Quality - Mine

LEARNING MORE ABOUT
PROCESS
Chemistry and Physics of
Clinker Burning
Conducted By
KHD Humboldt Wedag
Chemistry and Physics of Clinker Burning
I. Raw Materials
II. Composition of Clinker Phases
III. Characteristic Clinker Parameters

IV. Blending of raw meal & Impacts
V. Examples of Raw Mix & Clinker
VI. Simple calculation practice

Clinker Clinker Simple
Raw Materials Blending Examples
Phases Parameters Application
Raw Materials
Typical Components for Raw Mixture:
Lime Component (CaCO3) ~ 80 %
Clay Component (SiO2, Al2O3, Fe2O3) ~ 15%
Additives, Corrective Components (SiO2, Al2O3, Fe2O3) ~ 5%
Example for raw mix composition (on ignited basis)
CaO 65 – 68 %
SiO2 20 – 23 %
Al2O3 4–6%
Fe2O3 2–4%
MgO 1–5%
Mn2O 0,1 – 0,5 %
TiO2 0,3 – 0,5 %
SO3 0,1 – 1 %
K2O 0,1 – 1 %
Na2O 0,1 – 0,5 %
Lime Component
Natural deposit of calcium carbonate (CaCO3)
- Limestone
- Chalk
- Marble
 The hardness of limestone (grindability) depends on the composition and geological

age.
 A natural admixture of CaCO3 with silica (SiO2), alumina (Al2O3) and iron (Fe2O3) is
called Marl.
Lime Component
From High Grade Limestone to Clay
Description CaCO3 Content [Ma-%]
High Grade Limestone 96 – 100 %
Marlaceous Limestone 90 – 96 %
Marlstone or Calcareous Marl 75 – 90 %
Marl 40 – 75 %
Clayey Marl 10 – 40 %
Marlaceous Clay 4 – 10 %
Clay 0–4%
Clay
The other important raw mix component is Clay.
Main components in Clay:

– Silica (Si)
– Alumina (Al)
– Crystalline bound water.
Clays are divided in two main groups:

Montmorillonite Al2 [ (OH)2 Si4O10]·n H2O
Kaolinite Al4 [ (OH)8 Si4O10]
The chemical composition of natural Clay can contain considerable amounts of Quartz
(Si), Calcite (CaCO3), Gypsum (CaSO4·2 H2O), Iron Hydroxide (FeOH), Pyrite (FeS2),
Alkali Metals (K, Na) …
Corrective Components
If it is not possible to get an adequate raw mixture only with the two components
Limestone and Clay, than it is necessary to admix a corrective component.
Corrective components are enriched in mainly of one chemical component, e.g.:

Main Alumina Iron Iron Silicon
Component
Name Bauxite Pyrite Cinders Iron Ore Sand
L.O.I. 15 – 20 5 – 12 0,2
SiO2 16 – 22 6,6 – 25 20 – 25 99,2
Al2O3 44 – 58 2 – 16 3–9
Fe2O3 10 – 16 62 – 87 45 – 60 0,5
CaO 2–4 0,7 – 0,9 0,5 – 2,5
MgO 0,2 – 1 0,2 – 2 1,5 – 7
SO3 0,8 – 8 0,3 – 0,6
Raw Materials Belding Examples
Raw Mix
The following table shows a typical Raw Mix composition as example (raw, containing L.O.I.).
Important: Ash from the fuel (e.g. coal) is part of the raw mix. The raw mixture must consider
the fuel ash amount and chemical composition.
Component Limestone Clay Iron Ore Raw Mix

Share [Ma-%] 75,0 24,0 1,0 100
L.O.I. 42,0 10,0 5,0 34,5
SiO2 3,0 55,0 10,5 14,0
Al2O3 0,8 14,0 7,0 3,5
Fe2O3 0,3 7,5 75,0 2,1
CaO 53,0 5,5 3,0 44,0
MgO 0,6 1,95 4,0 0,9
SO3 0,25 0,50 1,0 0,5
K2O 0,2 1,8 0,9 0,3
Na2O 0,1 0,8 0,3 0,15
Cl 0,001 0,008 0,04 0,005
Raw Materials Benlding Examples
Raw Mix
Target is to get a raw mixture to hit the
“Area of OPC” in clinker.
Typical percentages of these elements in

clinker, expressed as oxides, are:
CaO = 65 ± 3%,
SiO2 = 21 ± 2%,
Al2O3 = 5 ± 1.5%,
Fe2O3 = 3 ± 1%.
Left is shown the three-component phase

diagram for the CaO–SiO2–Al2O3 system.
The area indicated as Portland Cement is

the only area that will yield acceptable
cement properties.
Preheating / Calcination / Sintering / Cooling
1. Evaporation of free water of kiln

feed at temperatures up to 100°C
2. Removal of adsorbed water in

clay materials (Si, Al, Fe) 100°C -
300°C
3. Pyrolysis of clay material and

formation of reactive oxides 450°C
- 900°C
4. Calcination of carbonate
materials
CaCO3 → CaO + CO2 (Δh>0) )
700°C - 850°C
5. Formation of Belite (C2S),

aluminates (C3A) and ferrites
(C4AF) 800°C - 1250°C
Preheating / Calcination / Sintering / Cooling
6. Start of sintering with increasing

the amount of liquid phase
>1250°C
7. Formation of Alite (C3S) 1300°C

- 1450°C
8. Cooling of clinker to solidify

liquid phase 1300°C - 1240°C
9. Final clinker microstructure

frozen in clinker (avoid reverse
reaction) <1200°C
10. Clinker cooled in cooler

1350°C - 100°C
Composition of Clinker Phases
Typical Clinker Granules


Calculation of potential clinker phases according to Bogue
For AM>0,638 (standard Portland Cement Clinker)
C3S = 4,071 CaO - 7,6 SiO2 - 6,718 Al2O3 - 1,43 Fe2O3

C2S = 2,867 SiO2 - 0,754 C3S
C3A = 2,65 Al2O3 - 1,692 Fe2O3
C4AF = 3,043 Fe2O3
For AM<0,638 ( C3A-free Clinker)
C3S = 4,071 CaO - 7,6 SiO2 – 4,475 Al2O3 – 2,863 Fe2O3

C2S = 2,867 SiO2 - 0,754 C3S
C2F = 1,702 Fe2O3 - 2,665 Al2O3
C4AF = 4,766 Fe2O3
Real Life: Formation of Mixed Crystals

Abbrevia
Mineralogical Phase Portion of clinker [%]
tion
CaO Free lime CaOfree <2
3 CaO·SiO2 Alite C3S ca. 40-80
2 CaO·SiO2 Belite C2S ca. 0-30
3 CaO·Al2O3 Calciumaluminate C3A ca. 7-15
4 CaO(Al2O3, Fe2O3) Calciumaluminateferrite C4AF ca. 4-15


Alite, C3S (3 CaO·SiO2)
Alite is the main mineral for the formation of strength in cement, respectively in
concrete.
Belite, C2S (2 CaO·SiO2)

Belite is less reactive compared to Alite and therefore responsible for the formation of
concrete strength to a later time.
Calciumaluminate, C3A (3 CaO·Al2O3)

Aluminate is high reactive with water. It has fast setting behavior in concrete with low
strength properties. The setting time of concrete can be influenced by the amount of
gypsum during finish grinding process.
Calciumaluminateferrite, C4AF (4 CaO.Al2O3. Fe2O3)

Ferrite is less reactive compared to Aluminate. Ferrite favoured the sulphate resistance
properties of concrete.
Clinker Early Final Setting Water demand

Phase strength Strength time
(> 28 d)
C3S ↗ ↗ - -
C2S ↘ ↗ - -
C3A ↗ ↘ ↘ ↗
C4AF ↘ ↗ - ↘
Free lime ↘ -
Periclase - - - -
Alkali- ↗ ↘ - ↗
metals
↗ = increase ↘ = decrease - = no effect

Characteristic Clinker Parameters
Clinker Moduli
100 CaO
lime saturation factor II: LSF II = (LSF II = 90-96)
2,8 SiO2  1,18 Al 2 O3  0,65 Fe 2 O3
SiO 2
silica ratio: SM = (SM = 2,0-2,7)
Al 2 O3  Fe 2 O3
Al 2 O3
aluminia ratio: AM = (TM = 1,0-1,6)
Fe 2 O3
Raw Materials Bending Examples

100 CaO
Lime Saturation Factor II: LSF II = (LSF II = 92-98)
2,8 SiO2  1,18 Al 2 O3  0,65 Fe 2 O3
The Lime Saturation Factor describes the stoichiometric composition between Ca and its
reaction partners Si, Al, Fe.
The lower the number so much better to “burn” this mixture in the rotary kiln. However,
the quality of the produced clinker is than low (low C3S (Alite) content).
It is easier to maintain a low free lime content in clinker with a low LSF raw mixture.
A high LSF value will lead to a high quality clinker (high C3S content). The burnability of
this raw mix is more difficult compared to a low LSF raw mix. Often it needs more fuel
energy to maintain a clinker with adequate free lime content.
SiO 2
Silica Ratio: SM = (SM = 2,0-2,7)
Al 2 O3  Fe 2 O3
The Silica Ratio describes the amount of solid and liquid phase of the raw material in the kiln.
Si reacts with Ca to C2S and C3S mainly in solid phase. Al and Fe containing minerals mainly
exist in the liquid phase.
Generally
Silica Ratio high: - dusty kiln atmosphere
- poor coating conditions in the sintering zone
Silica Ratio low: - heavy coating formation or ring formation in the rotary kiln
- non-uniform clinker size formation, very coarse clinker and formation of

boulders (instead of clinker granules).
- Tendency of “Snowman” formation on clinker cooler

Al 2 O3
Aluminia Ratio: AM = (TM = 1,0-1,6)
Fe 2 O3
The Alumina Ratio describes the viscosity of the liquid phase. A mixture with high Fe content
tends to a liquid phase with low viscosity and a mixture with high Al content tends to a liquid
phase with high viscosity properties.
Generally
Alumina Ratio high: - high viscosity liquid phase (tenacious properties)
- non-uniform clinker size formation, very coarse clinker and formation of
boulders (instead of clinker granules)
- risk of heavy coating formation or ring formation into the rotary kiln
Alumina Ratio low: - low viscosity liquid phase (thin fluid properties)
- tends to very fine clinker granule formation
- often only very thin and unstable coating formation into the rotary kiln
Coating Behaviour
Alumina Ratio, AR
Thick coating, clinker ball Very thin coating,

or sinter ring formation dusty clinker
(plenty of viscous melt phase) (little of viscous melt phase)
1.6
1.3 NORMAL
COATING
1.o
Thin coating, Thin coating
refractories attack (little of fluid melt phase)
(plenty of fluid melt phase)
2 2.5 2.8 Silica Ratio, SR

Effects of minor oxides on process & Products
Oxides Effect on Process Effects On Products Limits
MgO Ring, Flux Concrete Expansion <5% in clinker
Setting time ,Mechanical <1.3% Depending on

Alkali-Aggregate reactions , Flux,
K2O,Na2O Strength, Chemical the Process ,<0.6 % for
Volatilization
resistance Low Alkali Clinker
SO3 Flux, Ring, Emission Setting Time 1-2% on Alkali Content
TiO2 Liquid Phase, Burnability <1%
Setting time, mechanical

CL Volatilization,Emmissions,Corrosion <.02% in Kiln feed
strength

Sodium Equivalent: Na2O-Eq. = 0,658 K2O + Na2O
Liquid Phase acc. to LEA:
MgO > 2,0 M-% = 2,95 Al2O3 + 2,2 Fe2O3+ (MgO - 2,0) + K2O + Na2O
MgO < 2,0 M-% = 2,95 Al2O3 + 2,2 Fe2O3+ K2O + Na2O
Degree of Sulfatisation of Alkalies:

100 SO3
SG =
0,85 K 2O  1,29 Na2O  1,13 Cl
The chlorine content will be considered only if exceeding 0,015 % (free of ignition).
Theoretical Heat Demand for clinker formation acc. to ZUR STRASSEN:
Qtheor. = 7,646 CaO – 5,116 SiO2 + 4,11Al2O3 – 0,59 Fe2O3 + 6,48 MgO [kcal/kgCLI]
Blending of Raw meal
 It must provide a kiln feed of constant chemical composition & finess

 It must provide intermediate stroage of raw meal which allows maintanance of raw Mill
 Blending silo can only bled what is within the silo.It is important to run silo a full as
possible all time.
 Belding silo also make sure that homogenasation is well in controlled with pre heater
dust loss, Specially when raw mill is in stop condition
 Blending helps to maintain good chemistry in kiln feed without any varions.Specially
CaO,LSF & CaCO3.
 Belding of raw meal is important process for Acheiving Stable pyro process operation.
Limits of Standard deviation requirements kiln feed
 Std.Dev <1% for LSF

 Std.Dev <0.1% for CaO
 Std.Dev < 0.2 % CaCO3
 Std.Dev < 3 % C3S
 Stable operation is possible only if we maintain thses limits undercontrol

 Fuel Consumption of pyro system will be changing by 1.5Kcal/kgcl for every increament
on standard deviation of kiln feed
 By experience no further improvement in kiln stability or clinker quality can be
expected through additional homogenisation
Phases Parameters
parameters Application
Standard Deviation Examples

Kiln feed LSF
Time Day 1 Day 2 Day 3 Day 4 Day 5 Day 6 Day 7
Example -Kiln feed LSF Deviation (X- Plant)
0 103 105 95 96 94 108 99 4.50
1 103 102 99 101 94 98 97 4.23
2 103 99 97 112 100 96 98 4.00
3 104 96 94 106 102 90 97 3.64
3.50 3.44
4 106 100 94 103 101 92 96 3.23
5 98 102 100 103 96 96 98 3.00 2.94
6 102 100 97 101 100 96 101 2.74
7 100 95 94 105 100 99 94 2.50 2.50
8 102 99 98 103 101 95 99
9 104 92 97 100 98 96 95
10 97 96 97 103 96 98 100 LSF Deviation
11 102 100 103 102 102 101 103
12 106 94 106 103 99 103 105
13 103 99 99 104 96 95 102
14 103 102 - 102 94 96 104 1.As you see on Table & Graph About 2.5 – 4.23 standard
15 - 101 - 101 95 99 103 Deviation of Kiln feed LSF observed.
16 - 102 - 101 94 94 103 2.The main causes for this Can be Either inefficient silo
17 - 98 - 97 100 99 99 performance or Input material to the silo itself having more
18 - 102 - 94 98 99 98 variation
19 - 99 - 94 101 98 100 3.This Basically should be identified by plant personnel by
20 - 104 - 99 95 94 100 performing various analysis & Calculations
21 - 101 - 98 99 98 -
22 - 100 - 95 96 96 -
23 - 104 - 97 100 98 -
Stdev 2.5 3.2 3.4 4.2 2.7 3.6 2.9
Phases Parameters
Kiln Feed ,Clinker analysis & ASH analysis
Kiln Feed Clinker Fue l ASH Analysis

LOI 36.50 SiO2 21.28 Ash 22.84
SiO2 13.34 Al2O3 4.21 VM 26.73
Al2O3 2.61 Fe2O3 3.60 LOI 0.62
Fe2O3 2.06 CaO 63.82 SiO2 50.22
Al2O3 27.28
CaO 42.20 MgO 4.48
Fe2O3 6.65
MgO 3.20 SO3 0.55
CaO 6.84
SO3 0.05 K2O 0.26 MgO 1.92
K2O 0.14 Na2O 0.06 Sulpher 0.81
Na2O 0.17 LSF 0.95
1.It is important to
Total 100.02 SM 2.78 mentioned that coal ASH
LSF 101.13 AM 1.18 also Considered as a Input
due to ASH Absorption
SM 2.87 F/CaO 1.93 2.Higher the coal ASH
AM 1.27 C3S 56.04 Content will lead into higher
kiln feed LSF for ASH
C2S 18.68 absorption which is mainly
due to silica content in coal
C3A 5.01 Ash
C4AF 10.71
Phases Parameters
Simple Calculations for applications
Clinke r Analys is
CaO (%) 67.8
SiO2 (%) 22.1
Al2O3 (%) 5.8
Fe2O3 (%) 3.9
MgO (%) 0.8
SO3 (%) 0.6
K2O (%) 0.9
Na2O (%) 0.1
P2O5 (%) 0.1
TiO2 (%) 0.2
LSF % ?
SM % ?
AM % ? Calculate these by using
C3S (%) ? formulas from training
presentation ?
C2S (%) ?
C3A (%) ?
C4AF (%) ?
L/P (%) ?
Phases Parameters
HG -Lime LG -Lime
Composition Sand Stone Iron Ore Raw Mix
Stone Stone
LOI 38.03 37.39 0.67 5.29 ?
SiO2 9.78 11 92.22 6.34 ?
Al2O3 2.41 2.59 0.8 4.04 ?
Fe2O3 1.23 1.39 5.97 83.2 ?
TiO2 0.14 0.14 0.04 0.22 ?
CaO 45.83 45.02 0.15 0.32 ? Calculate final Raw Mix
according to Proportion
MgO 1.78 1.7 0.05 0.18 ? as Indicated in RED ?
SO3 0.03 0.03 0.02 0.13 ?
K2O 0.82 0.8 0.02 0.14 ?
Na2O 0.25 0.24 0.01 0.25 ?
Cl 0.007 0.003 0.007 0.002 ?
P2O5 0.04 0.02 0.03 0.12 ?
Dry Mix % 4 92.87 1.91 1.21 100
Phases Parameters
HG -Lime LG -Lime Raw

Composition Sand Stone Iron Ore LOI Basis
Stone Stone Mix
LOI 38.03 37.39 0.67 5.29 36.3221 -
SiO2 9.78 11 92.22 6.34 12.44502 ?
Al2O3 2.41 2.59 0.8 4.04 2.565897 ?
Fe2O3 1.23 1.39 5.97 83.2 2.46084 ?
TiO2 0.14 0.14 0.04 0.22 0.139044 ?
CaO 45.83 45.02 0.15 0.32 43.65001 ? Calculate Final
Clinker Parameters
MgO 1.78 1.7 0.05 0.18 1.653123 ? on LOI Basic?
SO3 0.03 0.03 0.02 0.13 0.031016 ?
K2O 0.82 0.8 0.02 0.14 0.777836 ?
Na2O 0.25 0.24 0.01 0.25 0.236104 ?
Cl 0.007 0.003 0.007 0.002 0.003224 ?
P2O5 0.04 0.02 0.03 0.12 0.022199 ?
Dry Mix % 4 92.87 1.91 1.21 100 -
Thank You
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LEARNING MORE ABOUT

II. Composition of Clinker Phases

III. Characteristic Clinker Parameters

V. Examples of Raw Mix & Clinker

VI. Simple calculation practice

 The hardness of limestone (grindability) depends on the composition and geological

From High Grade Limestone to Clay

Description CaCO3 Content [Ma-%]

High Grade Limestone 96 – 100 %

Marlstone or Calcareous Marl 75 – 90 %

The other important raw mix component is Clay.

Main components in Clay:

Clays are divided in two main groups:

Corrective components are enriched in mainly of one chemical component, e.g.:

Component Limestone Clay Iron Ore Raw Mix

Typical percentages of these elements in

Left is shown the three-component phase

The area indicated as Portland Cement is

Preheating / Calcination / Sintering / Cooling

1. Evaporation of free water of kiln

2. Removal of adsorbed water in

3. Pyrolysis of clay material and

5. Formation of Belite (C2S),

Preheating / Calcination / Sintering / Cooling

6. Start of sintering with increasing

7. Formation of Alite (C3S) 1300°C

8. Cooling of clinker to solidify

9. Final clinker microstructure

10. Clinker cooled in cooler

Composition of Clinker Phases

Typical Clinker Granules

Composition of Clinker Phases

C3S = 4,071 CaO - 7,6 SiO2 - 6,718 Al2O3 - 1,43 Fe2O3

For AM<0,638 ( C3A-free Clinker)

C3S = 4,071 CaO - 7,6 SiO2 – 4,475 Al2O3 – 2,863 Fe2O3

Real Life: Formation of Mixed Crystals

Composition of Clinker Phases

CaO Free lime CaOfree <2

3 CaO·SiO2 Alite C3S ca. 40-80

2 CaO·SiO2 Belite C2S ca. 0-30

3 CaO·Al2O3 Calciumaluminate C3A ca. 7-15

4 CaO(Al2O3, Fe2O3) Calciumaluminateferrite C4AF ca. 4-15

Composition of Clinker Phases

Belite, C2S (2 CaO·SiO2)

Calciumaluminate, C3A (3 CaO·Al2O3)

Calciumaluminateferrite, C4AF (4 CaO.Al2O3. Fe2O3)

Composition of Clinker Phases

Clinker Early Final Setting Water demand

↗ = increase ↘ = decrease - = no effect

Characteristic Clinker Parameters

Characteristic Clinker Parameters

Characteristic Clinker Parameters

Silica Ratio high: - dusty kiln atmosphere

- poor coating conditions in the sintering zone

- non-uniform clinker size formation, very coarse clinker and formation of

- Tendency of “Snowman” formation on clinker cooler

Characteristic Clinker Parameters

Characteristic Clinker Parameters

Thick coating, clinker ball Very thin coating,

2 2.5 2.8 Silica Ratio, SR

Effects of minor oxides on process & Products

Oxides Effect on Process Effects On Products Limits