Chemistry Handbook

NARMADA CEMENT CHEMISTRY - HANDBOOK
CEMENT CHEMISTRY
Table of Contents
1. INTRODUCTION
1.1
INTRODUCTION
1.2
DEFINITIONS - cement, concrete, cement types, raw materials etc.
2. COMPOSITION
2.1
COMPOSITION - basic calculation/formulas - chemical shorthand
etc.
2.2
MODULES
2.3
MINERAL COMPOSITION
3. TYPES OF CEMENT
3.1
TYPES OF CEMENT
3.2
CEMENT STANDARDS
3.3
CEMENT QUALITY - MAIN FACTORS
4. MANUFACTURE
4.1
MANUFACTURE OF CEMENT - grey, mixed and white
cement - wet, dry and semi-dry process
4.2
RAW MIX
4.3
RAW MATERIALS
4.4
CHEMICAL COMPOSITION AND CONTROL OF RAW MIX
4.5
PHYSICAL CONTROL AND COMPOSITION OF RAW MIX
4.6
BURNABILITY OF RAW MIX
4.7
CLINKERISATION
4.8
INFLUENCE OF THE RAW MIX ON CLINKER FORMATION
AND BURNABILITY
5.PROCESS AND KILNS
5.1
TYPES OF KILNS - wet, dry & semi-dry
5.2
WET KILN - main features - process
5.3
DRY KILN
5.3.1 LONG KILN
5.3.2 SP KILN
5.3.3 ILC-E KILN
5.3.4 ILC KILN
5.3.5 SLC KILN
5.3.6 SLC-S KILN
5.3.7 SLC-I KILN
5.4
ASH ABSORPTION
5.5
VOLATILE MATTER
Chemistry Bible Rev.0; 7 Dec 00

5.6
MAIN FEATURES DURING BURNING
6. HEAT OF REACTION & HEAT TRANSFER

7.FUEL
7.1
TYPES OF FUEL
7.1.2 COAL
7.1.3 FUEL OIL
7.1.4 GAS
7.1.5 WASTE FUELS
8.COMBUSTION
9. COAL & OIL
9.1
9.2
9.3
9.4
9.5
9.6
FINENESS OF COAL
DRYING OF COAL
ASH CONTENT
GAS CONTENT
MINOR COMPONENTS
REQUIREMENT FOR AIR
10. PROCESS GAS
1.1
INTRODUCTION
Cement is a material that binds together solid bodies ( aggregate) by hardening

from a plastic state. Many materials act as adhesives or cement according to this
definition. The cement referred to above, which is used for civil engineering and
the construction industry, is portland cement. Portland cement is hydraulic and
develops strength primarily by the hydration of the di- and tri-calcium silicates it
contains. Hydraulic means that the paste of cement and water will harden under
water. Lime, on the other hand, will harden due to the reaction with carbon
dioxide from the air.
In 1793, an Englishman by the name of Smeaton found that a form of hydraulic
cement was produced when a mixture of limestone and clay were burned
together. He was the first producer of portland cement. Another Englishman,
Joseph Aspdin obtained the first patent for portland cement in 1824. He burned
a mixture of chalk and clay in a lime kiln to form a clinker and ground the clinker
to cement. Aspdin is regarded as the inventor of portland cement. The early
product did not have the same quality of cement currently produced today.
Two main developments have improved the quality of cement:
Addition of gypsum to regulate the setting time
Higher burning temperature to obtain higher lime containing silicates
Today, portland cement (portland cement clinker with a small addition of gypsum)
is used worldwide and is the primary construction material for roads, bridges,
runways, tunnels, and buildings. In addition, blended cements are produced
using portland cement clinker, a small amount of gypsum and another additive
such as blast furnace slag, fly ash, or other pozzolans. Some blended cement
has improved performance over ordinary portland cement with greater resistance
to alkali and sulfate attack.
1.2
DEFINITIONS - cement, concrete, cement types, raw materials
Cement:
cement is a mix of cement clinker and gypsum

ground together into a powder.
Gypsum:
calcium sulfate is used to regulate setting time.
Concrete:
concrete is a mix of cement (13%), water (7%), fine

aggregate 6mm (32%), and coarse aggregate +6mm
(48%) which hardens to solid mass
Cement types:
there are numerous types of cement for many

different applications. ASTM defines the
chemical and physical requirements
Ordinary
general-purpose concrete
Rapid hardening
precast concrete
Alkali resistant
used with reactive aggregates
Sulfate resistant
used in applications requiring resistance

against sulfate attack
White cement
special architectural concrete
Low heat
massive concrete like dams
Masonry cement
Blended cements
mortar bonding brick or block
use an addition of slag or other pozzolans to

achieve some of the properties of alkali or
sulfate resistance
Raw Materials:
The common raw materials for manufacture of

Portland cement are:
Limestone / Marble / Marl
Clay / Shale
Sand
Iron ore or pyrite ash
Limestone and clay are primarily found near the plant, where as, sand and
iron ore are usually brought in because of their preferred chemical
composition.

Today, there is considerable interest by our society for the reuse of waste
materials. Some of these can be utilized in the raw mix feed to the kiln. Other
materials such as waste oils and solvents can be safely disposed of in the
burning zone of the rotary kiln because of the high temperatures.
2.1 COMPOSITION - basic calculation/formulations - chemical shorthand
The most common compounds in cement chemistry are:
Formula
Name
Source
SiO2
silicium dioxide
quartz, sand
Al2O3
aluminium oxide
Fe2O3
iron oxide
CaO
calcium oxide
lime
CaCO3
calcium carbonate
limestone, marble, marl
MgO
magnesium oxide
MgCO3
magnesium carbonate
K2O
potassium oxide
Na2O
sodium oxide
H2O
water
N2
nitrogen
79 volume percent in air
O2
oxygen
21 volume percent in air
CO
carbon monoxide
CO2
carbon dioxide
SO2
sulfur dioxide
A typical analysis of clinker is given in the table below:

Table 1
CLINKER COMPOSITION
SiO2
Al2O3
Fe2O3
CaO
MgO
K2O+Na2O
SO3
Insoluble residue
Ignition loss
Total
Free CaO
Clinker
%
22.51
5.16
2.55
64.97
2.61
1.7
0.22
0.1
0.06
99.88
0.8
Min limit %
17
4
0.1
62
0
0.3
0
0
0
Max limit %
26
10
5
69
4
2
1.5
1
3
2.5
* In the table, the term ignition loss is defined as the loss in weight by heating the sample to a temperature of
~900C.
2.2 MODULES
Modules determine the proportioning of the raw mix. The three commonly used
modules are:
SILICATE MODULUS
MS
ALUMINA MODULUS
MA
LIME SATURATION FACTOR
LSF
The silica modulus is defined as the ratio of silica to the sum of alumina and iron
oxide:
MS
SiO2
Al2 O3 Fe2 O3
The silica modulus for clinker is normally between 2.4 and 2.7. The amount of
melt phase in the burning zone is a function of MS, when MS is high, the amount
of melt is low. Therefore, when the MS is too high, the formation of nodules
might be too slow, resulting in less nodulization. The material becomes dusty
and impedes the kiln operation. Generally, a higher MS relates to a harder
burning mix.

The alumina modulus is defined as:
MA
Al2 O3
Fe2 O3
The alumina modulus for clinker varies between 1.6 and 2.0. The temperature by
which the melt forms depends on the MA. The lowest temperature is obtained
when the MA is 1.6. The MA also affects the color of clinker and cement. The
higher the MA, the lighter the cement.
The lime saturation factor, LSF, is defined as the ratio of available lime to the
theoretical lime required by the other major oxides in the raw mix to form clinker
and is determined from the following equation:
LSF
CaO
2.8* SiO2 118
. * Al2 O3 0.65* Fe2O3
The LSF is usually expressed as a percentage. The LSF for clinker is in the
range of 88 and 98%. The theoretical maximum amount of lime, CaO, that can
be combined with the acidic oxides has been derived from phase diagrams and
can be calculated as follows:
CaOmax = 2.80*SiO2 + 1.18*Al2O3 + 0.65*Fe2O3
For cement, a variation of the previous equations has to be used to account for
the addition of gypsum to cement. The amount of CaO has to be reduced by the
amount bound in gypsum CaSO4.
The LSF formula for cement is then:
CaO 0.7 * SO3

2 .8* SiO2 1.18* Al2 O3 0.65* Fe2 O3
LSF
2.3 MINERAL COMPOSITION

During burning in the cement kiln, the lime is combined with the acidic oxides to
form cementitious minerals. The main minerals are:
Table 2
CLINKER MINERALS
Formula
Alite
Belite
2CaO.SiO
Tricalcium aluminate
3CaO.Al O
Calcium alumino ferrite
formula
weight %
weight %
70
35
45
20
18
15
0.5
CS
3
CA
2
4CaO.Al O .Fe O
Free lime
Min
CS
2
Max
3CaO.SiO
Short
C AF
CaO
Note: The short formula designation is used throughout the cement industry.
It is possible to calculate the amount of the four main minerals by using the
BOGUE formulas, however, the calculation is only approximate. The actual
amount present of any mineral can be determined by microscopy or faster by Xray diffraction. Using % wt., the BOGUE formulas for clinker are:
CS=
4.07*CaO 7.60* SiO 1.43* Fe O 6.72* Al O

2
CS=
8.60* SiO + 1.08* Fe O + 5.07* Al O 3.07*CaO

2
(or C S= 2.867*SiO -0.7544* C S )

3
CA =
2.65*Al O - 1.69* Fe O
C AF =
3.04*Fe O
As mentioned above, other minerals are present and have to be taken into
4
account. These are free lime (CaO) , calcium sulfate (CaSO ) and periclase
(MgO). The free lime should be under 2.0%. A higher amount indicates poor
burning or faulty composition of the raw mix. Too high a free lime will result in
volume instability in the cement mortar or concrete. Calcium sulfate in cement
3
comes from the addition of gypsum and from clinker. In clinker, SO comes from
2
the sulfur in the fuel used and from sulfur in the raw materials ( pyrites FeS ). MgO
can cause late expansion in concrete. A maximum of 6% MgO is allowed in
ordinary portland cement. Cements with higher MgO contents 4-5%, rapid
cooling of the clinker is of more value for offsetting the adverse effects of high
magnesia contents. For other types of cement, the maximum limit varies.
The minerals in clinker are mainly found as crystals. A smaller amount is present
in the so-called glass phase. During burning, some liquid phase is formed at the
high temperature in the burning zone (BZ). The liquid phase ranges from 20 to
27% in normal clinker, however, some of the liquid does not have time to form
crystals during cooling. The liquid phase @ 1450C is determined by the
following equation:
% Liquid Phase = 3.00A + 2.25F + (MgO + K O + Na O + SO )
3. TYPES OF CEMENT
The clinker from the kiln system is ground to cement with a small addition of
gypsum in order to control the time of setting. If no gypsum is present, the
cement will set rapidly when water is added. The amount of gypsum added is 3
to 5% by weight. The formula for gypsum is:
4
CaSO ,2H O
4
- which is the di-hydrate form
CaSO ,0.5H O
- which is the hemi-hydrate form (plaster of paris)
CaSO
- which is the anhydrite form
The gypsum molecule is crystallized with two molecules of water. Gypsum occurs
in nature as gypsum rock. Other sources of gypsum are waste gypsum from
exhaust gas desulfurisation at power plants, surplus gypsum from fertilizer
factories or cement manufacturing exhaust gas scrubbers. Other materials can
be added to clinker and gypsum to make cement. If the addition rate is small, the
product can still be called portland cement.
The most common types of cement can be divided into three main groups:
a) PORTLAND CEMENTS:
10
ORDINARY PORTLAND CEMENT

RAPID HARDENING CEMENT
SULFATE RESISTANT CEMENT
LOW HEAT CEMENT
WHITE CEMENT
b) COMPOSITE CEMENTS
BLASTFURNACE CEMENT
FLY ASH CEMENT
POZZOLAN CEMENT
OTHER BLENDED CEMENTS
c) OIL WELL CEMENTS
a) PORTLAND CEMENTS are by far the most common type of cements

produced around the world. The most widely used type is
ORDINARY PORTLAND CEMENT.
RAPID HARDENING CEMENT is a portland cement that develops strength faster
than ordinary portland cement. It is manufactured by grinding the clinker and
gypsum finer in the cement mill. Good clinker quality is needed and the addition
of gypsum is a little higher to maintain setting time and increase strength
development.
SULFATE RESISTANT CEMENT is used where a higher resistance is required
11

3
to sulfate-bearing waters. The cement composition has a lower content of C A,

less than 8%.
LOW HEAT CEMENT is used where low heat development during hardening is
required, i.e. in large concrete structures like dams. The rate of strength
development is lower than that of ordinary portland cement. Although, the final
strength may be higher.
WHITE CEMENT is used where a white color is wanted for a facade of buildings.
It is manufactured from raw materials with low content of iron chromium and
manganese.
b) COMPOSITE CEMENTS also known as blended cements start with Portland

cement clinker and gypsum but also have the addition of another material. Some
additions become hydraulically activated as they react with the Portland cement
clinker. To mention a few:
Blastfurnace slag cement is a cement made by grinding together portland cement
clinker and granulated blastfurnace slag in the proper proportions.
Masonry cement is a combination of portland cement clinker, limestone, and a
small addition of an air-entraining agent to produce a more workable, rapid
hardening mortar than ordinary portland cement. It can also be made by
intergrinding mixtures of portland cement with hydrated lime, granulated slag, or
other waterproofing agents with inert fillers.
Pozzolanic cements are produced by mixing together portland cement and a
pozzolana. A pozzolana is a material which is capable of reacting with lime in the
12
presence of water at ordinary temperatures to produce cementitious compounds.
c) OIL WELL CEMENTS

Oil well cements are used for cementing the steel casing of gas & oil wells to the
walls of the bore-hole and to seal porous formations. Usually, portland cements
more coarsely ground than normal, with the addition of special retarders to allow
for slow-setting conditions are used.
Cement standards define the various types of cement. Today, there are two main
standards:
The US standard defined in ASTM C 150

The European standard EN 197-1
ASTM uses 5 main classes for Portland cement. There are also a number of
composite or blended cements defined by ASTM. The European standard has
three main strength classes each divided into two subgroups or 6 classes in all.
Tables 3 and 4 show some of the physical requirements defined by ASTM.

Table 3
ASTM CEMENT TYPES

Compressive Strengths for ASTM C109 Cubes
Number
Type of Cement
3 days
7 days
28 days
compressive
compressive
compressive
strength
strength
strength
MPa
MPa
MPa
13
Ordinary Portland cement
12
19
IA
OPC air entraining
10
16
II
Moderate sulfate resistant
10
17
14
Moderate heat of hydration

II A
II + air entraining
III
High early strength
24
III A
III + air entraining
19
IV
Low heat of hydration
High sulfate resistance
17
15
21
Note: SI units are the standard .To convert to psi : SI * 142.23.
Table 4
ASTM CEMENT TYPES
Air Content, Fineness, Soundness and Setting Time
14
ASTM
Air content
TYPE
Fineness
Autoclave
Setting
Blaine
expansion
minutes
vol%
I
IA
II
II A
III
III A
m /kg
Initial ,min
max
Max 12
>280
<0.80
45
375
Min=16,max= 22
>280
<0.80
45
375
Max 12
>280
<0.80
45
375
Min=16,max= 22
>280
<0.80
45
375
Max 12
<0.80
45
375
Min=16,max= 22
<0.80
45
375
IV
Max 12
>280
<0.80
45
375
Max 12
>280
<0.80
45
375
15
Table 5
European Standard EN 197-1 Types of Cement
Cement type
Designation
Notation
Clinker , K ,%
Additive
Portland cement
95-100
Gypsum
Filler
II
Portland slag
II/A-S
80-94
S=Granulated
cement
II/B-S
65-79
blastfurnace slag
Portland silica fume
II/A-D
90-94
D=Silica fume
Portland pozzolana
II/A-P
80-94
P=Natural pozzolana
cement
II/B-P
65-79
II/A-Q
80-94
II/B-Q
65-79
Portland fly ash
II/A-V
80-94
cement
II/B-V
65-79
II/A-W
80-94
W=calcareous
II/B-W
65-79
fly ash
Portland burnt shale
II/A-T
80-94
T=burnt shale
cement
II/B-T
65-79
Portland l/st cement
II/A-L
80-94
II/B-L
65-79
Portland composite
II/A-M
80-94
cement
II/B-M
65.79
Blastfurnace cement
III/A
35-64
III/B
20-34
III/C
5-19
IV/A
65-89
IV/B
45-64
V/A
40-64
V/B
20-39
cement
III
IV
Pozzolanic cement
Composite cement
16
Q=industrial pozzolana
V=siliciceous fly ash
L=limestone
M=different materials
All of the above European types of cement are the result of many years of work
on a unification for the different standards. In European standards, the three
main strength classes are divided into two subgroups or 6 classes in all.
Table 6
European Standards for Strengths
Type
Class
2 days
7 days
28 days
compressive
compressive
compressive
strength
strength
strength
MPa
MPa
MPa
>=16
32.5-52.5
I,II,III,IV, & V
32.5
I,II,III,IV, & V
32.5 R
>=10
32.5-52.5
I,II,III,IV, & V
42.5
>=10
42.5-62.5
I,II,III,IV, & V
42.5 R
>=20
42.5-62.5
I,II,III,IV, & V
52.5
>=20
>=52.5
I,II,III,IV, & V
52.5R
>=30
>=52.5
For both ASTM and EN, there are a number of other physical requirements. For
these it is necessary to reference the two standards. The standards also specify
some chemical requirements. For ASTM they are:
17
Table 7
ASTM Chemical Specifications
Cement type
I and I A
II and II A
III and III A
IV
SiO , min.%
2
20.0
Al O , max %
2
6.0
Fe O , max%
MgO, max%
6.0
6.0
6.0
6.0
6.0
6.0
3.0
3.0
3.5
2.3
2.3
3.5
Not applicable
4.5
Not applicable
Not applicable
Ign.loss, max%
3.0
3.0
3.0
2.5
3.0
Ins.res.max%
0.75
0.75
0.75
0.75
0.75
SO , max%
3
C A <= 8%
3
SO , max%
3
C A > 8%
C S ,max%
35
C S,min%
40
C A, max%
4
15
C AF+2(C A),max%
25
Optional requirements:
3
C A max%,for
moderate sulfate
res.
18

3
C A max%,for high
sulfate rest.
3
C S+C A, max
58
%,mod. heat of
hydration
2
Na O+0.658K O,
0.60
0.60
0.60
0.60
0.60
max%, low alkali
3.3 CEMENT QUALITY - MAIN FACTORS
Cement quality is just as important for the manufacturer of the product as it is for
the producers of concrete and concrete products, contractors and the private
consumer.
The cement manufacturers have to meet the standards, the clients requirements
and at the same time be competitive. The plants also have a role in fulfilling
environmental requirements and assisting in the disposal of various waste
products.
The consumer has a range of requirements for the cement depending on the
type of concrete product, i.e. all purpose ready mix, precast, or pumped concrete
to mention a few.
The end user wants a durable concrete which will stand up to heavy usage on
infrastructure, be frost resistant, withstand alkali aggregate reaction and at the
same time have a good appearance in the finished structure.
19
The cement quality depends on the clinker manufacturing process, the cement
milling, the fineness, and any changes to the cement after milling.
Composition can also vary within a single type of cement. Even ordinary
portland cement has subtle differences. For example, the gypsum addition rate
and with limestone where up to 5% might have been added during grinding.
The cement fineness can be varied during grinding with a finer product reacting
faster. Fineness is expressed as: specific surface area (Blaine), residue and
particle size distribution.
The chemistry of the clinker is important. The clinker mineral composition has to
be considered. The main minerals in the clinker are:
3
C S, C S, C A,C AF
The main reactions at hydration in an idealized form are:
1) C S + (3-x+y) H O = C SH + (3-x) Ca(OH)

2
2) C S + (2-x+y) H O = C SH + (2-x) Ca(OH)

3
19
3) C A + 13.5 H O = (C AH + C AH )
3
4) C A + 6 H O = C AH
3
19
5) C A + Ca(OH) + 18 H O = C AH
20

3
31
6) C A +3 CaSO + 31H O = C A.3 CaSO .H

3
12
7) C A + CaSO + 12H O = C A. CaSO .H

4
8) C AF reactions similar to C A
2
9) CaO + H O = Ca(OH)
2
10) MgO + H O = Mg(OH)

4
11) CaSO + 2 H O = CaSO ,2 H O

4
12) CaSO , / H O + 1 / H O = CaSO ,2 H O
In all of the above reactions, water reacts with the hydration product minerals
increasing the volume of the solid phase. Each reaction differs in velocity, volume
change, and in the nature of the hydration products. These reactions are the
background for the setting time and strength development to the solid state from
the plastic phase when water is first added to the cement.
Of prime importance is the state of the gypsum, as di-, hemi-, or anhydrite, in the
cement as it first reacts with water. Depending upon that state, the gypsum and
3
C A reactions with water can result in normal, false or flash set.
False set is the premature stiffening of the cement paste due to most of the
gypsum being either hemi-hydrate or soluble anhydrite due to overheating. Upon
mixing with water, crystallization of reformed gypsum causes stiffening. This
stiffening can be broken upon remixing without additional water. False set can
happen either by fast set of gypsum hemi-hydrate or because of a slow reaction
21

3
between C A with water. The slow reacting C A can be caused by prehydration

2
or by carbonation with CO . False set can be prevented by lowering the mill exit
temperature, thereby, reducing the degree of gypsum dehydration, the amount of
gypsum added to the mix, or replacing part of the gypsum with a natural insoluble
anhydrite.
On the other hand, flash set occurs if the C A is more reactive than gypsum with
water. The setting is characterized by a high evolution of heat and short setting
time. Flash set can be prevented by adding more gypsum to the cement or by
dehydrating the gypsum to a more reactive form, i.e. hemi-hydrate or anhydrite.
Therefore, as the cement is being ground, the mill material temperature must
carefully be controlled. Between 90-130C, the gypsum changes into calcium
sulfate hemihydrate (plaster of paris) by releasing 1.5 molecule water:
4
CaSO ,2H O
4
CaSO ,H O
CaSO , H O + 1 H O
4
(a)
CaSO + H O
(b)
The cement mill material temperature is controlled primarily by cooling the mill
with an internal water spray in the second compartment. Additional cooling is
accomplished with air in the separator. The cement mill exit temperature should
not reach 130C and is usually targeted at 110C.
22
Finally, if the cement material temperature has not been controlled in the mill
system, the cement might enter the storage silo at too high a temperature
causing dehydration of the gypsum. The rate of the transformation increases
with temperature and with falling dew point. The change after equation (a) is
rapid at a temperature of 90-130C. The water molecule released can give rise to
formation of lumps in the cement and to scaling on the storage silo wall by
2
.
4
formation of Syngenite K SO CaS0 H O.
4. MANUFACTURE
4.1
MANUFACTURE OF CEMENT - grey, mixed and white

cement - wet, dry and semidry process
The manufacture of Portland cement is divided into the three main parts:
a)
b)
c)
Preparation of the kiln feed

Burning in the kiln
Grinding of the clinker with gypsum and other additions
The description here will concentrate on the process for ordinary grey cement
with some comments on the other types of cement.
The dry process is used to make the majority of the cement produced in the
world. The wet process, however, is still used where fuel cost has allowed it. The
wet process can furthermore be justified where the raw materials are very wet
such as chalk, a soft limestone, and clay.
An intermediate solution is the semi-dry process where the raw mix is prepared
as slurry. The slurry can then be filtered to remove a portion of the water before
the burning or the slurry may be pumped directly into a dryer crusher working in
unison with the kiln.
4.2
RAW MIX
23

The raw mix must have a composition that will produce a clinker of the proper
analysis. The difference in the composition of the raw mix and the clinker is
threefold. First, is the change in each of the materials as they are heated up in
the kiln. The changes are due to a loss in weight mainly from the release of
carbon dioxide and water. Second, is a change due to absorption of ash from
coal used as fuel. There is also a change due to absorption of sulfur in the fuel.
Finally, there is a change due to the small dust loss in the exhaust gas. Some of
this dust is returned to the process but some might be wasted as in a bypass. In
a wet process, the dust may be discarded in order to reduce the alkali content in
the clinker.
The raw mix must therefore compensate for these changes and losses;
otherwise, the clinker will not have the correct chemical and mineralogical
composition. The way in which this is done will be explained below.
4.3
RAW MATERIALS
Many raw materials are suitable for the production of cement. In principle, as
long as they can be mixed to give the right composition of the clinker, they can be
used. There are some restrictions naturally. They must be available in large
quantities and be economically feasible. In addition, there might also be
restrictions on use due to minor components in the raw materials.
Limestone is the largest component used in producing cement. It is available as
CaCO3 in marble, limestone, chalk and marl. Limestone is sometimes found
together with magnesium carbonate. Only small amounts of MgO can be
tolerated in cement due to the risk of the expansion reaction in the concrete.
Limestone containing a large amount of magnesium carbonate is called dolomite.
In nature, limestone is found in many places mixed with clay and/or shale. Clay
and shale contain SiO2, Al2O3 and Fe2O3. In some cases a type of limestone is
found that is quite close in chemical composition to the cement composition.
When the limestone is of a higher purity than the requirement for the raw mix,
24

then other raw materials must be added to the mix. The amount of limestone is
calculated using the formula below:
LSF
CaO
2.8* SiO2 118
. * Al2 O3 0.65* Fe2O3
Sand is a mineral very rich in silica, SiO2. It is a very hard and abrasive mineral. It
is used when the mix is insufficient in silica. It will increase the MS or the silica
ratio:
MS
SiO2
Al2 O3 Fe2 O3
Iron can be used in the form of iron ore, usually an iron oxide, or as a waste
product from the fertilizer industry, such as pyrite ash. It is used to regulate or
reduce the alumina modulus, the ratio of alumina to iron oxide:
MA
Al2 O3
Fe2 O3
Bauxite an alumina mineral rich in Al2O3 and can be used to increase the MA.
Fly ash, one of the waste materials from the power generation industry is also
used as a raw material. This is known as pulverized fly ash, PFA. Typically, this
is higher in SiO2 content.
The number of components used in the raw mix is typically 4-5 raw materials
depending upon the need for correction of the three main modules: LSF, MS,
MA.
The physical nature of a raw material is also important. Very wet materials can
be the reason for choosing the wet or semi-dry process. Very abrasive materials
like sand and basalt are costly to crush and grind to the fine state needed in the
raw mix. The chemical variation in the raw material is also important. If there are
great variations, more homogenization will be required.
25

4.4
CHEMICAL COMPOSITION AND CONTROL OF RAW MIX
The chemical composition of the raw mix has to be prepared correctly to yield a
good clinker. Also, the variation in the raw mix going to the kiln has to be small to
obtain good burning conditions for the kiln and preheater. The first step in the mix
design is the determination of the chemical composition of the raw materials. It is
common to have an approximate analysis of each raw material and use this for
the calculation of the mix ratios. A sample after the raw mill is easily obtained for
analysis. An analysis can be performed quickly using X-ray fluorescent analysis,
XRF. Timely adjustments can then be made to the raw mill weighfeeders.
A typical calculation of a raw mix and the corresponding clinker can be made
using a simple spreadsheet like EXCEL with its SOLVER function, i.e. as shown
in table no.8 below.
The calculations made in the table show that 5 raw materials have been available
at this plant. This has made it possible to satisfy 4 conditions, one less than the
number of raw materials. The four conditions here are:
LSF
94
MS
2.75
MA
1.90
Na2O+ 0.658*K2O
0.64
The alkalies often have to be restricted to satisfy a requirement for low alkali
cement. Low alkali cement is needed when the aggregate contains reactive
silica, which can give an expansion in concrete.
26
Table 8
Calculation of Raw Mix
RAWMIX NO:
HEAT CONSUMPTION
COAL HEAT
VALUE Hi
COAL ASH
750
7420
9.4
Limeston
e
980257
Shale
Fly ash
Sand
Bottom
ash
980576
980578
980575
980577
SiO2
Al2O3
Fe2O3
CaO
MgO
Mn2O3
5.52
0.58
0.23
51.81
0.36
0.02
54.84
15.12
7.33
0.81
1.33
0.07
54.58
26.72
9.42
1.49
0.71
0.08
78.41
3.76
1.70
5.84
1.43
0.02
39.39
18.30
28.69
3.34
0.76
0.14
14.47
3.40
1.64
43.49
0.47
0.03
TiO2
P2O5
K2O
Na2O
SO3
LOI @900 oC
0.03
0.02
0.14
0.06
0.19
40.74
0.83
0.04
2.76
0.34
8.71
7.95
1.56
0.17
2.05
0.35
0.45
2.15
0.17
0.02
1.07
0.88
0.08
6.53
0.83
0.12
1.50
0.31
4.14
2.44
TOTAL
ClC
Free CaO
LSF(SO3)
LSF
Na2O+0.658*K2O
MS
MA
99.70
0.006
0.03
100.13
0.012
0.07
99.73
0.009
0.68
99.91
0.006
0.17
99.96
0.030
0.17
X-PLANT
Raw meal
Coal
ash
(LOI free)
970988
22.14
5.19
2.51
66.53
0.72
0.04
36.28
17.09
31.98
8.48
0.79
0.13
22.28
5.31
2.79
65.98
0.73
0.04
0.19
0.03
0.44
0.13
0.61
34.64
0.29
0.05
0.67
0.20
0.93
0.00
0.78
0.11
1.09
0.32
2.48
0.29
0.05
0.68
0.20
0.95
0.00
99.53
0.007
0.085
99.29
0.010
0.130
99.53
0.000
99.29
0.010
94
95
94
95
2.87
2.07
2.87
2.07
Raw
meal
317
318
-3
0
1
1
3
3
0
2
6.81
2.52
2.44
2.06
1.51
2.84
14.36
2.21
0.84
0.64
Clinker
0.00
93
93.7
0.64
2.75
1.90
CaO(SO3)
C3S
C2S
C3A
C4AF
Min. weight%
Weight % (X)
Max. weight %
65.32
56.87
21.28
9.34
8.49
80.00
83.11
90.0
4.00
4.09
10.0
2.50
7.00
7.0
1.00
4.14
5.0
0.00
1.47
5.0
99.80
99.80
100.2
99.05
0.95
100.00
The chloride content is also shown. Chloride is a volatile component and can
form coatings together with alkalies in the preheater. The chloride content has to
be restricted in preheater kiln systems to 0.015% by weight in the kiln feed.
.
4.5
PHYSICAL CONTROL AND COMPOSITION OF RAW MIX
The raw mix must contain the proper fineness and be homogenized before
27
Setpoint
94
0.67
2.75
1.90

entering the kiln. For the old fashioned wet process and for the semi-dry process,
the kiln feed is slurry with water content of 33 to 40%. In the dry process, the kiln
feed is a dry powder with a typical moisture content of 0.5 to 1.5%. The fineness
of the raw mix is measured on sieves .The normal sieves with respective
residues used are:
90 or 0.09 mm
10-20% retained
(equivalent to ASTM 170)
200 or 0.20 mm
0.5-1.5% retained
(~ equivalent to ASTM 70)
Also, the composition of the residue is important. Free silica ( quartz) will for
instance result in poor reactivity or burnability of the material in the burning zone.
When the coarse particles have a similar composition to the kiln feed ( less quartz)
then a greater amount of residue can be tolerated.
In the wet process, the slurry moisture should be as low as possible but still be
transportable via slurry pumps. The amount of water that is evaporated from
slurry with a moisture content of 30% is 0.66 kg/kg clinker, while a moisture
content of 35% requires evaporation of 0.83 kg water/kg clinker.
4.6
BURNABILITY OF RAW MIX
The reactivity of the kiln feed for slurry or raw meal is checked by the burnability test in the
laboratory. The procedures can vary from different kiln suppliers but in principle a few small
nodules are made of the raw mix ground to a fixed sieve residue. Usually, three sets of nodules
each of different sieve residues (5, 10 and 15% residue on 0.09-mm sieve) are burned for a
given time and at a given temperature. The clinker formed is then crushed and ground
determining the amount of free CaO. The free CaO is compared to the free CaO content
expected or found on a standard raw mix and classified as hard, normal or easy burnability.
If the raw mix is hard to burn, then the raw mix may have to be ground finer or the composition
might have to be altered. The first changes would normally be made to the MS or LSF. The
burnability can be estimated from the below formula:
28

CaO (1400oC) = 0.35*(LSF-96)+1.58*(MS-1.6)+0.55*(A44)+0.12*(R125)
where: A44= acid insoluble residue> 44 in %
R125 = total residue > 125 in %
4.7
CLINKERISATION
The reaction zones that occur as the raw mix is fed to the pyro system are:
1)
Drying Zone: < 100C, evaporation of free water
2)
Preheating Zone: 100-750C, loss of bound water in clays
3)
Calcining Zone: 750-1000C, decomposition of carbonates CaCO 3, MgCO3 and

others in the calcination zone. The CO2 leaves the kiln with the exhaust gas. CaO
and MgO are formed.
4)
Burning Zone: 1000-1450C, some liquid is formed and the fusion forms clinker
minerals C2S and then C3S.
5)
Cooling Zone: 1450-1300C, the melt solidifies and the material crystallizes,
cooling zone.
For dry preheater kilns without a precalciner, the material entering the rotary kiln is 40 to 50%
calcined. When a calciner is installed, the material is 80 to 95% calcined when entering the
kiln. A calciner temperature of ~ 875C will usually result in a calcination of approximately 9095%.
The advantages of a modern dry kiln with a preheater compared to a long wet kiln are:
- Smaller kiln
- Lower fuel consumption
- Less replacement of refractory due to longer lining life in the burning zone
- Better process control
- Larger production capacity
The advantages of a precalciner dry kiln compared to a preheater kiln are:
- Smaller kiln
- Better and easier process control
- Longer refractory life in the burning zone
29

- Two step firing with approx. 60% firing in the calciner and 40% firing in the kiln.
- Larger production capacity
4.8
INFLUENCE OF THE RAW MIX ON CLINKER FORMATION AND

BURNABILITY
The clinker formation is very important for plant operation and for cement quality.
Fine dusty clinker will be difficult to handle in the grate cooler and a large dust
circulation may start between the cooler and the burning zone. The coating in the
burning zone can become quite porous and unstable. Grinding of fine clinker
calls for a higher power consumption in the cement mill.
The two factors determining the clinker formation and the clinker size are:
a)
Agglomeration and nodulization in the burning zone due to liquid

formation
3
b)
Formation and growth of C S crystals working against nodulization
The nodulization depends on the liquid to bind the fine particles together. The
formation is a function of particle size and the amount of liquid. In the rotary kiln,
o
the liquid phase will start forming around 1340 C and amounts to 20-25 %. An
increase in temperature does not increase the amount of melt substantially.
30

3
Formation of C S starts, the rate increases and the size of the crystals increase.
The formation and growth of crystals in the burning zone eventually stops the
agglomeration. Four main characteristics of clinker formation are:
Alite size: measure of kiln burning zone temperature rise 1200-1450C where
belite is combining w/ CaO to form alite crystals. Rapid heating is desirable

w/ alite size ranging from 15-20, whereas, slow heating results in sizes of
60 or greater.
Belite size: reflects retention time in burning zone above 1400C. Maximum
retention time is desired w/ average crystal length of 25-40. Shorter

retention time = 5-10.
Belite color: rate of initial cooling to below 1000C. Rapid cooling is desired
resulting in clear crystals. Slower cooling gives yellow to amber colored

crystals.
Alite Birefringence: difference between refractive indices of blue/red light
related to maximum kiln temperature which is desired, birefringence of 0.008-
31
0.010. A cooler burning zone yields ~ 0.002.

Figure 1
Melt Formation as a Function of Temperature
Figure 2
% Liquid as a Function of MS, MA and LSF
32
The raw mix chemistry has a major influence on the process. A high MS will
result in less liquid phase formation and require a higher burning temperature.
Lowering the MS will give better burning and nodulzation. A lower MA results in a
3
higher liquid phase at a lower temperature. A higher LSF will give more C S
formation. Depending upon the level of LSF, a higher LSF will result in a higher
burning zone temperature and above a certain level the nodulization is impeded
and the clinker gets more dusty.
5. PROCESS AND KILNS

5.1
TYPES OF KILNS - wet, dry & semi-dry
The dry process is used predominantly today because of the lower heat
consumption and the better process control compared to the wet process. The
wet process is only used when fuel is very cheap or the raw materials are very
wet not making it economically feasible to replace it.
5.2
WET KILN
The wet kiln was for many years the standard equipment in the industry. Fuel
was cheap and the process of slurry preparation was easy. Homogenization in
silos and large slurry basins blended the slurry perfectly. The wet kiln had to
perform drying, preheating, calcination, burning and often clinker cooling in one
piece of equipment. However, the wet kiln has some limitations:
-Heavy fuel consumption
-Process control difficult
33

-Production over 1500 tpd clinker difficult
-High refractory cost
5.3
DRY KILN
A brief review of the FLS/FULLER dry kiln types is found in table no.9 below.
The table is included because there is a connection between cement chemistry and the
choice of kiln type. The layout of the different kiln types is shown on the figure on
enclosure 2.
5.3.1 LONG DRY KILN
The long dry kiln with a cross section for heat exchange is not installed any more. It has
been superceded by the more efficient preheater kiln systems
5.3.2 SP KILN
The Suspension Preheater type, SP, has preheater cyclones but no calciner. The number of
cyclones is 4 to 6. The material going into the kiln after the preheater has a degree of
calcination of 40 to 50 %. The last half of the calcination takes place in the kiln. This means
that the necessary amount of heat exchange in the kiln is larger than in the kiln types with a
separate calciner. The kiln has to be larger for a given production. Due to the calcination in the
kiln, the charge is fluidized by CO2 giving the material a chance to flow freely.
5.3.3 ILC-E KILN
The In-Line-Calciner using Excess Air type, ILC-E, has no tertiary air duct as all the air
passes through the kiln. A small calciner is built into the riser duct and the air for
combustion is drawn through the kiln.
5.3.4 ILC KILN
The In-Line-Calciner type, ILC, has a calciner in line with the kiln. The preheater is a
single string with the calciner built into the riser duct. Combustion air is drawn from the
grate cooler through a separate tertiary air duct. A damper in the tertiary air duct allows for
balancing the air between the calciner and the kiln.
5.3.5 SLC KILN
34

The Separate-Line-Calciner type, SLC, is a double string preheater with the calciner in
one string. The calciner is placed in parallel to the kiln riser duct. The combustion air for
the calciner is atmospheric air heated in the grate cooler and transported through a
tertiary air duct. The gas from the calciner and the gas from the kiln are not mixed and
pass through two separate strings of preheater.
.
5.3.6 SLC-S KILN
The Separate-Line-Calciner Special type, SLC-S, is a single string system with the
calciner placed at the side of the riser duct from the kiln. The gas stream from the calciner
is mixed with the gas from the kiln riser duct and pass through one string of preheater
cyclones. There is only one main ID fan. An adjustable restrictor at the top of the riser
duct makes the distribution of air between the calciner/tertiary air duct/cooler and the
kiln/riser duct.
5.3.7 SLC-I KILN
Separate-Line-Calciner with In-line-calciner in kiln string type, SLC-I. The system is a
development of the SLC system. It has the two strings as the SLC system but with a
calciner also in the kiln string. The SLC-I system can be used for upgrading of a SLC
system by the installation of a small calciner in the kiln string. The firing in the two
calciners will be:
-SLC-calciner:
40-50% of total firing
-ILC-calciner:
10-15% of total firing
Table 9
Comparison of Kiln Systems
Type
SLC
SLC-I
SLC-S
ILC
ILC-E
SP
tertiary air
Yes
Yes
yes
Yes
no
no
production, mtpd
11000
9000
4500
7500
4000
3500
calciner, % fuel
55/60
55/60
55/60
15/25
30
60
25
30
yes
medium
no
bypass, max% of kiln gas
100
55
SLC:40/50
ILC:10/15
100
inferior fuel in calciner
Yes
Yes
35

UNAX, KWh/t
FOLAX, KWh/t
12/14
11/13
22/24
22/24
22/24
22/24
18/20
17/19
40
40
70
70
70
70
min.production
max.content
Na2Oeq
1.0-1.5
1.0-1.5
1.0-1.5
1.0-1.5
1.0-1.5
1.0-1.5
in %
SO3
0.8-1.2
0.8-1.2
0.8-1.2
0.8-1.2
1.0-1.6
1.0-1.6
(clinker basis)
Cl
0.015
0.015
0.015
0.015
0.023
0.023
5.4
ASH ABSORPTION
The ash from the coal used for combustion will be absorbed in the clinker. This is
shown on the calculation sheet above (table 8). In the example, a coal with a
heat value of 7420 kcal/kg and an ash content of 9.4% is used. The heat
consumption in the kiln is 750 kcal/kg. The amount of ash absorbed is then:
Ash absorption = (750/7420) * 9.4 = 0.95 % of clinker
Therefore, it is necessary to analyse the coal ash to allow for this addition to the
raw mix.
5.5
VOLATILE MATTER
Some of the chemicals in the materials going into the burning zone evaporate.
The components can come from the raw materials, fuel and waste products. The
four most important are: potassium, sodium, sulfur and chloride. There are others
but they are normally of minor importance. These minor materials, heavy metals
or certain organic compounds can have important implications on the
environment for a given plant. The plant should be aware of the different minor
constituents to prevent any problems.
The four volatile elements mentioned above evaporate in the burning zone and
condense again in the colder parts of the kiln system. The colder parts are the
outer walls causing coating and build-up. Volatiles will also condense on the raw
meal particles, as they are colder than the gas carrying the volatiles.
36

Some of the volatiles may escape from the kiln system partly being caught in the
filter or escaping into the atmosphere. The volatiles that do not leave the system
with the exhaust gas either remain in circulation in the kiln system or leave with
the clinker. The volatiles can accumulate in the kiln and preheater causing
problems with in build-up in the cyclones and riser duct. It is important to be able
to foresee any problems that may occur before the start up of a new plant or a
conversion of an existing plant to prevent the possibilities of plugging.
A certain portion of the volatiles in the material flowing into the burning zone of
the kiln will evaporate at the high temperature. The portion that evaporates is
defined as the evaporation factor called (epsilon). A portion of the volatile
material leaves the system with the exhaust gas. This is referred to as a valve V.
An internal circulation of volatiles takes place and the circulation factor is called
K. The part of the volatile leaving the kiln with the clinker is the residual part
called R. A simple layout of a kiln system is shown below:
Figure 2
Circulation of volatile in simple kiln system
37
Evaporation factor
= d/b= (b-c)/b=1- c/b
Valve
V = e/d= (a-c)/(b-c)
Circulation factor
K = b/a
Residual component
R = c/a
For one unit of feed: a = 1 the material balance is:

K*(1- ) + K V = 1; K = 1/(1- (1-V)) ;
R = K*(1- )
The circulation factor K is the amount of compound going to the burning zone
when feeding a unit of 1 (one) to the system. R is the amount going into the
clinker. It is possible to calculate the circulation K and the residual in clinker R
when the evaporation factor and the valve V are known. The enclosed table
and figure give evaporation factors and valves for typical cases.
Table 10
Melting and Boiling Points of Alkali Salts
COMPOUND
Na
38
Melting
Boiling
Melting
Boiling
temp.
temp.
temp.
temp.
-oxide
Decompose
350
Sublime
1275
-carbonate
894
Decompose
850
Decompose
-sulfate
1074
1689
884
Decompose
-chloride
768
1411
801
1440
-hydroxide
360
1320
328
1390
39
Table 11
Evaporation factor
Kiln valve,wet kiln,nodule
operating
Kiln valve,wet kiln, dust
Typical values for and V

Symbol
K2O
Na2O
0.20-0.40
0.10-0.25
0.50
0.70
Vo
Cl
SO3
0.990-0.996
0.35-0.80
0.70
0.60
Vo
0.40
0.60
0.60
0.40
0.20
0.50
0.60
0.40
0.55
0.80
0.60
0.35
0.70
0.85
0.80
0.60
~1
~1
~1
~1
~1
~1
~1
~1
Cyclone preheater valve 1-
Vo
Vo
Vo
Vo
Vo
Vc
0.35
0.50
0.35
0.45
stage
Vc
0.20
0.45
0.20
0.30
stage
Vc
0.15
0.40
0.05
0.15-0.50
0.60
0.70
0.50
0.55
0.60
0.80
0.70
0.30
Cooling tower valve
Vc
Vm
Vkt
~1
~1
~1
~1
Electrostatic precipitator
Vf
0.40
0.70
0.30
0.50-0.80
operating
Long dry kiln
Kiln valve,1-stage kiln
Kiln valve,precalciner kiln
stage
Dedusting cyclone valve
Raw mill valve
valve
The evaporation of alkalies is larger when chloride is high. This is at times used
to increase the evaporation in the burning zone by adding CaCl 2.
Sulfur is difficult to evaluate. Some sulfur in the raw mix is present free in various
organic compounds or in pyrites. Approximately, 50% of the sulphur burns off in
the top stages of the preheater tower. CaCO3 assisted by moisture catches some
of it in the rawmill. SO2 in the preheater also reacts with calcium carbonate with a
maximum around 800C.
Sulfur in combination with alkalies behaves differently than SO 2 from fuel. Excess
sulfur, sulfur not bound as alkali sulfates, can be calculated as:
40

Excess S = 1000*%SO3- 850*%K2O-650*%Na2O < 250 g/100 kg clinker
where: All percentages are calculated on clinker basis
SO3 is total from rawmix + fuel
To ensure trouble free operation of a preheater kiln the following limits apply:
Table 12
Limits for Volatiles
Raw mix burnability
Na2O + K2O (% clinker basis)
Cl (% on clinker basis)
SO3 (% on clinker basis) from raw mix + fuel ;
Easy
Hard
Max 1.5 %
Max 1.0 %
Max 0.023 % Max 0.023 %

Max 1.6 %
Max 1.0%
Or excess sulfur under 250 g/100 kg clinker

If the natural valves are insufficient, then a kiln bypass can be installed. The
bypass will take part of the kiln gas before the preheater and transport it to a
separate cooling and dedusting system. The bypass gas has to be cooled
immediately to 350oC to avoid clogging. The cooling takes place in a swirling
chamber with atmospheric air. Some dust will be removed with the bypass gas
(2-3% with 10% bypass.)
5.6
MAIN FEATURES DURING BURNING
Chemical control during operation of the kiln system is divided into the following:
-Feed composition
-Product quality of clinker
-Emission control
-Fuel
-Preheater
The raw meal must have the correct quality with little variation. The standard
deviation for LSF should be less than 1% and corresponding less than 0.1 for MS
and MA. Large variations will result in irregular kiln operation resulting in
problems with ring formation and coating in the preheater, as well as, requiring
41

higher fuel consumption.
Performing a free lime analysis on an hourly basis monitors the product quality of
the clinker. The analysis can be made either on an average hourly sample or on
an hourly spot sample.
Environmental authorities stipulate emission control in many countries. The
plants have to control and continuously register plant emission of dust, SO 2 and
other constituents in the exhaust gas. The results have to be reported back to
the authorities.
The type of fuel used in cement production is either pulverised coal, fuel oil,
natural gas, or waste products.
Pulverised coal is usually produced at the site in a coal mill that dries and grinds
the raw coal to a fineness of approximately 15% retained on the 0.09-mm sieve
and moisture content of 1 to 2 %. The residue and the moisture content vary
according to the type of coal. Some types of coal with high gas content have a
high tendency toward self-ignition, which has to be taken into account. Coal with
low content of volatiles like semi-anthracite has to be ground very fine to promote
ignition.
An important component in heavy fuel oil and coal is the sulfur content. The
sulfur has to be taken into account together with the alkalies. Sulfur content in
heavy fuel oil above 5% will usually cause build up problems. Fuel analysis
should be made regularly by either the supplier or the plant laboratory.
The preheater has to be kept free from coating that can clog the cyclone outlet or
increase the pressure drop in the riser duct. This can be followed by regular
sampling of the material going into the kiln and analyse for chloride, sulfur, and
alkalies.
6. HEAT OF REACTION & HEAT TRANSFER

42
The chemical change from raw material to clinker requires heat for two reasons.
The first is due to the heat of reaction for the transformation to clinker.
Secondly, because the clinker process is not an ideal or 100 % effective process,
heat is lost from the kiln system as:
Radiation loss from all outer surfaces
Heat loss with the gasses from the kiln
Excess hot air from the clinker cooler
Heat loss with hot clinker
Heat effects the chemical reactions, the formation of solutions and changes in
the state of aggregation such as melting or vaporization. The heat effects are
called exothermic, when a reaction is accompanied by heat evolution. When heat
is absorbed, then the reaction is endothermic.
The dissociation of CaCO3, calcium carbonate, is a typical endothermic reaction:
CaCO3
CaO + CO2 422 kcal/g
The double arrow signifies that the reaction can be reversed. In the preheater,
this is called recarbonation. The order of magnitude of the heat of recarbonation
is normally evaluated from the temperature profile and the temperature difference
between the lowermost and second lowermost cyclone in the preheater tower.
When planning a new plant or when making a kiln conversion it is important to
know the heat of reaction for the process. The analysis is made in the laboratory
of the equipment supplier. Basically, there are the following heat changes:
Table 13
Reactions During Heating
Temp C
<100
100 - 400
400 - 750
Reaction
Evaporation of free water
Absorbed water evaporates
Decomposition of clay minerals,
43
Heat change
Endothermic
Endothermic
Endothermic
600 - 900
600 - 1000
800 - 1300
Kaolinite
metakaolinite
Decomposition of metakaolinite to free reactive oxides
Decomposition of carbonates to free reactive oxides
Reactive oxides form intermediate or final clinker
Endothermic
Endothermic
Exothermic
1300 - 1380
1250 - 1500
minerals
Formation of clinker melt from aluminates and ferrites
formation of aliteC3S the principal clinker mineral
Endothermic
Endothermic
The reactions within the kiln system take place at a slightly negative pressure
and in an oxidizing atmosphere. Reduction does not normally take place in the
kiln system apart from a reducing zone in the riser duct of the preheater to
reduce the emission of NOx. The first five reactions in the table take place rapidly
with a velocity determined by the transfer of heat from the gas to the solid
material. The last two reactions are determined first by the contact rate of the
reactive components present in the solid phases and later in the burning zone by
diffusion of the reactive components in the clinker liquid phase. The total of the
heat reactions during clinker formation is endothermic. An example of the heat of
reaction is:
Table 14
Heat of reaction
Evaporation of combined water
Decomposition of clay minerals
Dissociation of carbonates
Formation of clinker minerals
Kcal/kg
20
35
475
-130
Combustibles in the raw mix

Total heat of reaction
-15
385
The heat of reaction is the theoretical heat consumption for the kiln system.
44

Since the process is not ideal, heat losses exist in the system. The losses of
heat come from the following:
Hot exhaust gas
Heat loss from surfaces of the kiln system, i.e. radiation loss
Excess air from the clinker cooler
Heat lost with clinker after the cooler
Some of the loss can be utilized for drying of the raw materials and of raw coal.
Table 15
Typical Heat Consumption for Different Systems
Specific heat consumption for kiln systems

Wet kiln
Long dry kiln
1-stage preheater kiln
Semi-dry kiln w/ preheater & calciner
5-stage kiln w/ preheater & calciner
5-stage preheater kiln w/calciner and latest cooler type
kcal/kg clinker
1400
1100
1000
900
800
950
725
690
The dry process is always chosen unless the raw materials have moisture
contents above 20-30%.
The efficiency of the heat exchange in a cyclone is the same as the separation
efficiency due to the rapid heat transfer between material and gas. Usually, there
is only a temperature difference of 5C between the exit gas and material leaving
the cyclone. There is, however, a variation in efficiency between the cyclones as
we go lower down in the preheater. This is due to the change in the design of the
cyclones. At the high temperature in the lower cyclones these cyclones do not
usually have an internal vortex. The vortex or central pipe is difficult to construct
in a material that will last at the high temperatures.
7.FUEL
45
7.1
TYPES OF FUEL
The most common types of fuel are: coal, fuel oil and natural gas. The most
common fuel is coal with heavy fuel oil being second. Natural gas is used where
available and is an excellent fuel. Many waste products from a variety of
industrial sources are also used as a fuel source.
7.1.2 COAL
Coal is found all over the globe. Coal originates from plants, that over many
millenniums have been transformed into coal. The age of coal results in different
composition and quality. Anthracite and hard coal are old types, while lignite and
peat are younger types.
Raw coal is a combination of coal, ash and water. The carbon is the main
constituent in the coal, but there are also hydrocarbons, oxygen, nitrogen and
sulfur often as pyrites FeS2. Heating the coal in a non-oxidising atmosphere
drives out some of these constituents as gas also referred to as volatiles and tar.
The coal is then changed into coke. Younger coal has a higher gas content than
older coal. They are easier to ignite than the older coal. They are also prone to
self-ignition during storage.
Table 16
CLASSIFICATION OF COALS
Lignite
Bituminous coal
Anthracite
%
%
%
%
40-50
40 50
10-25
5-25
5-10
10 40
1-3
10-20
03
5
1
5-10
C
H
S
N+O
Hs
Hi
%
%
%
%
Kcal/kg
Kcal/kg
56
4
1
19
5120
4820
70
3
1
3
6625
6310
78
2
1
2
7100
6900
weight
volume
Kg/kg
Nm3/kg
7.1
5.5
9.2
7.1
9.9
7.6
Total moisture
Volatiles
Hygroscopic water
Ash
Examples of commercial grades of coals

Chemical composition:
Carbon
Hydrogen
Sulphur
Nitrogen + oxygen
Heat value
Gross
Net
Combustion air and gas

Combustion air required
46

Composition
Wet , 0%
of combustion
oxygen
gases
Total
Nm3/kg
6.0
7.4
7.8
CO2 + SO2
H2 O
N2
Dew point
vol%
vol%
vol%
C
17.8
10
72.2
46
17.6
6.5
75.9
38
18.9
4.5
76.6
31
Table 17
Typical Petroleum Cokes
Type
%H2O
%Volatiles
%Fixed C
%Ash
%Sulfur
Gross Heat
Hardgrove
60-100
25-30
Green delayed
11
82
0.5
Value (kcal/kg)
8000
Fluid
86
1.0
8000
Proximate analysis of coal:

The proximate analysis of a coal sample gives values for moisture, volatile
matter, ash and fixed carbon. It is performed under detailed laboratory
procedures, which can be found in other reference material. The volatile matter is
the portion of the coal when heated to 900 C without air is driven off as gases.
Fixed carbon is the residue remaining after the volatile matter is driven off. The
ash content is found by heating the sample to 800 C. The moisture in coal is
divided into free moisture and hygroscopic moisture, where the free moisture is
the moisture lost by air-drying. The volatile matter, fixed carbon, ash, and
moisture add up to 100%.
The amount and composition of ash varies from one coal to another. The amount
47

of ash and its composition has to be known, as it will be a part of the clinker.
Some coals have a very abrasive ash and a high wear index, which is of value
especially for vertical coal mills.
Coal dust can be dangerous and cause explosions. It can also self-ignite at room
temperature. For that reason a safety index for a particular coal is assigned
according to the characteristics of the coal.
The common safety index is the ratio of % fixed carbon to % volatiles. A high
safety index means a lower chance for a coal dust explosion. The safety index
for coal varies from 1 for high volatile lignite up to 15-16 for petcoke and
anthracite.
Ultimate analysis of coal:
In the ultimate analysis of coal, carbon, hydrogen, sulphur, nitrogen and oxygen
are determined.
Chemical analysis:
In the chemical analysis of coal, the inorganic composition is determined on the
coal ash. The values are used for the calculation of the raw mix and clinker
composition.
Heat value:
The heat value or calorific value is important for the evaluation of the coal and for
the heat economy of the kiln. The difference between the gross and net heat
value is the heat of evaporation of the water from combustion and the
evaporation of the water. The approximate calculation is:
Hnet = Hgross 5.85(9*%H + % Water in sample)
48
[kcal/kg]
7.1.5 WASTE FUELS

A variety of waste fuels are burned at cement plants. They consist of old tires,
used lubrication oil, and used solvents, i.e. waste plastic. Proper precautions
have to be in effect to protect not only the personnel but the environment as well.
Cement plants have accepted the responsibility for disposing of these many
different wastes and in some cases are financially rewarded.
Table 21
Typical Waste Fuel Analysis
Type of Waste
Heating value
Volatiles
Moisture
Ash
Sulfur
Dry Combustible
Density
(%wt.)
84.6
84.9
93.6
53.3
81.2
(%wt.)
10.2
20.0
10.0
72.0
1.04
(%wt.)
6.0
1.0
2.5
16.0
21.2
(%wt.)
0.20
0.05
0.13
0.52
0.79
(%wt.)
(lb/ft3)
Paper
Wood
Rags
Garbage
Coated fabric:
(Btu/lb)
7572
8613
7652
8484
10996
78.8
23.9
rubber
Coated felt:
11054
80.87
1.5
11.39
0.80
88.61
10.7
vinyl
Coated fabric:
8899
81.06
1.48
6.33
0.02
93.67
10.1
vinyl
Polyethylene
19161
99.02
0.15
1.49
98.51
5.7
film
Foam: scrap
Tape: resin-
12283
7907
75.73
15.08
9.72
0.51
25.3
56.73
1.41
0.02
74.7
43.27
9.1
9.5
13202
11428
100.0
75.06
1.72
0.56
0.13
4.56
0
0.02
99.87
95.44
6.4
23.4
covered glass
Fabric: nylon
Vinyl scrap
8.COMBUSTION
Combustion is the chemical reaction between oxygen and fuel. The main
component of coal and fuel oil is carbon, which is oxidised, or burns to carbon
49

dioxide CO2 with the evolution of heat.
The oxidisation of coal can start at room temperature with a coal of high reactivity
or high volatile content. Ignition of the raw coal can take place in the storage area
if the material is not stacked properly. If the temperature surpasses a certain limit,
the ignition temperature, a fire can easily start if oxygen is available. The ignition
temperature for coals varies in relation to the gas or volatile content. Lignites and
bituminous coals with volatile content over 30% have low ignition temperatures
whereas anthracite, petcoke and semi-anthracite require a high ignition
temperature.
In the burner, fuel is mixed with primary air as the two streams exit the burner
nozzle. The mixing depends on the direction of the stream and of the mixing
energy or velocity. The temperature of the primary and secondary air is also
important. The temperature of the flame can be calculated under ideal
conditions. The maximum theoretical flame temperature is found by fuel ignition
with the stoichiometric air requirement. The practical value is approximately 80
to 85% of the calculated one.
For coal, the water will evaporate first followed by gas evolution from the volatile
portion of coal. The rest of the fine and porous coal particles burn with a visible
flame due to the emission from the fine particles in the flame. In contrast, natural
gas can burn with hardly any visible flame. The fine coal particles will oxidise to
CO and later to CO2 as more oxygen becomes available. The flame front travels
with a certain velocity increasing with temperature and is also dependent on the
injected air/fuel stream for a steady combustion to be maintained. Coal with a low
content of gas like anthracite and semi-anthracite requires a high ignition
temperature, and usually a small amount of primary air is used.
The conditions for fuel oil are similar to coal. The oil droplets evaporate to gas
that ignites and burns. The flame is luminous because carbon or soot particles
are formed during the combustion. The ignition of oil is more difficult than with
50

coal due to the slower mixing of air and oil and to the evaporation of the oil
droplets.
The heat is transferred from the flame to the lining and the charge in the kiln by
radiation. The radiation follows:
R= e*k*( T14- T24)
[kW/m2]
e = coefficient of emission, max=1.
K is a constant
T1 and T2 are surface temperatures in Kelvin
The coefficient of emission for coal e is close to ~1 at the coal flame temperature.
This is due to the content of particles in the coal flame. For oil, the value of e is
0.7 to 0.9 and for gas only 0.2 to 0.6.
Radiant heat is transferred quickly to the lining and to the charge surface. But the
transfer of heat by conduction into the charge from the charge surface and from
the lining is a lot slower. This is one of the determining factors for the length of
the burning zone. The heat transfer is better when the charge is turning over
rather than sliding on the lining.
9. COAL & OIL

9.1
FINENESS OF COAL
The coal has to be dried and ground in a coal mill. The coal mill can be an airswept ball mill with separator or a vertical mill. The coal fineness depends on the
type of coal as seen from table 22:
Table 22
Coal Properties
Type
Volatiles %
Ash %
Hygroscopic water, %
Anthracite
Semi-
<5
5 15
5
3-5
<2
26
Anthracite
Low volatile bituminous coal
15 20
58
26
51
Sieve residues
of coal meal
5-7% +0.09 mm
1 % + 0.2 mm

Bituminous coal
High volatile bituminous coal
Lignite
20-30
30 40
40 50
8 10
10 20
15 30
26
26
10 25
residues
increasing to
coarser values
30% + 0.09 mm
3 4 % + 0.2 mm
The grindability is usually given as a hardgrove index number. The relationships

between the hardgrove index and the grindability in kWh/t for different types of
grinding applications are given below. The Hardgrove index for coals can vary
from 40 to over 100 for very soft lignite or petcoke.
An important aspect for the choice between a ball mill and a vertical mill is the
wear index. Some coals have a high ash content with an abrasive constituent
resulting in a high rate of wear. In such cases, a ball mill might be chosen or a
vertical mill with stronger wear resistant parts.
Figure 3
HARDGROVE-GRINDABILITIES
40
spec.grindability- KWh/t
35
30
25
20
15
10
5
0
40
50
60
70
80
Hardgrove index
ballmill, 5%+ 0.09 mm
ballmill, 10% + 0.09 mm
ballmill, 20% + 0.09 mm
vertical mill, 5%+0.09mm
vertical mill, 10% +0.09 mm
Vertical mill, 20% + 0.09 mm
52
90
HA
RD
ROV
G
E -G R
DAB
IN
I L
IT IE
40
35
s pe c.g rin da bi lity -K W h/ t
30
25
20
15
10
5
0
9.2
50
60
bal
i l,5
lm
bal
ver
il l,2 0% +
m
tica lm il, 10
+0
%
70
H ar dg rov e ind ex
.09 m m
b alm il ,10
.0 9 m
v ert
% +0. 09 m V ert
80
% +0 .09
ical m il,5 %+0.

ica lm il, 20% +
90
mm
09 m
0. 09 m
DRYING OF COAL
Raw coal contains varying amounts of water. The raw coal has to be dried to
facilitate grinding and handling but the drying must not go beyond the limit of
safety. The coal is dried in the coal mill only to the recommended minimum
residual moisture content to reduce the risk for fires and explosions. This
residual moisture content is found by using the graph in figure 4 below
according to the actual hygroscopic moisture of the coal. The plant laboratory
determines the hygroscopic moisture and residual moistures at various drying
temperatures. A detailed procedure to determine surface and hygroscopic
moisture of coal meal is found in another reference. Presented here is an
overview of the program.
Free moisture, or surface moisture, is the water lost by air drying a prepared coal
sample at an ambient temperature of 30C. Further drying of the coal sample at
various temperatures between 30 and 105C drives off the remaining water. The
ratio of the change in sample weight between 30 and 105C divided by the
weight at 105C, represents the hygroscopic moisture. A graph of the residual
moistures at various drying temperatures shows the correct operating
temperature for the outlet of the coal mill.
Usually, a coal mill outlet temperature of between 60 and 80 C is correct. The
inlet temperature to the coal mill can be as high as 300 to 350 C. The inlet
temperature depends on the quantity of air through the mill, and requires the dew
point of the outlet air after the coal mill to be 20 C higher than the outlet air
temperature to avoid condensation and clogging in the transport system following
the mill. For example, to dry one kg of coal with 10% moisture 1.2 kg drying air
Chemistry Bible
Rev.0; 7 Dec
00
1
2
53
12
10
8
6
4
2
0
4
Hygroscopic w ater,%
Residual moisture,%
Figure 4
Recommended moisture in coal dust

at 300C is required.
9.3
ASH CONTENT
The ash content in various coals differs in quantity as well as composition. It is

necessary to know the exact composition of the ash because it combines with
the raw mix in the kiln system. The ash analysis is performed by the plant
laboratory or by the coal supplier.
The ash content of coal will consume some heat during combustion due to
chemical changes of the minerals in the coal. This reduces the flame
temperature. In coals with a high ash content, it can be difficult to obtain a
sufficiently high flame temperature for the process.
9.5
MINOR COMPONENTS
Coal also contains alkalies, sulfur and chloride. These constituents have to be
taken into consideration for the calculation of the raw mix and of the clinker
composition. These volatile components will participate in the internal circulation
of volatile components in the kiln, calciner and preheater.
9.6
REQUIREMENT FOR AIR
The combustion of fuel requires air to oxidise the carbon, hydrogen and sulfur in
the flame into the combustion products of carbon dioxide, sulfur dioxide and
water. In addition, a certain amount of excess air is used to obtain complete
combustion without formation of carbon monoxide. The reactions are:
C+ O2 CO2 + heat
4H + O2
2H2O + heat
S + O2
SO2 + heat
The water content in the coal is evaporated.
54

The minimum amount of oxygen required for combustion, O min, can be calculated
by:
Omin = (0.01)*(32/12*C+16/2*H +32/16*S+32/14*N-O) [kg O/kg fuel]
Therefore the required amount of air, Lmin, is:
Lmin = (Omin / 1.429)
[Nm3O/kg fuel]
Lmin = [Omin / (0.21*1.429)]
[Nm3air/kg fuel]
The total volume of the combustion gas is:

Vmin= 0.0889*C +0.2231*H 0.0263*O + 0.0333*S +0.0124*H2O [Nm3gas/kg fuel]
Where: C, H, S, N, O, H2O are in %wt. of the fuel
Combustion takes place with surplus air to ensure complete combustion. The
surplus of air is referred to as excess air and is symbolised by the Greek letter
lambda, . The excess air in the combustion air is calculated from the formula:
= 1/(1-79/21*O2/(100-CO2-O2))
For example, the amount of excess air is 1.20% when O 2= 3.6 vol% and
CO2=15.4 vol%. If there is incomplete combustion CO is present and the formula
cannot be used. Incomplete combustion increases the heat consumption of the
kiln appreciably and it is dangerous for the precipitator.
The kiln exhaust will also contain CO2 from the decarbonation of carbonates in
the raw mix. For a normal raw mix, the amount of CO2 is 0.55 kg or 0.28 Nm3 per
one kg of clinker.
10. PROCESS GAS

The process gas contains combustion products from the fuel with some excess
air, as well as, products from heating the raw mix. The various components are
described further. The amount of combustion gas can be calculated from the
55

equation:
min
V = 0.0889*C +0.2231*H 0.0263*O + 0.0333*S +0.0124*H O [Nm gas/kg fuel]
This amount has to be increased by the excess air:
= 1/(1-79/21*O2/(100-CO2-O2))
The CO2 released by the heating of carbonates in the preheater, calciner and kiln
must also be added. The amount for a normal clinker is approximately 0.55 kg
per kg of clinker or 0.28 Nm3. Finally, there is the additional volume from
evaporation of water in the raw mix.
In most systems, the preheater gases are taken to a raw mill and/or coal mill and
used for drying the respective material. SO2 is present in the exhaust gases from
oxidation of the fuel S and decomposition of sulfates. Most of the SO 2 is totally
scrubbed in the preheater by K2O, Na2O, and CaO. Due to the lower volatility, the
alkali sulfates will most likely leave the system with the clinker. However, the
calcium sulfate ends up evaporating in the burning zone leading to an internal
cycle condensing at the backend of the kiln. The exhaust gas also contains SO 2
from the sulfides and pyritic sulfur present in the raw materials. They are oxidised
in the preheater and a portion escapes with the exhaust gas. By having the
exhaust gas go to a raw mill and/or conditioning tower, scrubbing of the SO 2
takes place reducing the emissions.
NOx is formed by combustion in the kiln and calciner. Fuel NOx is formed when
combustion occurs below 1200C. The amount of fuel NOx depends on:
Amount of N in fuel
Excess oxygen
Flame temperature
When combustion temperatures are higher than 1200 C, the NOx formed is
thermal NOx. This happens in the kiln-burning zone. The NOx formed is
56

predominantly NO, a small part (5%) of which in the colder parts of the preheater
is oxidised to NO2. Thermal NO increases with flame temperature above 1200C,
with retention time, and with increasing free oxygen. Thermal NO produced in
the kiln-burning zone is related to:
Flame temperature
Flame shape
Type of fuel
Excess oxygen
Gas retention time in the burning zone
Load temperature
Load retention time in the burning zone
A short, hot flame, excess combustion air and high secondary air temperature will
all increase NO formation. While fuel moisture, dust insufflation, or a high dust
entrainment in secondary air will reduce the NO. A harder burning mix will always
lead towards a higher NO, however, overburning should be avoided. It is
x
common to express NO as NO for regulatory purposes.
The NOx formed can be reduced in different ways. Ammonia can be injected in
the top cyclone. Another way is to have a reduction zone in the calciner, which is
the feature of the low-NOx calciner. In the reduction zone, the following reaction
takes place between 800-1100C reducing the NO x emissions:
[N] + NO
N2 + [O]
Another component sometimes found in the exhaust gas is CO. CO is usually
57

formed from incomplete combustion of the fuel. At temperatures around 680C,
oxidation of CO to CO2 takes place in the presence of excess oxygen. CO
emissions at the stack may be contributed from poor mixing of the
fuel/combustion air or not enough combustion air in the burning zone.
Organic C found in the raw materials tend to oxidise at temperatures below
680C with roughly 20% of the oxidation forms CO regardless of the amount of
oxygen present. The above holds true when the level of organic C in the raw
material is 1.4 g/kg clinker or more. For example, 2 g C/kg clinker with a 15%
conversion rate corresponds to about 250 ppm CO at 5% oxygen.
58

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NARMADA CEMENT CHEMISTRY - HANDBOOK

Chemistry Bible Rev.0; 7 Dec 00

NARMADA CEMENT CHEMISTRY - HANDBOOK

MAIN FEATURES DURING BURNING

6. HEAT OF REACTION & HEAT TRANSFER

10. PROCESS GAS

Chemistry Bible Rev.0; 7 Dec 00

NARMADA CEMENT CHEMISTRY - HANDBOOK

Cement is a material that binds together solid bodies ( aggregate) by hardening

Addition of gypsum to regulate the setting time

Higher burning temperature to obtain higher lime containing silicates

DEFINITIONS - cement, concrete, cement types, raw materials

Chemistry Bible Rev.0; 7 Dec 00

NARMADA CEMENT CHEMISTRY - HANDBOOK

cement is a mix of cement clinker and gypsum

calcium sulfate is used to regulate setting time.

concrete is a mix of cement (13%), water (7%), fine

there are numerous types of cement for many

used with reactive aggregates

used in applications requiring resistance

special architectural concrete

massive concrete like dams

mortar bonding brick or block

use an addition of slag or other pozzolans to

The common raw materials for manufacture of

Chemistry Bible Rev.0; 7 Dec 00

NARMADA CEMENT CHEMISTRY - HANDBOOK

limestone, marble, marl

79 volume percent in air

21 volume percent in air

A typical analysis of clinker is given in the table below:

Chemistry Bible Rev.0; 7 Dec 00

NARMADA CEMENT CHEMISTRY - HANDBOOK

LIME SATURATION FACTOR

Chemistry Bible Rev.0; 7 Dec 00

NARMADA CEMENT CHEMISTRY - HANDBOOK

Chemistry Bible Rev.0; 7 Dec 00

NARMADA CEMENT CHEMISTRY - HANDBOOK

CaO 0.7 * SO3

2.3 MINERAL COMPOSITION

Calcium alumino ferrite

4.07*CaO 7.60* SiO 1.43* Fe O 6.72* Al O

Chemistry Bible Rev.0; 7 Dec 00

NARMADA CEMENT CHEMISTRY - HANDBOOK

8.60* SiO + 1.08* Fe O + 5.07* Al O 3.07*CaO

(or C S= 2.867*SiO -0.7544* C S )

Chemistry Bible Rev.0; 7 Dec 00

NARMADA CEMENT CHEMISTRY - HANDBOOK

% Liquid Phase = 3.00A + 2.25F + (MgO + K O + Na O + SO )

- which is the di-hydrate form

- which is the hemi-hydrate form (plaster of paris)

- which is the anhydrite form

Chemistry Bible Rev.0; 7 Dec 00

NARMADA CEMENT CHEMISTRY - HANDBOOK

ORDINARY PORTLAND CEMENT

c) OIL WELL CEMENTS

a) PORTLAND CEMENTS are by far the most common type of cements

Chemistry Bible Rev.0; 7 Dec 00

NARMADA CEMENT CHEMISTRY - HANDBOOK

to sulfate-bearing waters. The cement composition has a lower content of C A,

b) COMPOSITE CEMENTS also known as blended cements start with Portland

Chemistry Bible Rev.0; 7 Dec 00

NARMADA CEMENT CHEMISTRY - HANDBOOK

4.07CaO 7.60 SiO 1.43* Fe O 6.72* Al O

(or C S= 2.867SiO -0.7544 C S )