the bottom.

• In the preheating; limestone is heated from ambient

to 8000C by direct contact with the gases leaving the
calcining.(i.e. Products of combustion, excess air and
CO2 from calcination)

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 Vertical Kilns

• In the calcining; fuel is burned in preheated air from the

cooling and in additional combustion air added with the
fuel. This produces a temperature of over 9000C and
causes dissociation of the lime into quicklime and CO2.

• In the cooling; quicklime leaving the calcining zone at

9000C is cooled by direct contact with cooling air, part of
all of the combustion air, which in return is preheated.

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 Figure 1. Vertical shaft kiln
12/08/21 Ballice, 2010 105
 • MANUFACTURE

• The carbonates of calcium and magnesium

are obtained from deposits of limestone ,
marble, dolomite.

• For chemical purposes, a rather pure

limestone is preferred as a starting material.

• The reactions:

• CALCINATION
• CaCO3(s) ↔ CaO (s) + CO2 H1200-
1300 oC = 4 Gj/t of lime produced

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 • HYDRATION

• CaO(s) + H2O (l)  Ca(OH)2(s) H

= -66.5 kj

• During calcination the volume

contracts During hydration the volume
swell

• For calcination the average fuel ratios,

using bituminous coal, are 3.23 kg of
lime for 1 kg coal in shaft kilns
• and 3.37 kg in rotary killns.
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 • The calcination reactions is
reversible. Below 650 oC the
equilibrium decomposition
pressure of CO2 is quite small.

• Between 650-900 oC, the

decomposition pressure
increases rapidly and reaches
101 kPa at about 900 oC.

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 • The total heat required for calcining per ton of lime
produced may be divided into two parts:

• 1. Heat to raise the rock to decomposition

temperature

• 2. Latent heat of dissociation.

• Theoretical heat requirements per metric ton of lime

produced.

• if the rock is heated only to a calcining temperature

of 900 oC, are approximately 1.4 Gj for sensible
heat and 2.7 Gj for latent heat.

• Actual calcining operations (rock is heated to 1200-

1300 oC), sensible heat requirements increases by
about 370 kj.

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 • The practical heat requirements
are approximately 4 Gj/t of lime
produced in a vertical killn.
About 40 percent is sensible
heat, the rest is latent heat of
decomposition.

12/08/21 Ballice, 2010 110

 • The sequence steps connected with
manufacturing in the kiln

• - Blasting down of limestone from a quarry

face or occasionally from underground
veins.
• - Transportation from the quarry to mills,
generally by an industrial railroad.
• - Crushing and sizing of the stone in jaw and
gyratory crushers
• - Screening to remove various sizes
• - Carting of large stones to top of vertical
kilns
• - Conveying of small stones to a rotary kiln.
• - Conveying of fines to a pulvarizer to make
powdered limestone for agricultural and
other demands
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 • Burning of limestone according to
size, (vertical kilns to give lump lime,
or in horizontal rotary kilns to furnish
fine lime)

• - Packaging of the finished lime in

barrels or sheet-iron drums or
conveying it to a hydrator.

• - Hydration of lime

• - Packing of slaked lime in 25 kg

paper bags.
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 • Rotary Kiln (some properties)

• -The exterior of the rotary kiln is heavy steel and

interior is lined with refractory brick.

• - The kilns have a slope of 4 percent and rotate

counterclockweise at a speed of 0.6 to 2 rpm.

• - Rotary kilns have the highest capacity and produce

lime of the most uniform quality but required the
greatest capital investment, have a high energy
consumption, and need very expensive dust-
collecting system.

• -Before calcination, lime is preheated to reduce fuel

consumption and may be as hot as 980 oC when it
enter the kiln. Heat for preheating is furnished by hot
air and gases from the kiln.

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 • GYPSUM

• Gypsum is hydrated calcium sulfate , with

the formula CaSO4.2H2O. When heated
slightly, the following reaction occurs:

• CaSO4.2H2O (s)  CaSO2.1/2 H2O (s) + 3/2

H2O(g) H25 oC= 69 kj

• If the heating is at a higher temperature,

gypsum loses all its water and becomes
anhydrous calcium sulfate, or anhydrite.

• Calcinated gypsum is used for wall plaster

by the addition of a filler material such as
asbestos, wood pulp, or sand.

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 • Calcination of Gypsum

• The temperature is raised to about 120 to

150 oC, with constant agitation to maintain a
uniform temperature. In this case, the
material in the kettle is known as first-settle-
plaster, and it can be sold at this point.

• or it may be heated further to 190 oC to give

a material known as second-settle-plaster.

• First-settle-plaster: the half hydrate

CaSO4.1/2H2O

• Second-settle-plaster: Anhydrous
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 • Hardening of plaster

• The hardening of plaster is essentially a

hydration chemical conversion as
represented by the equation.

• CaSO4.1/2H2O + 3/2H2O  CaSO4.2H2O

H= - 2.9 kj

• This is the reverse reaction of dehydration

reaction.

• Hydration with liquid water takes place at

temperature below about 99 oC and thus
gypsum must be heated above 99 oC for
practical dehydration.

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 • MISCELLANEOUS CALCIUM COMPOUND

• Calcium Carbonate: Calcium carbonate is very widely

used industrial chemical, in both its pure and impure
state.

• As marble size: as a filler for artificial stone.

• for the neutralization of acids

• Marble dust: as abbrasive and in soaps.

• Crude and pulvarized: to sweeten soils in large

tonnes

• After wet grinding and levigating: as whitting

• and in the paint , rubber and paper industry

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 • Calcium Sulfide

• Calcium sulfide is produced by

reducing calcium sulfate with coke.

• Using area:

• as depilatory in tanning industry and

incosmetics.

• Polysulfides such as CaS2 and CaS5,

made by heating sulfur and calcium
hydroxide, are consumed as
fungicides.
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 • Halide salts

• Calcium chloride is obtained

commercially as a by-products of
chemical manufacture and from
natural brines which contains
more or less magnesium
chloride.

12/08/21 Ballice, 2010 120

 • Using area:

• to lay dust on highway (because

it is deliquescent and remain
moist) to melt ice and snow on
highways in winter and as
antifreeze for concrete.

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 • Calcium bromide and iodide

• is produced by action of the

halogen acids on calcium oxide
or calcium carbonate.

• using area:
• for use in medicine and
photography (in hexahydrate
form)
• and swimming pool sanitation.
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 • Calcium Arsenate

• Calcium arsenate is produced by the

action of calcium chloride, calcium
hydroxide and sodium arsenate or
lime and arsenic acid.
• 2CaCl2 (aq) + Ca(OH)2(s) + 2
Na2HAsO4(aq)  Ca3(AsO4)2(s) +
4NaCl(aq)+2H2O(l)
 H= -27.8 kj
• Using area:
• as an insecticides and as fungicides

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 • Calcium Organic Compounds

• Calcium acetate and lactate are prepared by

the reaction of calcium carbonate or
hydroxide with acetic or lactic acid.
• Calcium acetate is formerly pyrolyzed in
large amount to produce acetone, but now
is used in dying of textiles
• Calcium lactate is sold for use in medicine
and foods as a source of calcium.
• Calcium soaps such as stearate, palmitate
are made by the action of 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.

12/08/21 Ballice, 2010 124

 • MAGNESIUM COMPOUNDS

• Magnesium is one of the most widely

distributed elements, occupying 1.9
% of the earth's crust.
• It is found in the form of
• - chloride
• - silicate
• - hydrated oxide
• - sulfate
• - carbonate

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 • Raw material and uses

• Important domestic sources of the

magnesium salts are
• - seawater
• - dolomite
• - magnesite (MgCO3)
• Using area:
• - Extensively for refractories and insulating
• - manufacture of rubber, printing
inks,pharmaceuticals and toilet goods
• - air pollution control systems for the
removal of sulfur dioxide from stack gases

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 • Manufacture
• The manufacture of magnesium compounds
by seperation from aqueous solutions
• may be divided into four processes:
• 1. Manufacture from seawater without
evaporation ,
• - using seawater and lime as the principal
raw materials. Magnesium hydrate is
dissolved in 10 % hydrochloric acid to
furnish a solution of magnesium chloride
• - Concentration of aqueous solution in
direct-fired evaporators and producing 76
% magnesium chloride
• - Electrolytic processing of magnesium
chloride to produce metallic magnesium

12/08/21 Ballice, 2010 127

 • 2. Manufacture from bitterns of
mother liquors from the solar
evaporation of seawater for salt

• 3. Manufacture from dolomite and

seawater

• 4. Manufacture from deep-well brines

• - Brines (20.7 % CaCl2, 3.9 % CaCl2,
3.9 % MgCl2 and 5.73 NaCl) is
precipitated by calcined dolomite to
produce a slurry containing 45 %
Mg(OH)2 and this is calcinated at high
temperatures to produce MgO.

12/08/21 Ballice, 2010 128

 • Success in obtaining of magnesium
compounds form seawater depends upon:

• - means to soften the seawater cheaply,

generally with lime or calcined dolomite

• - preparation of purified lime or calcined

dolomite slurry

• - economical removal of the precipitated

hydroxide from large volume of water

• - purification of the hydrous precipitates

• - development of means to filter the slimes

12/08/21 Ballice, 2010 129

 • The reactions occurs

• MgCl2 (aq) + Ca(OH)2 (s)  Mg(OH)2 (s) +

CaCl2 (aq)
 H= + 9.46 kJ

• MgSO4 (aq) + Ca(OH)2 (s) + 2H2O (l) 

Mg(OH)2(s)+CaSO4.2H2O(s)
 H= -13.3 kJ

• it is possible to produce of magnesium

compound in this way because of

• insolubility of magnesium hydroxide in

water.

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 • If calcined dolomite uses instead of calcium
carbonate;

• the reactions;

• Calcination of dolomite :

• 2CaMg(CO3)2 (s) 2CaO(s) +2MgO(s)+4CO2

(g) H= + 610.9 kJ
•
• Slaking :

• 2CaO (s) + 2MgO (s) + 4H2O (l)  2Ca(OH)2

(s) + 2Mg(OH)2 (s) H= -168 kJ

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 • Precipitation:
•
• 2Ca(OH)2(s)+2Mg(OH)2 (s) +
MgCl2 (aq)+MgSO4 (aq) +H2O (l)
 4Mg(OH)2 (s) + CaCl2 (aq) +
CaSO4.2H2O (s)

 H= -22.6 kJ

12/08/21 Ballice, 2010 132

 • Calcination:

• 4Mg(OH)2 (s)  4MgO (s) + H2O (g)

 H= +248.3 kJ

• Hydrochlorination:

• Mg(OH)2(s) + HCl(aq)  MgCl2(aq) + 2H2O

(l)
H= + 44.7 kJ
• 7 % of calcined dolomite is needed for
softening the saewater and the rest is used
for precipitating crystalline Mg(OH)2 and
then filtered and washed.

12/08/21 Ballice, 2010 133

 • Miscellaneous magnesium
compounds

• Magnesium Carbonates

• dense MgCO3 is used in magnesite

brick to the low density
4MgCO3.Mg(OH)2.5H2O and
3MgCO3.Mg(OH)2.3H2O

• using area:
• as fillers in inks, paints and varnishes

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 • Oxide and Hydroxide of Magnesium
•
• On heating magnesium carbonate or
hydroxide , magnesium oxide (MgO)
is formed.

• using area:

• in the vulcanization of rubber ,

material for making other magnesium
compounds, as an insulating
materials, as a refractory material, as
an abrasive.
12/08/21 Ballice, 2010 135
 • Magnesium peroxide

• the product of reaction between magnesium

sulfate and barium peroxide
• and is used as an antiseptic and a bleaching
agent.

• Magnesium Sulfate

• is prepared by the action of sulfiric acid on

magnesium carbonate or hydroxide
• It is sold in many form one of which is the
hydrate MgSO4. 7H2O (Epsom salt)
• using area:
• extensively as sizing and as a fireproofing
agent.
12/08/21 Ballice, 2010 138
 • Magnesium Chloride

• is produced from hydrochloric acid

and magnesium hydroxide

• using area:

• in ceramics, in the sizing of paper,

and in the manufacture of oxychloride
cement and making of metallic
magnesium

12/08/21 Ballice, 2010 139

 • Magnesium Silicates

• Two widely used naturally occuring compounds ,

asbestos and talc.
• Asbestos is a magnesium silicate mixed with varying
quantities of silicate of calcium and iron. This is used
for manufacturing of fireproof and insulating
materials.
• But it has cancercausing chracteristics of its fibers.
• Talc is a rather pure magnesium silicate in the form
of 3MgO.4SiO2.H2O found naturally in soapstone.

• using area:

• as a filler in paper and plastics and in many cosmetic

and toilet preparation.

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