The clinker burning process and its influence on

the refractory material

Hugo Ordóñez
What is the goal of clinker burning ?
 The production of

GOOD QUALITY
cement...
OF COURSE !
What is cement quality?

Cement quality is defined in terms of characteristics & properties

such as:

•Chemical composition (Oxides content limits)

•Physical properties (Strength, Workability, Setting behavior etc)

in Standard Norms (DIN, ASTM, ISO) and is measured used

standard methods.
Factors influencing cement quality

Mechanical handling of clinker

(grinding)

Chemical & mineralogical

composition of raw mix

Chemical & mineralogical

composition of clinker
QUALITY
Burning process

Chemical composition of fuels

Circulation phenomena
Cement is produced by grinding clinker together with some
admixtures: gypsum, slag, pozzolan, limestone, among others.
And consists mostly from mineral phases

C3S

C2S

C3A

Free lime

C4AF

Gypsum
The most important mineral phases come from clinker
Some cement quality properties correlate with clinker mineralogical
parameters: strength=F(stereological data)

90 days compressive strength N/mm2

Wt,% (Alit+Belit)

DhAlit. Wt.% Alit + DhBelit. Wt.% Belit

100 100
Grindability of clinker in dependance of clinker mineralogical
parameters : (Ak= belit corrected specific alit content)
 Clinker Burning
Air

Raw meal Fuel

Flue Gas

Clinker
Chemical Composition of cement raw materials and mix

Limestone Marl Clay Sand Raw mix

Weight %
Ig. Loss 40-44 2-42 1-20 Up to 5 32-36
SiO2 0,5-3 3-50 37-78 80-99 12-16
Al2O3+TiO2 0,1-1 1-20 7-30 0,5-3 2-5
Fe2O3+Mn2O3 0,1-0,5 0,5-10 2-15 0,5-2 Up to 2
CaO 52-55 5-52 0,5-25 0,1-3 40-45
MgO 0,5-5 0,5-5 Up to 5 Up to 0,5 0,3-3
SO3 Up to 0,1 0,1-4 Up to 3 Up to 0,5 Up to 1,2
K2O Up to 0,3 Up to 3,5 0,5-5 Up to 1 0,2-1,4
Na2O Up to 0,1 Up to 0,2 0,1-0,3 Up to 0,5 Up to 0,3
Cl- 0,01-0,1
F- 0,02-0,07
Raw materials are mostly obtained from open Quarries
Calcite (CaCO3) Chrystals

Rhombo Cubic
Silica containing materials

quartz Silica sand

Clays
Kaolinit Raster Electron
Microscope picture.
Caolinit Picture width 20 micrometers
 Chemical and Mineralogical processes during clinker burning
Mass, relative

35%

100%
Raw meal

Clinker
65%
Clay minerals

Temperature°C
Summary of Reactions During Clinker Burning

• Below 200 °C: Drying: free water evaporation. No chemical-

mineralogical changes

• Above 200 °C and below 450 °C : Dehydration: loss of

chemically bonded water. chemical and mineralogical changes
beginn.
Summary of Reactions During Clinker Burning..continued

Between 400 °C and 700 °C: Decomposition of clay

minerals. Formation of metakaolinite

Al4(OH)8Si4O10Æ2(Al2O3.2SiO2)+4H2O

and highly reactive forms of silicic acid

 Summary of Reactions During Clinker Burning..continued

Between 600 °C and 900 °C:

Decomposition of metakaolinite and other compounds. Formation of

highly reactive oxide mixtures

Al2O3.2SiO2ÆAl2O3 + 2SiO2
Summary of Reactions During Clinker Burning..continued
Between 600°C and 1000 °C

Decomposition of limestone

CaCO3ÆCaO+CO2
Formation of calcium silicates and aluminates

3CaO+2SiO2+ Al2O3Æ2(CaO.SiO2) +CaO.Al2O3

Summary of Reactions During Clinker Burning..continued

Between 800-1300 °C
Uptake of lime by CS CA,

CS + C Æ C2S
2C+S Æ C2S
CA + 2C Æ C3A

Formation of C4AF

CA + 3C + F Æ C4AF
Summary of Reactions During Clinker Burning..continued

Between 1250-1450 °C: Further uptake of lime by belite and

formation of alite.
C2S + C ÅÆ C3S
 Thermo-Chemical profile of a long wet kiln

chains

Preheating zone CALCINING ZONE TRANS. SINTER COOLING

33 min ZONE 25 ZONE ZONE 5 MIN
75 MIN
MIN

TIMEÆ
Thermo-Chemical profile of a 4 stage preheater kiln

Length/diameter.......aprox. 14/1
DiameterXLength (2500 tpd) 4.8 X67 and 5x74 (mxm)
Speed of rotation.......aprox. 2 rpm
Secundary firing.....none
Calcination extent in pre-calciner....aprox 40 %
Thermo-Chemical profile of a pre-calciner kiln

Length/diameter.......aprox. 14/1
DiameterXLength (2500 tpd) 4.0 X56 and 4.4x64 (mxm)
Speed of rotation.......aprox. 3 rpm
Secundary firing.....up to 65% with tertiary air
Calcination extent in pre-heater....up to 95%
 CALCINATION
CaCO3ÅÆCaO+CO2
Decomposition rate of limestone is increased by

CaCO3ÅÆCaO+CO2

• Increase in temperature of raw meal

• Lowering CO2 partial pressure in combustion gases
• Lowering dust load of combustion gases
• Lowering particle size of raw meal
• Decreasing crystal content of CaCO3
• Silicic acid formed by decomposition of clay minerals
 Heating Rate and Dissotiation Speed of limestone
CaCO3ÅÆCaO+CO2
• Low HR (100 °K/min): DS depends on transport phenomena (gas-heat): heat
flow to and gas transport from the inner of the limestone particles.
• High particle size and HR (250 °K/min): DS hindered by low heat conductivity
and high CO2 partial pressure.
• High HR (450 °K/min): Increased reactivity of CaO with SiO2 (from 800 to
1000°C). No recrystalization and deffects in crystal lattice.
• Kiln speed: lower rpm produce higher HR.
• Alkalies (up to 2%) increase DS by lowering activation energy for limestone.
 Sintering (Reactions with liquid phase)
• Starts at 900-1000 °C (calcium silicates and
aluminates. No C3S formation)
• Free CaO starts decreasing at above 1250 °C (as melts
appear and C3S formation accelerates).
• Viscosity of melt affected by circulation phenomena
(low melting point compounds) and AR.
• Reversion from C3S to C2S can ocurr at isothermal
conditions. C3S Æ C2S + C
Sintering Temperature

• At 1250 °C: mostly C2S forms

• Below 1450 °C: C3S formation too slow.
• Reversion from C3S to C2S possible
• Above 1450 °C: quantity of melt increases,
viscosity decreases. Sintering reaction rate
increases.
• Above 1500 °C: cost/benefit too high.
 Heating rate •High HR at 1450°C: high
between 900-1300 °C reactivity, no
recrystalization
•High HR at 1700 °C good
strength due to high C3S
with small crystal size. Too
expensive.
Free lime
•Belite cement: possible
through very fast cooling,
1000 °K/min (crystal lattice
defects/disturbances) but
technically unfeasible...yet!
Reaction Equilibria
Belite + CaO ÅÆ Alite
Shift in reaction equilibria by changes in:
• Temperature (+R;-L)

• Quantity of melt ((+R; -L)

• Melt viscosity (+L; -R)

• Heating Rate between 1200-1450 °C (+R; -L)

• Clinker cooling rate 1450-1200 °C (+eq. “Freezes” -L)

• Time at isothermal conditions (above 1350°C) (+L; -R)

• Fe++ content in Alite (reducing atmosphere) (+L; -R)

Fluxes
Lower melting temperature Effects on quality
and melt viscosity • (-) Sett. time
•Heavy metals (Ba, Sr, Ce,
• (+)Strenght (Cr)
Cr, P,Ti, Zn) act as fluxes at • (+)Grindability
up to 3% Wt. (V2O5,Cr2O3, BaO)
at 0,5% wt.
•They must bind with
clinker to be active.
Mineralizers
•Accelerate C3S formation Effects on quality
without melt appearance. (+)Grindability (V2O5,Cr2O3,
•Ba, Cr, P, SO3 act as Min. BaO) at 0,5% wt.
At optimun conc. of 0,2-
1% Wt. Cr at up to 0,5% enhances
•Ce, Cr, Mn, Ti, Zn, Co, Pb C3S formation.
at up to 4% act as Min. At +0,5%, decomposes C3S
•F enables complete Increase late strength (F)
sintering at 1200-1300 °C (-) grindability (F)
(at 0,3-0,6% Wt.)
Kiln Atmosphere

Oxidating atmosphere is required by economic and quality reasons.

Clinker produced under Reducing conditions is brown
Cement produced with clinker burned under reducing atmosphere:
1. Sett faster
2. Show lower mechanical stength at late age. (C3S incorporates Fe++ in gitter
structure which makes it instable, lowering C3S content.
3. C3A content is higher as per calculations of Bogue.( Fe++ can not build C4AF).
4. Effects 2 and 3 are enhanced by slower cooling between 1450-1200°C!.
5. Excess O2 measured at kiln or preheater outlet is by no means “guaranty”
that oxidating conditions prevail in all parts of the system.
6. AF and Petcoke use tend to cause “local” reducing atmospheres.
Chemical Composition

LSF = 100CaO 1. Stoichiometric relationship.

2,8SiO2+1,18Al2O3+,65Fe2O3 2. Burnability of raw mix

Change in theorethical Sintering Temperature

in dependence with LSF

1510
1500
1490
°C 1480
T=50 °C
1470
1460
1450 Lsf=6
1440
88 90 92 94 96 98
lsf
Are 50 °C that important?

In reactions at ambient temperature, an increase of 10°K in

temperature duplicates the reaction rate

Absolute
Temperature
°K
 Influence of temperature on reaction time in accordance with
Ahrrenius „Law“

Reaction Time at different temperatures

700
600
500
Time sec. 400
300
200
100
0
-1001440 1450 1460 1470 1480 1490 1500 1510
T °C
 LSF Accumulated deviation from set point
(211 hours, random period )

8,00 T2
7,00
T3 T4
6,00

5,00
T1
4,00

3,00

2,00

1,00

0,00
7
1

73
79
85
91
97
13
19
25
31
37
43
49
55
61
67

175
181
187
193
199
205
211
103

127
133
139

163
169
109
115
121

145
151
157
-1,00

-2,00
Chemical Composition of raw meal..continued
SiO2 Solid
SR = =
Al2O3+Fe2O3 Liquid

High SR values decrease burnability due to

•Increased probability of having big SiO2 particles in raw meal
•Decreased amount of clinker melt
•A tendency for decreased homogeneity of raw meal (segregation)

Caution: increase in sinterization rates achieved by an

increase in the quantity of liquid phase result in harder
clinker as grindability of clinker varies inversely with
porosity. Therefore, for economic reasons complete sintering
with lowest posible temperature and quantity of melt shall be
looked after!
Silica Ratio

Solid/liquid Ratio
Chemical Composition of raw meal..continued
Al2O3 viscous
AR = =
Fe2O3 fluid

AR values are relevant for the viscosity of the clinker melt.

•Low viscosity increase sinter rate
•Alkalies and MgO can the viscosity of clinker melt lower.
•At AR=1,38 clinker melt achieves optimun properties to promote
sintering at lowest possible temperatures (1280-1340 °C).
Alumina Ratio
Typical particle size for selected materials

Raw Secund.
Meal Crusher
Ground
Micro
Coal Primary
Silica
Crusher
CEMENT
Quarry
Fineness of raw meal
Appropiate surface area for chemical
reaction shall be available Scanning electron microscope
photograph of a quartz grain
Kaolin; picture width 200 200 micrometer average
micrometer diameter
Big quartz grains sourronded by belite ring do not let sintering
to C3S to proceed due to lower reaction rate (low surface
area).

1620
Alite crystal
Too big quartz grains (20x) hinder alite formation
Raw mix has to be homogeneous before burning!

INHOMOGEN HOMOGEN
Particle size criteria

Tolerance for particles with average diameter + 100 micrometer

(raw meal):

Calcite, < 1%
Quartz < 6%
(by Weight)
Optimun calcite average size for C3S formation
15 microns
 Raw meal preparation

RM1 RM2 RM3 RM4 Homogeneization factor

should be between 7-10:
feed
SDEVin/SDEVout=10
Separator

Coarse return
Product Blending
Silo
Kiln feed
Mill

Storage
Silo

Kiln feed
 Dust from kiln dust collector:
Problems? •High alcali content
•Partially calcinated (requieres less energy)
•Concentration of fine particles

Fresh feed

Separator With Kiln feed

Coarse return
Product Blending
Silo

Mill

Chemical Storage
Composition: Silo
broad
fluctuations Kiln feed
 Variability criteria
Allowed variability of LSF, SR, AR in terms
of variation coefficient:

VC= Std. Dev./Average < 1%

(clinker; hourly data)

Another example: Raw meal and AFR Feed

RM

AFR
LSF Clinker (24 hours

S.C. DE CLINKER
102
Raw meal
100

98
AFR1
96

94

92
AFR3 AFR2
90
88
1% AFR 99% raw meal
86

84
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24
time
Silica Ratio: Clinker+AFR´s

2,70
AFR1

2,60

2,50 AFR2

2,40

Raw Meal AFR3

2,30

2,20 1% AFR, 99% raw meal

2,10
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24
Time
 Alumina Ratio: Clinker+AFR

1,45
AFR1

1,40

1% AFR, 99% Raw meal

1,35
Raw Meal AFR3
AFR2
1,30

1,25
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24

Time
ASR in raw meal

Normal value with brick Introduction of AFR with

wear rate of 9 mm/month. high Na content
Red spot in UTZ
Life expec. 18 months
 AFRS May Contain Fluxing and
Mineralizing Compounds in Dangerous
Concentrations !!!!
Thank you very
much for your
attention!