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TECHNOLOGICAL ADVANCEMENT IN CEMENT

MANUFACTURING INDUSTRY

Aspdin’s “Bottle” Kiln

The furnace used in 1824 was a dome kiln of approximately 11 m in height and 5 m in
diameter with a production of approximately 15 tons per charge. It took several days to
produce each charge.

Later Developments -- Different systems.

 Vertical Shaft Kiln

 Rotary Kiln-Wet process, Dry process, Suspension Preheaters and precalciners

Rotary kiln was developed in 1885 by Frederik Ransome, England

Suspension preheater was developed in 1934 by Vogel Johenson, Germany
Precalciner was developed in 1970 by I.H.H. Industries, Japan.

Sizes of the rotary kiln in different systems for an output of 2000 t/day.

System Length Diameter

Wet 200 m 5.6 m
Dry 162 m 5.4 m
Suspension preheater 64 m 4.6 m
Precalciner 40 m 4.0m.
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RAW MIX DESIGN AND OPTIMIZATION

OF KILN OPERATIONS
Optimization of Kiln Operations
 Optimization of kiln operations is achieved by its stable operations.
 Stable kiln operations are controlled by
 Chemical composition of kiln feed
 Uniformity of kiln feed
 Fineness of kiln feed

Stable kiln operations result in:

 Higher clinker production rate
 Lower fuel consumption/kg of clinker
 Improved refractory life and lower refractory cost
 Increased kiln operating time
Raw Mix design

Certain moduli or ratios had been developed for designing a suitable mixture of raw
materials for the production of clinker of consistent quality. The theoretical chemical
composition of clinker is calculated on loss on ignition basis from the raw meal or kiln feed
analysis.
While using coal, fuel ash has to be taken into consideration. In case, chemical composition
of kiln feed and % of various oxides in the clinker are not known but only % of various
compounds/phases in the cement desired are known, as given below, then SiO2, Fe2O3,
Al2O3 , CaO desired in clinker on gypsum free basis can be worked out as per formulae
given below:
Average % of compounds/phases in various Portland cements
Classification
Types of Portland Cements C3S C2S C3A C4AF
ASTM British
Ordinary Portland 52 22 10 8 Type I O. P.
Rapid-hardening 62 13 10 7 Type III(a) R. H.
Low-heat 30 45 4 12 Type IV(b) L. H.
Sulphate-resistance S. R.(e)
Moderate 51 24 6 11 Type II(c)
High 46 30 3 12 Type V(d)
a) C3A content not exceeding 15% d) C3A content not exceeding 5%
b) C3A content not exceeding 7% e) C3A content not exceeding 3.5%
c) C3A content not exceeding 8%

Formulae for Calculating Chemical Composition of Clinker from its Compound

Composition

SiO2 (%) = C3S x 0.2632 + C2S x 0.3488

Fe2O3 (%)= C4AF x 0.3286
Al2O3 (%) = C3A x 0.3774 + Fe2O3 x 0.639
CaO (%) = C3Sx0.7368 + C2Sx0.6512 + C3Ax0.6226 + C4AFx0.4616 + free CaO
Example
Compound composition of clinker
C3S = 59.85%
C2S = 17.81%
C3A = 8.60%
C4AF = 8.46 %
Chemical composition of clinker (oxide)
SiO2 = C3S x 0.2632 + C2S x 0.3488
= 59.85 x 0.2632 + 17.81 x 0.3488 = 21.96%
Fe2O3 = C4AF x 0.3286
= 8.46 x 0.3286 = 2.78%
Al2O3 = C3A x 0.3774 + Fe2O3 x 0.639
= 8.6 x 0.3774 + 2.78 x 0.639 = 3.25+1.77 = 5.02%
CaO = C3Sx0.7368 + C2Sx0.6512 + C3Ax0.6226 + C4AFx0.4616 + free CaO
= 59.85 x 0.7368 + 17.81 x 0.6512 + 8.60 x 0.6226 + 8.46 x 0.4616 + 1.5
= 66.46%
CHEMICAL COMPOSITION OF KILN FEED 3
Raw materials mix should be properly designed and various parameters should be kept in
view.

LSF
Greater than 100 indicates the possibility of free lime. Requires more retention time in the
burning zone. Less than 90, easy to burn.

Higher contents of lime require more heat for its calcinations.

CaCO3  CaO+CO2
800 – 900 oC
750 kcal/kg CaO

Heat required for clinker with 65% CaO:

CaO (0.65) x (750 kcal/kg) = 487.5 kcal/kg clinker

Heat required for clinker with 60% CaO:

CaO (0.60) x (750 kcal/kg) = 450.0 kcal/kg clinker

Extra heat required for burning clinker from 60 to 65% CaO = 37.5 kcal/kg clinker
1% reduction in lime shall result in saving of 7.5 Kcal/kg of clinker

Lowering lime saturation factor of clinker from 99% to 96.5 results in saving of 80-90 Kcal/kg
of clinker.

S.M/SR
Higher the SM-higher is the clinkering temperature. Reduces liquid phase. Results in
abrasion of refractory lining. Clinker is dusty.
Lower SM-liquid phase increases.
Lowering of silica modulus by 0.2% is estimated to reduce clinkering temperature by about
10 °C reducing heat consumption by about 10 kcal/kg.

A.M/AR
Higher A.R. reduces liquid phase, results in hard burning and more fuel consumption.
Lower A.R. increases liquid phase. Clinker usually hard to grind.
Higher is the alumina ratio, higher is the clinkering temperature.
Lowering of AM ratio by about 0.2 can result in lowering of clinker temperature by about 20
kcal.kg of clinker.

Liquid Phase
At a temperature between 1260 oC and 1310 oC, first melting takes place in the kiln, known
as sintering or clinkering. With rise in temperature, the proportioning of liquid increases to
20-30% at 1450oC.

Fluxing components in the mix are alumina, iron, magnesia and alkalies. These fluxes in the
kiln govern the liquid present at clinkering temperature. The higher is the percentage of liquid
at this temperature, the easier the clinker to burn.

Rapid formation of C3S through dissolution of C2S and CaO takes place which is very
important reaction.
Influence of feed on Burnability
The burnability of a kiln feed is the relative ease or difficulty with which the feed is changed
into clinker in the kiln .It is an indication of the amount of fuel required to burn the kiln feed
into clinker.. Every time feed composition changes burnability in the kiln will also change.

Burnability Index (B.I.) = _____ C3S ______

(C3A + C4AF+M+alkalies)
Very Easy 2, Easy 3, Difficult 5.

Burnability Factor (B.F.) = 100 LSF + 10(S R) - 3 (M + N + K) = 110-115

Silicic acid ratio = S/A = 3.5-4.5

TiO2 to be added to Al2O3 if TiO2 concentration is relatively high

.Coating Index or value = 20-25

A.R. ³ 0.64 = C3A + C4AF + 0.2C2S + 2F
A.R. < 0.64 = C2A + C4AF + 0.2C2 S + 2F
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EFFECT OF SILICA PARTICLES IN RAW MEAL
ON CLINKER QUALITY
Free silica if present in the raw materials, causes high wear in the crusher and in the
grinding mill. Raw materials containing silica must be ground very finely. Free silica acts as
an abrasive on the kiln lining and no coating is formed unless there is a reasonable amount
of flux, mainly iron. The fuel consumption also increases. Kiln feed should not contain more
than 3% of free silica; this percentage mainly depends on the particle size of the free silica
and the fineness of the kiln feed.
Presence of silica in the form of quartz results in coarser fraction making the chemical
reaction difficult. It results in heterogeneity in the clinker. SiO2 not fully combined results in
lower amounts of C3S and C2S and clinker strength development is reduced. Also some of
the SiO2 remains un-reacted and amount of lime remains as free lime which causes
unsoundness in cement and leads to long term expansion of concrete.

According to F.L. Smith, poor burnability is primarily caused by the presence of coarse grains
calcite +124 m and quartz +45 m

Figure given below shows the influence of silica on burnability of clinker

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CHEMICAL UNIFORMITY OF KILN FEED
Homogenity is a major requirement for obtaining clinker of uniform composition for ensuring
steady burning conditions. Otherwise pockets consisting of different phases will occur in the
clinker.
Uniform kiln feed is defined by the standard deviation of various parameters of kiln feed. The
standard deviation is based on the evaluation of a statistical series of measurements.
Given below are the maximum allowable standard deviation limits found necessary for
stable kiln operation.
Maximum Acceptable Standard Deviation of Kiln Feed Parameters

Kiln feed parameter Maximum acceptable standard deviation

C3S, % 3.0
LSF 1.0
Silica ratio/alumina ratio 0.15
Liquid phase 0.5
Calcium carbonate % 0.25
In tables 9-4 to 9-7, changes in chemical composition of clinker by 0.25 %,0.50 %,.0.75 %
and 1.0% in basic oxides and effect on various parameters had been shown.
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RAW MEAL FINENESS
The rate at which reactions take place are generally dependent on the particle size of the
reactants i.e. reactive surface areas. The raw meal fineness should be such that the
particles react completely. With smaller particles, the reaction times are shorter. Sintering
rate of the raw mix is roughly proportional to the particle size.

The finer the raw meal, more easier to burn and the lower the clinkering temperature. With
coarse material, lime combining degree decreases with coarse material and free lime
increases as shown in the graph with three different fineness (5.10 and 15% on 170 mesh).
The figure reproduced below shows the free lime content as a function of raw mix fineness
and burning temperature.

Coarse fraction in the kin feed is more significant than the fine fractions in relationship to
burnability. Each plant needs to test and specify a limit of allowable fractions on 30-50 mesh
sieve.

Actual maximum acceptable fine size depends upon raw materials, the composition of the
kiln feed and the type of pyroprocessing system.

Kiln feed also affect the amount of dust entrained in the kiln exhaust and lost from a kiln.
With finer feed, more dust will be entrained in the exit gas stream.

CaO (%)

4.0
LSF = 95
SR = 2.5

15%
3.0

10%

2.0

5%

1.0

1450 1500 1550 1600 (°C)

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USE OF FLUXES
Calcium fluoride (Fluorspar, CaF2) is considered to be most effective fluxes. By using fluxes,
the temperature of the burning zone may be lowered by 50- 100°C and give an energy
saving of 2-3%. The usefulness of an appropriate flux has to be evaluated by actual trials.
Fluxes used should not have any harmful effect on the quality of cement and environment.

Trials carried out in some cement plants in America and other countries has revealed that
kiln production may increase from 5 to 10% by using 0.25-0.30% of CaF 2. Fuel consumption
also may reduce by about 2.3-4.5%.

Composition of fluorspar (%)

S 18.33
A 0.78
F 2.06
C 45.13
M 0.30
F (fluorine) 29.85
LOI 3.3
Total: 99.75

THEORETICAL HEAT OF FORMATION OF CLINKER

Endothermic reactions Kcal Kg. Exothermic reactions Kcal Kg.

Dehydration of clay 40 Crystallization of dehydrated 10
clay
Dissociation of CaCO3 475 Heat of formation of clinker 100
minerals
Heat materials 1450° 490 Crystallization of melt 25
Heat of melting 25 Cooling clinker 335
Cooling of CO2 120
Cooling of water 20
Total: 1030 Total: 610

Net theoretical heat required to form 1 kg clinker = 1030-610 = 420 kcal

(Endothermic heat – Exothermic heat)

Simple formula to work out heat of formation commonly used is:

489 x Al2O3 714 x CaO 587 MgO

   73 kcal/kg/Cl
100 100 100
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Effect of coal ash on composition of clinker
The percentage of coal ash absorbed in the clinker can be calculated from the loss-free analysis of the ash, raw
mix and clinker is as follows:

Constituents Raw Coal Clinker Clinker

(%) Mix Ash (theoretical) (Actual)
Silica (S) 13.85 49.41 21.43 22.00
Alumina (A) 3.65 26.76 5.65 6.05
Ferric oxide (F) 2.20 16.73 3.40 3.80
Calcium oxide (C) 42.82 1.54 66.49 65.85
Loss on ignition 35.60 -- -- --

22.00 – 21.43
100 = 2.04
49.41 – 21.43
6.05 – 5.65 On the average, quantity of the coal
100 = 1.90
26.76 – 5.65 ash absorbed by the clinker during the
3.80 – 3.40 burning process is 2.4% of clinker
100 = 3.00 produced.
16.73 – 3.40
65.85 – 66.49
100 = 2.70
42.82 – 66.49
Absorption of Coal Ash

Coal consumption based on clinker 16 %

Percentage of ash in dry coal 15%
Ash absorption factor 1

Therefore ash absorbed per 100 parts of clinker = 16 x 0.15 x 1 = 2.4%

2.4 x 100
Ash per 100 parts of kiln feed = = 1.60
97.6 x1.54
1.54 is the conversion factor of raw mix to clinker

Effect of fuel ash on the composition of the clinker may be observed from the following example in
which 1.6 parts of ash combines with 98.4 parts of raw mix:

Raw Raw Mix Clinker

Constituents (%) Mix Ash 98.4+Coal Ash (theoretical)
1.6
Silica (S) 14.00 43.04 14.47 22.1
Alumina (A) 4.12 28.22 4.51 6.89
Ferric oxide (F) 1.84 6.46 1.91 2.92
Calcium oxide (C) 43.07 11.93 42.57 65.0
Loss on ignition 35.00 4.2 34.51 -
L.S.F. - - - 0.90
S.M - - - 2.25
A.M - - - 2.36
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TYPICAL COMPOSITION OF RAW MEAL, CLINKER,
AND RELEVANT PROCESSING PARAMETERS
Parameters Raw Meal Loss free Coal ash Clinker
SiO2 14.4 22.3 54.3 22.6
Al2O3 3.2 5 26.2 5.2
Fe2O3 1.8 2.8 16.7 2.9
CaO 42.4 65.7 0.6 65
MgO 1.3 2.02 0.8 2
SO3 0.37 0.57 0.1 0.6
K2O 0.6 0.93 1.2 0.9
Na2O 0.17 0.26 0.1 0.3
TiO2 0.17 0.26
Mn2O3 0.12 0.19
P2O5 0.11 0.17
Cl 0.03 0.05
LOI 35.5 0 0 0
SR 2.9 2.9 1.3 2.78
AR 1.8 1.8 1.6 1.77
LSF 91.7 91.7 0.3 91.1
C3S 30.6 60.6 610.1 53.6
C2S 18.3 18.3 616 24.4
C3A 8.4 8.4 41.2 8.8
C4AF 8.5 8.5 50.8 8.9

Effect of 2 per cent ash absorption on composition

No ash absorption 2% ash absorption

SiO2 20.09 20.69
Al2O3 6.43 6.80
Fe2O3 2.30 2.45
CaO 68.61 67.34
Free lime 1.00 1.00
Lime saturation factor 1.05 0.99
Silica modulus 2.30 2.24
Alumina Modulus 2.80 2.78
C3S 76 64
C2S 0 11
C3A 13.2 13.9
C4AF 7.0 7.5
 WASTE DERIVED FUELS

Characteristics of Some Commonly Used Waste Derived Fuels

Type of fuel Percentage of Composition by Weight (Kcal/Kg)
Heating Value Moisture Ash Volatile FC Sul (Net)
% % % % %
Old Types - - - 70-80 1.3 7000

Wood Waste 25-60 1.0* 82.0* 17.0* - 4944

Oil Shale 15.0 43.0 42.0 - - 3500

Bagasse 45-50 1.8 - 46.3 - 4610

Rice Straw or Hulls 7.0 19.8 59.0 13.8 - 3400

Paper 20 26.9 47.6 5.5 - 4170

Garbage 10.2 6.0 84.6 - 0.20 4200

Foam Scarp 72.0 16.0 53.3 - 0.52 4700

Waste oil 9.72 25.30 75.73 - 1.41 6820
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GLOBAL WARMING-REDUCTION CARBON DIOXIDE