02-01-PODFA-Basic Know How of Clinker Production

Clinker Production
– Basic know how of clinker production

Training PODFA
New Kiln 7 Dry Line Project - JSC Podilsky Cement / Ukraine
November 2010
Polys ius
Clinker Production – chemistry basics - Content
What is cement?
Clinker minerals
Raw material
Clinker production
Phase diagram
Burnability index BI
Grinding fineness
Separation factor SF
Phase composition
Calculation with Bogue formula
Basic know how of clinker production

Training PODFA
November 2010
2 Polysius
What is cement ?
Answer (EN 197-1)
Cement is a hydraulic binder,

i.e. a finely ground inorganic matter
which mixed with water to cement paste
solidifies by hydration and hardens to cement stone
of a defined strength. The solidified cement
remains dimensionally stable and
maintains it strength also under water.

Training PODFA
November 2010
3 Polysius
Clinker minerals - Topics
Alite 3CaO  SiO 2 C3S
Belite 2CaO  SiO 2 C2S
Calciumaluminate 3CaO  Al2O 3 C3A
Brownmillerit 4CaO  Al2O 3  Fe 2O 3 C4AF
Dicalciumferrit 2CaO  Fe 2O 3 C2F
Free lime CaO CaOfr.

Training PODFA
November 2010
4 Polysius
Clinker minerals
Tricalciumsilicate, Alite
C3S C2S C 3A C4AF
Formation:
Above 1250°C by a reaction of C2S and C
Can be metastably by rapid cooling
Phases / Structure:
Melts at 2070°C
Decomposition at temperatures lower than 1250°C

Training PODFA
November 2010
5 Polysius
Clinker minerals
Tricalciumsilicate, Alite
C3S C2S C 3A C4AF
Properties:
Highly hydraulic, high initial strength, good afterhardening,
moderate setting heat, average tendency towards shrinkage
Smaller alite crystals are:

More reactive, easier to grind
Size depends on:

Amount and viscosity of melt
Fine quartz and calcite favour small crystals
Steep temperature profile, short retention time
Amount of foreign atoms
C3S can incorporate up to 3% SO3( but lower hydraulicity)

Training PODFA
November 2010
6 Polysius
Clinker minerals
Electron microscopy record of alite
C3S C2S C 3A C4AF

Training PODFA
November 2010
7 Polysius
Clinker minerals
Dicalciumsilicate, Belite
C3S C2S C 3A C4AF

Properties:
Slower hardening than alite, reduced setting heat.
Same strength as alite in the long term.
Takes up larger amounts of SO3 than alite
- modification stabilized by alkali

Normally only ß-modification found
Very difficult to quantify by X-ray diffraction
Hard to grind (harder than alite)
Spherical crystal shape

Training PODFA
November 2010
8 Polysius
Clinker minerals
Electron microscopy record of belite
C3S C2S C 3A C4AF

Training PODFA
November 2010
9 Polysius
Clinker minerals
Tricalciumaluminate
C3S C2S C 3A C4AF
Properties:
Responsible for early setting times ("rapid setting")
Fast hardening, high initial strength, high setting heat,
high tendancy towards shrinkage, susceptible to sulphate attack
Alkalies lead to a change in modification
cubic orthorhombic monoclinic changed reactivity
absolute amount of C3A rises with Na2O-content
Absolute content and reactivity important for gypsum optimization

Training PODFA
November 2010
10 Polysius
Clinker minerals
Brownmillerite
C3S C2S C 3A C4AF
Properties:
Low hydraulic properties, low setting heat,
Reduced tendency towards shrinkage
Can incorporate 3-4% MgO

Contains most of the alkalies
3-5 times higher conc. of K2O and 4-10 times more Na2O
than silicates alite and belite
Larger amounts of C4AF difficult to grind
Quick crystallization

Training PODFA
November 2010
11 Polysius
Clinker minerals
Alit 3CaO  SiO 2 C3S high medium low
Belit C2S 80 % 63 % 45 %
2CaO  SiO 2
Aluminat C3A 32 % 16 % 0%
3CaO  Al 2 O 3
Brownmillerit C4AF 14 % 8% 4%
4CaO  Al2 O 3  Fe 2 O 3
Dicalciumferrit 2CaO  Fe 2 O3 C 2F 15 % 11 % 7%
Free lime CaO CaOfr.
CaO SiO2 Al2O3 Fe2O3 MgO TiO2 Mn2O3 K2O Na2O

Training PODFA
November 2010
12 Polysius
Raw material
Enters raw mix as:

Massive limestone, marl, chalk, fossiliferous limestone
argillaceous limestone, blue lias, dolomite, feldspars, clay etc.
Burnability:
Large amounts of crystal defects in calcite favourable
Grain size influence less important than SiO2
Impurities of Si, Al, Fe lower decomposition temperature
Reactivity sequence:
easy: calcite > dolimite > ankerite > marble :difficult

Training PODFA
November 2010
13 Polysius
Raw material
Enters raw mix:

as quartz (coarse grained quartz)
as diatomite (fossile origin),Silex (very finly dispersed)
from clay minerals, feldspars, mica, slags (fine)
from fuel ash (fine)
Sequence of raw material reactivity:

quartz < chalcedony < opal < cristobalite
< silica from feldspars (albite, orthoclas)
< silica from mica / amphiboles
< silica from clay minerals < silica of glassy slags

Training PODFA
November 2010
14 Polysius
Raw material
Enters raw mix as:

Pyrite cinder Fe2O3 (industrial waste)
Hematite Fe2O3 (natural material)
Laterite Fe2O3 + FeOOH (natural material)
Hammer slag Fe3O4 ( industrial waste)
Clayous Fe2O3 carriers eg. ferric illite
Reactivity:
Important influence on burnability

Training PODFA
November 2010
15 Polysius
Raw material
Manganese oxide:
Leads to more dense clinker (lower viscosity)
Acts as mineralizer
Normally less than 2 %
Normally found in C4AF phase

Training PODFA
November 2010
16 Polysius
Raw material
Enters raw mix as:

Impurity in iron ores, from residual minerals like ilmenite, rutile
Effect:
Substitutes for Si, Al, Fe in clinker phases
Reduces surface tension of the liquid phase, drop in viscosity
Favourable for alite formation
Gives darker colour to clinker
Retards early hydration, slows down setting times
1% TiO2 can increase 3-90 day strength

Training PODFA
November 2010
17 Polysius
Raw material

Enters raw mix:
From nearly all main components used
especially dolomite (Ca, Mg)CO3, rarely magnesite
silcates like diopsite, chlorites etc.
Role in burning process:
MgO lowers viscosity of melt
Favours mineral formation
(increase for alite and C4AF, lowers C2S, C3A)
Effects:
Some authors: up to 3% MgO can increase cement strength ?
Creates defect lattices of alite and belite
Gives darker cement color
Approx. 2% can be incorporated in clinker phases
Training PODFA
November 2010
18 Polysius
Raw material

Enters raw mix:
From orthoclas, albite, plagioclas, micas, illite, montmorillonite
Effects:
Stabilisation of the -modification of belite
Preferably incorporated in belite and C3A (Na > K)
Negative effects in concrete (with active SiO2 )
Responsible for inner recycles
Increasing alkali volatization in the order
feldspars < micas < illit and montmorillonite
Increased volatility by
adding chloride (e.g. 0.5% CaCl2)
increase in H2O -partial pressure
Training PODFA
November 2010
19 Polysius
Clinker production
Preheater Transition-Zone Cooling-Zone

Precalciner
Calciner-Zone Sinter-Zone
M.-% T / °C
1400
1200
CaCO3
CaOfrei 1000
C3 S
800
C2 S 600
SiO2
400
Al2O3
C3A
C12A7 C2A,F Melt 200
Fe2O3 C4AF
5 10 15 20 25 30 t / min
Training PODFA
November 2010
20 Polysius
Clinker production
Temp. / °C Process Chemical reactions
20 … 200 Drying
Elimination of adsorbed
200 … 450
water
Decomposition of clay, Al (OH) Si O  2(Al O  2SiO )  4H O
4 8 4 10 2 3 2 2
450 … 600 formation of

metakaolinit
Decomposition of Al O  2SiO  Al O  2SiO
600 … 950 2 3 2 2 3 2
metakaolinit
Decomposition of CaCO  CaO  CO
3 2
800 … 1000 limestone, formation of 3CaO  2SiO  Al O  2(CaO  SiO )  CaO  Al O

2 2 3 2 2 3
CS and CA CaO  SiO 2  CaO  2CaO  SiO 2

CaO  Al2 O 3  2CaO  3CaO  Al2 O 3
Formation of clinker CaO  Al2 O 3  3CaO  Fe2 O3  4CaO  Al2O 3  Fe 2 O 3
1000 … 1300
minerals
2CaO  SiO 2  CaO  3CaO  SiO 2
1300 … 1450 Formation of C3S
Training PODFA
November 2010
21 Polysius
Phase diagram

0
100
20
80
n%
40
Oi
60
Ca
SiO 2
in %
60
40
PZ-Klinker
80
20
100
0 20 40 60 80 100
Al2O3 + Fe2O3 in %
Training PODFA
November 2010
22 Polysius
Phase diagram
Hydraulic Modulus

0
100
20
80
CaO
n%
HM  40
Oi
SiO 2  Al 2 O 3  Fe 2 O 3 60
Ca
SiO 2
in %
60
40
Limit value: 1.7 … 2.3
OPC-Clinker
Typical: ~ 2.0 80
20
100
0 20 40 60 80 100
Al2O3 + Fe2O3 in %
Training PODFA
November 2010
23 Polysius
Phase diagram
Lime standard I (Kühl)

0
100
20
80
100  CaO
in %
LS I  40
2,8  SiO 2  1,1  Al 2 O 3  0,7  Fe 2 O 3
O
60
Ca
SiO 2
in %
60
40
Limit value: 90 … 100
OPC-Clinker
Typical: 92 … 98 80
20
100
0 20 40 60 80 100
Al2O3 + Fe2O3 in %
Training PODFA
November 2010
24 Polysius
Phase diagram
Lime standard II (Lea, Parker)

0
100
20
80
100  CaO
in %
LS II  40
2,8  SiO 2  1,18  Al 2 O 3  0,65  Fe 2 O 3
O
60
Ca
SiO 2
in %
60
40
Typical: 92 … 98 OPC-Clinker
80
20
100
0 20 40 60 80 100
Al2O3 + Fe2O3 in %
Training PODFA
November 2010
25 Polysius
Phase diagram
Lime standard III (Spohn, Woermann, Knöfel)

0
100
20
80
100  CaO  0,75  MgO
in %
LS III  40
2,8  SiO 2  1,18  Al 2 O 3  0,65  Fe 2 O 3
O
60
Ca
SiO 2
in %
60
40
Typical: 92 … 98 OPC-Clinker
80
20
100
0 20 40 60 80 100
Al2O3 + Fe2O3 in %
Training PODFA
November 2010
26 Polysius
Phase diagram
Lime saturation factor

0
100
20
80
100  CaO
in %
LSF  40
2,8  SiO 2  1,65  Al2 O 3  0,35  Fe 2 O 3
O
60
Ca
SiO 2
in %
60
40
OPC-Clinker
80
20
100
0 20 40 60 80 100
Al2O3 + Fe2O3 in %
Training PODFA
November 2010
27 Polysius
Phase diagram
Silica ratio

0
100
20
80
SiO 2
n%
SR  40
Oi
Al 2 O 3  Fe 2 O 3 60
Ca
SiO 2
in %
60
40
OPC-Clinker
Typical: 2.2 … 2.6 80
20
100
0 20 40 60 80 100
Al2O3 + Fe2O3 in %
Training PODFA
November 2010
28 Polysius
Phase diagram
Silicic acid ratio

0
100
20
80
in %
SiO 2
SAR  40
O
Al2 O 3 60
Ca
SiO 2
in %
60
40
OPC-Clinker
Typical: 2.5 … 3.5 80
20
100
0 20 40 60 80 100
Al2O3 + Fe2O3 in %
Training PODFA
November 2010
29 Polysius
Phase diagram
Alumina ratio

0
100
20
80
in %
Al 2 O 3
AR  40
O
Fe 2 O 3 60
Ca
SiO 2
in %
60
40
OPC-Clinker
Typical: 1.6 … 2.0 80
20
100
0 20 40 60 80 100
Al2O3 + Fe2O3 in %
Training PODFA
November 2010
30 Polysius
Phase diagram
Sodium equivalent
Na 2 O (equ.)  Na 2 O  0,658  K 2 O

Training PODFA
November 2010
31 Polysius
Phase diagram
Liquid phase
LEA1400 C  2,95  Al2 O 3  2,2  Fe 2 O 3  MgO  Na 2 O  K 2 O
typical: 24 … 28

Training PODFA
November 2010
32 Polysius
Burnability Index BI
F1  CaO1350C  F2  CaO1400C  F3  CaO1450 C  F4  CaO1500 C

BI   F8
F5  x F6  CaO1350C  F7  CaO1500 C
very easy: < 60

easy: 60 – 80
normal: 80 – 100
slightly difficult: 100 – 120
difficult: 120 – 140
very difficult: 140 – 160
extremly difficult: >160
Training PODFA
November 2010
33 Polysius
Grinding fineness
180
extremly difficult
R 90µm ~ 12 - 18% KST 100
160
R 200µm ~ 1 - 3% very difficult
Burnability Index BI
140
difficult
KST 95
120
slightly difficult
KST 92
100
normal
KST 90
80
easy
60
very easy
40
4 6 8 10 12 14 16 18
Fineness %R90µm

Training PODFA
November 2010
34 Polysius
Separation Faktor SF
KST I ( 32µm)
SFLSF 
KST I (RM)
Difficulter burnability: > 1,2

Typical: 0,8 … 1,2
Easier burnability: < 0,8%

Training PODFA
November 2010
35 Polysius
Phase composition
Mixture No. 1
Raw mix compounds: content [%]
Limestone hard 77.15 heat consumption:
Kolub Marl 9.65 740 kcal/kg
Clay Mix 11.87
( Yellow : Diverse = 1 : 2 )
Iron Ore 1.33
Fuel: content [%]
Coal 7.29
Mixture No. 2
Raw mix compounds: content [%]
Limestone soft 75.80 heat consumption:
Kolub Marl 9.65 740 kcal/kg
Clay Mix 12.84
( Yellow : Diverse = 1 : 2 )
Iron Ore 1.71
Fuel: content [%]
Coal 7.32
Training PODFA
November 2010
36 Polysius
Phase composition
based on LOI free of free of free of
LOI LOI + ash LOI + ash
(based on 100%)
% LOI 36.30 --- --- ---
% SiO2 13.57 21.15 22.25 21.75
% Al2O3 2.78 4.33 4.76 4.66
% TiO2 0.14 0.22 0.24 0.23
% Fe2O3 2.18 3.40 3.59 3.51
% Mn2O3 0.20 0.31 0.31 0.30
% CaO 42.93 66.89 67.02 65.51
% MgO 1.02 1.59 1.64 1.60
% SO3 (total sulfur) 0.57 0.88 1.16 1.14
% P 2 O5 0.08 0.12 0.12 0.12
% Na2O 0.14 0.22 0.23 0.23
% K2O 0.57 0.88 0.96 0.94
% Cl 0.003 0.005 0.010 0.009
Total 100.47 100.00 102.30 100.00

Training PODFA
November 2010
37 Polysius
Phase composition
(based on 100%)
% LOI 36.30 --- --- ---
% SiO2 13.57 21.15 22.25 21.75
% Al2O3 2.78 4.33 4.76 4.66
% TiO2 0.14 0.22 0.24 0.23
% Fe2O3 2.18 3.40 3.59 3.51
% Mn2O3 0.20 0.31 0.31 0.30
% CaO 42.93 66.89 67.02 65.51
% MgO 1.02 1.59 1.64 1.60
% SO3 (total sulfur) 0.57 0.88 1.16 1.14
% P 2 O5 0.08 0.12 0.12 0.12
% Na2O 0.14 0.22 0.23 0.23
% K2O 0.57 0.88 0.96 0.94
% Cl 0.003 0.005 0.010 0.009
Silica ratio 2.56 2.50
Alumina ratio 1.23 1.28
Lime standard (KUEHL) 100.1 95.0
Training PODFA
November 2010
38 Polysius
Phase composition
(based on 100%)
% LOI 36.30 --- --- ---
% SiO2 13.57 21.15 22.25 21.75
% Al2O3 2.78 4.33 4.76 4.66
% TiO2 0.14 0.22 0.24 0.23
% Fe2O3 2.18 3.40 3.59 3.51
% Mn2O3 0.20 0.31 0.31 0.30
% CaO 42.93 66.89 67.02 65.51
% MgO 1.02 1.59 1.64 1.60
% SO3 (total sulfur) 0.57 0.88 1.16 1.14
% P 2 O5 0.08 0.12 0.12 0.12
% Na2O 0.14 0.22 0.23 0.23
% K2O 0.57 0.88 0.96 0.94
% Cl 0.003 0.005 0.010 0.009
% Liquid phase 25.6
(acc. to LEA 1400 °C)

Training PODFA
November 2010
39 Polysius
Phase composition
(based on 100%)
% LOI 36.30 --- --- ---
% SiO2 13.57 21.15 22.25 21.75
% Al2O3 2.78 4.33 4.76 4.66
% TiO2 0.14 0.22 0.24 0.23
% Fe2O3 2.18 3.40 3.59 3.51
% Mn2O3 0.20 0.31 0.31 0.30
% CaO 42.93 66.89 67.02 65.51
% MgO 1.02 1.59 1.64 1.60
% SO3 (total sulfur) 0.57 0.88 1.16 1.14
% P 2 O5 0.08 0.12 0.12 0.12
% Na2O 0.14 0.22 0.23 0.23
% K2O 0.57 0.88 0.96 0.94
% Cl 0.003 0.005 0.010 0.009
% C3 S ?
% C2 S ?
% C3 A ?
% C4AF
Training PODFA
November 2010
?
40 Polysius
C3S
C2S
LS  CaO -  2,8  SiO 2  1,65  Al2 O3  0,35  Fe 2 O3 
CaOfr.
C3A
C4AF Al2 O 3*
AR 
Fe 2 O 3*
C2F
AR > 0,638; LS = negativ  Calculation Group 1 A

AR < 0,638; LS = negativ  Calculation Group 1 B
AR > 0,638; LS = positiv  Calculation Group 2 A
AR < 0,638; LS = positiv  Calculation Group 2 B
* - molecular weights
Training PODFA
November 2010
45 Polysius
AR > 0,638; LS = negativ  Calculation Group 1 A
C3S  4.071  CaO  0.46   3.043  Fe2 O3   0.62   2.65  Al2 O3 - 1.692  Fe2 O3   1.87  SiO 2 
 4.071 CaO - 7.6  SiO 2  6.718  Al2O3  1.430  Fe 2O3
C2S  8.6   SiO
2.87 SiO 2 2 5.068
 0.26 Al O3  1.079  Fe2O3  3.071 CaO
 C23S
C3A  2.65  Al2 O3 - 1.692  Fe 2 O3
C4AF  3.043 Fe 2 O 3
C 4 AF C3A 3  CaO C3S C 2S

 3.043  1.692
Fe 2 O 3 Fe 2 O 3  0.62  4.071  2.87
C3A CaO SiO 2
C3 A
 2.65
Al 2 O 3 4  CaO 2  CaO SiO 2
 0.46  1.87  0.26
C 4 AF SiO 2 C3S
Training PODFA
November 2010
46 Polysius
AR < 0,638; LS = negativ  Calculation Group 1 B
C3S  4.071 CaO - 7.6  SiO 2  4.479  Al2 O3  2.860  Fe 2O3
C2S  8.6  SiO 2  3.379  Al2 O 3  2.157  Fe2O 3  3.071 CaO
C2F  1.702  Fe 2O 3 - 2.666  Al 2O 3
C4AF  4.766  Al 2 O 3

Training PODFA
November 2010
47 Polysius
AR > 0,638; LS = positiv  Calculation Group 2 A
C3S  3.8  SiO 2
CaOfr.  CaO - 2.8  SiO 2  1.65  Al2 O3  0.351 Fe2O3
C3A  2.65  Al2O 3 - 1.692  Fe 2 O3
C4AF  3.043  Al 2 O 3

Training PODFA
November 2010
48 Polysius
AR < 0,638; LS = positiv  Calculation Group 2 B
C3S  3.8 SiO 2
CaOfr.  CaO  2.8  SiO 2  1.1 Al2O3  0.702  Fe2 O3
C2F  1.702  Fe 2O3 - 2.666  Al2O3
C4AF  4.766  Al 2 O 3

Training PODFA
November 2010
49 Polysius
Phase composition
(based on 100%)
% LOI 36.30 --- --- ---
% SiO2 13.57 21.15 22.25 21.75
% Al2O3 2.78 4.33 4.76 4.66
% TiO2 0.14 0.22 0.24 0.23
% Fe2O3 2.18 3.40 3.59 3.51
% Mn2O3 0.20 0.31 0.31 0.30
% CaO 42.93 66.89 67.02 65.51
% MgO 1.02 1.59 1.64 1.60
% SO3 (total sulfur) 0.57 0.88 1.16 1.14
% P2O5 0.08 0.12 0.12 0.12
% Na2O 0.14 0.22 0.23 0.23
% K2O 0.57 0.88 0.96 0.94
% Cl 0.003 0.005 0.010 0.009
% C3S 63.0
% C2S 14.9
% C3A 6.5
% C4AF
11.6
Training PODFA
November 2010
50 Polysius
Training PODFA
November 2010
52 Polysius

02-01-PODFA-Basic Know How of Clinker Production

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Clinker Production

– Basic know how of clinker production

Basic know how of clinker production

Cement is a hydraulic binder,

Basic know how of clinker production

Alite 3CaO  SiO 2 C3S

Belite 2CaO  SiO 2 C2S

Calciumaluminate 3CaO  Al2O 3 C3A

Brownmillerit 4CaO  Al2O 3  Fe 2O 3 C4AF

Dicalciumferrit 2CaO  Fe 2O 3 C2F

Free lime CaO CaOfr.

Basic know how of clinker production

C3S C2S C 3A C4AF

Basic know how of clinker production

C3S C2S C 3A C4AF

Smaller alite crystals are:

Size depends on:

C3S can incorporate up to 3% SO3( but lower hydraulicity)

C3S C2S C 3A C4AF

Basic know how of clinker production

C3S C2S C 3A C4AF

- modification stabilized by alkali

Basic know how of clinker production

C3S C2S C 3A C4AF

Basic know how of clinker production

C3S C2S C 3A C4AF

Alkalies lead to a change in modification

cubic orthorhombic monoclinic changed reactivity

absolute amount of C3A rises with Na2O-content

Absolute content and reactivity important for gypsum optimization

Basic know how of clinker production

C3S C2S C 3A C4AF

Can incorporate 3-4% MgO

Basic know how of clinker production

Alit 3CaO  SiO 2 C3S high medium low

Free lime CaO CaOfr.

CaO SiO2 Al2O3 Fe2O3 MgO TiO2 Mn2O3 K2O Na2O

Basic know how of clinker production

CaO SiO2 Al2O3 Fe2O3 MgO TiO2 Mn2O3 K2O Na2O

Enters raw mix as:

Basic know how of clinker production

CaO SiO2 Al2O3 Fe2O3 MgO TiO2 Mn2O3 K2O Na2O

Enters raw mix:

Sequence of raw material reactivity:

Basic know how of clinker production

CaO SiO2 Al2O3 Fe2O3 MgO TiO2 Mn2O3 K2O Na2O

Enters raw mix as:

Basic know how of clinker production

CaO SiO2 Al2O3 Fe2O3 MgO TiO2 Mn2O3 K2O Na2O

Basic know how of clinker production

CaO SiO2 Al2O3 Fe2O3 MgO TiO2 Mn2O3 K2O Na2O

Enters raw mix as:

Basic know how of clinker production

CaO SiO2 Al2O3 Fe2O3 MgO TiO2 Mn2O3 K2O Na2O

CaO SiO2 Al2O3 Fe2O3 MgO TiO2 Mn2O3 K2O Na2O

Preheater Transition-Zone Cooling-Zone

Temp. / °C Process Chemical reactions

450 … 600 formation of

800 … 1000 limestone, formation of 3CaO  2SiO  Al O  2(CaO  SiO )  CaO  Al O