Clinker Manufacture Formation of Clinker

Overview
1. Introduction

2. Reaction Pathways Encountered During Clinker

Formation

Basic Sequence of Reactions

Mineralogical and Chemical Characteristics of Raw Mixes
Intermediate Products
Liquid Phase
The Overall Reaction Sequence

3. Reaction Mechanisms

4. Kinetics of Clinker Burning

Practical Considerations
Assessment of Raw Meal Burnability

5. Thermodynamics of Clinker Formation

2
28.11.2014/Mey

1. Introduction
Why study clinker burning?
"To understand the influence of changes in kiln
operation conditions"
Normal kiln operation

Influence of chemistry, fineness, mineralogy changes

Influence of new mix components (pozzolan, AFR, sand,
etc.)

Abnormal kiln operation

know causes of badly burnt clinker

understand why rings and deposits form
be able to suggest counter measures
3
28.11.2014/Mey

1. Introduction

Natural
Minerals

Temperature (T)
Pressure (p)

Synthetic Hydraulic
Minerals

Time (t)

Analogy to transformation of igneous and

sedimentary rocks
into metamorphic rocks
Difference in T, p, t
4
28.11.2014/Mey

1. Introduction
Two principal steps during transformation into clinker
Disintegration of original
structure
Mechanical crushing and

grinding
Thermal decomposition
Structural rearrangement on

Formation of new structures

Occurrence of intermediate

products
Genesis and growth of final

clinker minerals
Crystallisation of liquid phase

heating (e.g. polymorphism)

melt

5
28.11.2014/Mey

1. Introduction
Features characterising the clinker formation process
Complex system (series of diverse mechanisms)!
Requires mechanical, thermal and electrical energy
Reaction rate is slow (necessity of high temperatures,

finely dispersed material)

Clinker minerals are not stable at normal temperature!
Quality of product is determined by:

Clinker chemistry
Clinker microstructure

6
28.11.2014/Mey

1. Introduction
Control of burning process
Material technological aspects

Process technological aspects

Raw meal burning behaviour

Temperature profile

Burnability
Dust formation
Coating behaviour
Granulation of clinker
etc.
Quantity and properties of
liquid phase

Kiln atmosphere

Fuel type
Flame characteristics

etc.

7
28.11.2014/Mey

1. Introduction
Aspect

Characteristic feature

Reaction pathway

indicates the intermediate products

occurring between reactants and
products

Reaction mechanism

type(s) and reaction(s) taking place

Reaction kinetics

indicates rate at which the final

products are produced

Reaction thermodynamics

dictates whether reaction will be at

all possible, and what the heat and
temperature requirements will be
8
28.11.2014/Mey

Overview
1. Introduction

2. Reaction Pathways Encountered During Clinker

Formation

Basic Sequence of Reactions

Mineralogical and Chemical Characteristics of Raw Mixes
Intermediate Products
Liquid Phase
The Overall Reaction Sequence

3. Reaction Mechanisms
4. Kinetics of Clinker Burning

Practical Considerations
Assessment of Raw Meal Burnability

5. Thermodynamics of Clinker Formation

9
28.11.2014/Mey

2. Reaction Pathways
To fully describe the pathway of clinkering, it is
necessary to consider the following aspects:
the chemical and mineralogical content of the raw mix
the overall sequence of reactions
the chemical and mineralogical nature of the

intermediate products

10
28.11.2014/Mey

2. Reaction Pathways
Sequence of reactions occurring in a rotary kiln
Heating (C)
20 - 100
100 - 300
400 - 900
>500
600 - 900
>800
>1250
~1450

Evaporation of H2O
Loss of physically adsorbed water
Removal of structural H2O (H2O and OH groups)
from clay minerals
Structural changes in silicate minerals
Dissociation of carbonates
Formation of belite, intermediate products, aluminate and ferrite
Formation of liquid phase (aluminate and ferrite melt)
Completion of reaction and re-crystallization of alite and belite

Cooling (C)
1300 - 1240

Crystallization of liquid phase into mainly aluminate and ferrite

11
28.11.2014/Mey

2. Reaction Pathways
Typical chemical characteristics of raw mixes
Parameter

X mean

X min

X max

L.o.I.
SiO2
Al2O3
Fe2O3
CaO
SO3
Na2O

35.5
14.4
3.2
1.8
42.4
0.37
0.17

33.8
12.8
2.4
1.0
39.0
0.08
0.04

37.3
16.0
4.6
3.8
44.2
1.1
0.58

LS
SR
AR

94.0
2.9
1.9

85.4
1.8
0.7

103.4
3.9
3.2
13
28.11.2014/Mey

2. Reaction Pathways
Intermediate products encountered during clinker production
Type

Mineral Name

Formula

Simple Sulfates

Compound Carbonates
Simple Chlorides
Calcium Aluminates

anhydrite
arcanite
"sulfate"-spurrite
"calcium"-langbeinite
spurrite
sylvite
mayenite

Calcium Ferrites
Calcium Alumino-Silicates

gehlenite

CaSO4
K2SO4
2(C2S) Ca SO4
K2Ca2 (SO4)3
2(C2S) CaCO3
KCl
12 CaO 7 Al2O3
CaO Al2O3
2 CaO Fe2O3
2 CaO Al2O3 SiO2

Compound Sulfates

14
28.11.2014/Mey

2. Reaction Pathways
Reasons for the formation of intermediate products
Intermediate products are preferentially formed by

kinetically faster reaction rates

Intermediate products are the reaction products of

localised zones in the meal charge, i.e. local equilibrium

but not overall equilibrium was reached (e.g. gehlenite
formation)
Intermediate products are really the equilibrium products

at the given temperature and gas atmosphere, but not at

the final clinkering temperature (e.g. spurrite formation)

15
28.11.2014/Mey

2. Reaction Pathways
Liquid Phase

basically created by early melting compounds such

as Fe2O3 and Al2O3 and some minor compounds
such as MgO and Alkalis

The composition of the raw mix determines

temperature at which liquid will first be formed
amount of liquid formed at any given temperature
the physical properties of the liquid at any particular

temperature, especially its viscosity

16
28.11.2014/Mey

 Temperature of Liquid Formation

The following are the lowest melting temperatures of various

mixtures pertinent to Portland cement production:

Due to the inclusion of additional oxides (e.g. K2O, TiO2,

Mn2O3, etc.) the lowest formation temperature of the liquid

phase in clinker is in reality around 1250C.

17
28.11.2014/Mey

2. Reaction Pathways
Liquid Phase

Quantity of Liquid

Although most raw mixes show about the same

minimum temperature of liquid formation (eutectic

point), the quantity of liquid formed at this and
progressively higher temperatures varies according to
the raw mix chemistry.
In the Portland cement relevant parts of the system C -

S - A - F, in which melting begins at 1338 C, the

composition of the liquid is:
CaO
SiO2
Al2O3
Fe2O3

55 %
6%
23 %
16 %

Alumina ratio
(AR) = 1.38
18
28.11.2014/Mey

2. Reaction Pathways
Liquid Phase
Quantity calculation formulae acc. to LEA, considering different temperature:

1338 oC = 6.1 Fe2O3 + MgO + Na2O + K2O

8.2 Al2O3 5.22 Fe2O3 + MgO + Na2O + K2O

if AR 1.38
if AR 1.38

1400 oC = 2.95 Al2O3 + 2.2 Fe2O3 + MgO + Na2O + K2O

for MgO 2 %

1450 oC = 3.0 Al2O3 + 2.25 Fe2O3 + MgO + Na2O + K2O

for MgO 2 %

19
28.11.2014/Mey

2. Reaction Pathways
Quantitative change of
liquid phase with
temperature in several
group plants
(influence of
MgO, Na2O
and K2O
included)

SR
2.0

AR
1.7

2.7

1.1

3.0

1.9

20
28.11.2014/Mey

displays graphically the influence of Al2O3and Fe2O3 alone

on the quantity of liquid formed at 1338 C, the solid contours
representing the percentage of liquid formed.
It can be seen that the effect of adding Fe2O3or Al2O3on the
proportion of liquid formed at 1338 C is influenced strongly
by the alumina ratio.
in a clinker composition containing 4.5 % Al2O3 and 2 %
Fe2O3, for example, the Fe2O3 content is held constant and
the Al2O3 content is increased, the percentage of liquid
remains unchanged at 14 %, because the iso-Fe2O3 contour
lies parallel to the iso-liquid contour in this region.
21
28.11.2014/Mey

If, however, the iron content is increased and the

Al2O3content remains constant, the proportion of liquid
at first increases
rapidly until at 3.3 % Fe2O3 it attains a maximum of
21 %. With further increase in Fe2O3the quantity of
liquid decreases.
Therefore, the most effective use of Al2O3and Fe2O3with respect to liquid formation at 1338 C - occurs
when the two are used in the weight ratio of 1.38.
22
28.11.2014/Mey

2. Reaction Pathways
Influence of Al2O3 and
Fe2O3 alone on the
quantity of liquid
formed at 1338 C.
The most effective use
of Al2O3 and Fe2O3 with respect to liquid
formation at 1338 C occurs when the two
are used in the weight
ratio of 1.38
AR = Alumina ratio
OB, GM, UN, VN = Different Plants
At 1400 C and above increasing Al2O3 and / or
Fe2O3always result in a larger quantity of
liquid phase, Al2O3 being the one with the larger
influence.

23
28.11.2014/Mey

27
28.11.2014/Mey

2. Reaction Pathways

Variations in typical contents of phases

during the formation of Portland cement
clinker

28
28.11.2014/Mey

Overview
1. Introduction
2. Reaction Pathways Encountered During Clinker
Formation

Basic Sequence of Reactions

Mineralogical and Chemical Characteristics of Raw Mixes
Intermediate Products
Liquid Phase
The Overall Reaction Sequence

3. Reaction Mechanisms
4. Kinetics of Clinker Burning

Practical Considerations
Assessment of Raw Meal Burnability

5. Thermodynamics of Clinker Formation

29
28.11.2014/Mey

3. Reaction Mechanisms Definitions

Classification of reactions
2. according to the state of matter:

solid - solid

quartz and free CaO belite

solid - liquid

liquid phase crystallisation of

aluminate + ferrite

solid - gas

CaCO3 CaO + CO2

liquid - liquid

liquid - gas

drying process,
volatilisation of alkalis

gas - gas

CO + 1/2 O2 CO2
30
28.11.2014/Mey

3. Reaction Mechanisms Definitions

State of matter

solid

definitive volume and definite

shape

liquid

definitive volume, assumes shape

of container

gaseous

neither definitive volume nor

definite shape

31
28.11.2014/Mey

3. Reaction Mechanisms Definitions

Classification of reactions
1. according to their type:

structural change

high quartz low quartz

decomposition

CaCO3 CaO + CO2

combination

2CaO + SiO2 C2S

32
28.11.2014/Mey

3. Reaction Mechanisms Definitions

Classification of reactions
3. according to rate controlling step (kinetics of reaction)

diffusion

formation of alite

phase boundary

quartz + free CaO belite

(initial reaction)

nucleation

liquid phase crystallisation of

aluminate + ferrite;
alite formation

33
28.11.2014/Mey

3. Reaction Mechanisms Examples

Structural changes: Arrangement of the atoms in low
and high quartz

34
28.11.2014/Mey

3. Reaction Mechanisms Examples

Structural changes: Calcite Aragonite transition

35
28.11.2014/Mey

3. Reaction Mechanisms Examples

Decomposition reactions (during clinker production)
solid / gas type

De-hydroxylation of the clay minerals (kaolinite, etc.)

De-carbonation of the carbonate minerals (magnesite,
dolomite, calcite, spurrite)

solid / solid type

decomposition of alite

Characteristic of this reaction type is that the single

reactant is transformed into two products.
36
28.11.2014/Mey

3. Reaction Mechanisms Examples

Decomposition reaction: Decomposition of C3S at 1175 C
In the case of impure C3S,
i.e. clinker alite, the rate of
decomposition is
appreciably accelerated
by:
the presence of lime
and C2S nuclei

the presence of Fe2+ ,

H2O and K2SO4 / CaSO4
melts
38
28.11.2014/Mey

3. Reaction Mechanisms Examples

Combination reaction: Formation of Alite
Formation of alite only at T > 1250 C (lower stability
limit). At that temperature, the liquid phase is also starting
to form: The formation of alite is a liquid - solid reaction.

C2S + CaO

>1250 C

C3S

liquid phase

The formation of alite and its stabilisation depends on

the presence of the liquid phase.
The rate of reaction is dependent on:
the path distance that the diffusing species have to travel
quantity and viscosity of liquid phase
40
28.11.2014/Mey

Overview
1. Introduction
2. Reaction Pathways Encountered During Clinker
Formation

Basic Sequence of Reactions

Mineralogical and Chemical Characteristics of Raw Mixes
Intermediate Products
Liquid Phase
The Overall Reaction Sequence

3. Reaction Mechanisms
4. Kinetics of Clinker Burning

Practical Considerations
Assessment of Raw Meal Burnability

5. Thermodynamics of Clinker Formation

41
28.11.2014/Mey

4. Kinetics of Clinker Burning

kT

raw mix
(1 - )

kT Ae

clinker

Ea

RT
Arrhenius equation

kT = rate constant at temperature T

T = reaction temperature

A = frequency factor

R = gas constant

Ea = activation energy

Theoretical consequences:
Rate increases with higher temperature (but also costs!)
Rate decreases with higher activation energy
(different raw mix mineralogy)
Rate increases with higher frequency factor
(larger contact surface, i.e. finer mix)
42
28.11.2014/Mey

4. Kinetics of Clinker Burning

The rate of reaction
increases with temperature and contact surface

between raw mix components (frequency factor A)

decreases with higher activation energy Ea for raw mix

components.
To compensate for the slow reactivity of the less reactive
minerals, a higher burning temperature and / or longer
burning period (longer clinkering zone) is required.

43
28.11.2014/Mey

4. Kinetics of Clinker Burning

In practice, the most convenient method of following the

reaction is by measuring the rate of decrease of

non-combined lime (i.e. free lime).
This technique is illustrated in the following figures that

show two raw mixes, I and II,

of identical chemistry (LS = 95, SR = 3.2 and AR =
2.2) and similar fineness (R200m = 0.5 %, R90m = 7 %
and R60m = 15 %).
It is evident that the difference in mineralogy and

actual particle size of the individual crystals

influence both the mechanism and rate of reaction,
especially at start of the clinker formation.

46
28.11.2014/Mey

4. Kinetics of Clinker Burning

Raw Mix 1
Limestone
Calcite
Dolomite
Quartz
Chlorite
Illite and Micas
Pyrite
Feldspars

97 %
~2%
traces
traces
-

Shale A
Calcite
Dolomite
Quartz
Chlorite
Illite and Micas
Pyrite
Feldspars

~ 40 %
~ 25 %
~ 20 %
~ 10 %
~2%
~2%

Shale S
Calcite
Dolomite
Quartz
Chlorite
Illite and Micas
Pyrite
Feldspars

~ 10 %
~ 55 %
~ 10 %
~ 20 %
traces
traces

40 x

40 x

Raw Mix 2

40 x
47
28.11.2014/Mey

4. Kinetics of Clinker Burning

Assessment of Raw Meal Burnability
In practice, simple methods are mostly applied to asses

the burnability of a mix, i.e. the ease of formation of

the clinker minerals. Three distinct methods are
practiced at HGRS:

Holcim burnability test - involves the heating of a raw mix

under well defined laboratory conditions, and subsequent
laboratory determination of the non-combined lime.
Statistical burning model - in which ten material
parameters influence the rate of clinker formation. The
non-combined CaO value, of any raw mix, relative to that
of a standard raw mix is calculated.
Physicochemical burning model - requires no standard
raw mix. Only 4 parameters need to be considered.
50
28.11.2014/Mey

4. Kinetics of Clinker Burning

Holcim burnability test
The test is based on the isothermal burning at 1400 C

of raw meal nodules

The test allows the determination of the relative

influence of the various material parameters to be

ascertained, free from the influence of process
technological disturbances.
Evaluation
very good
good
moderate
poor
very poor

Free Lime %
0-2
2-4
4-6
6-8
>8
51
28.11.2014/Mey

4. Kinetics of Clinker Burning

Holcim burnability test

52
28.11.2014/Mey

4. Kinetics of Clinker Burning

Holcim burnability test

53
28.11.2014/Mey

4. Kinetics of Clinker Burning

Statistical Burnability Model
Quantitative evaluation of the data obtained by the

Holcim burnability test

The 1350, 1400 and 1450 free lime values of other raw
mixes from the same raw material components can be
determined based on one single burnability test of one mix
Chemical Parameters: lime saturation, silica ratio,
alumina ratio, K2O + Na2O, MgO
Physical Parameters:
residue on 200 m and 90 m
sieves, quantity of mica, quartz and iron minerals

The burnability model can be used as an

instrument for optimization of raw mixes
54
28.11.2014/Mey

4. Kinetics of Clinker Burning

Physiochemical Burnability Model
the amount of uncombined lime depends on

Specific reaction area (area of contact between grains)

Local oversaturation (grain size of individual minerals)
Ambient conditions (pressure, temperature, burning time)
Diffusion coefficient of CaO through the liquid phase
(composition of the liquid phase)
Amount of liquid phase formed during burning
Supply and demand of CaO

all these influencing factors may be incorporated in four

parameters: SR, LS, amount of oversized quartz

grains, amount of oversized calcite grains.
(Pressure, temperature and burning time are considered to be
constant.)
55
28.11.2014/Mey

4. Kinetics of Clinker Burning

Physiochemical Burnability Model
Silica ratio (SR) and lime saturation (LS)
The formation of C3S from C2S and CaO is governed by

the diffusion of CaO through the melt. The silica

modules and lime saturation are sufficient to describe
this chemical reaction quantitatively.
The amount of CaO which can be accommodated within

the liquid phase and in which it can diffuse and thus

react, is inversely proportional to the silica ratio. A linear
relationship exists between max. lime saturation and
silica ratio values at which no free lime can be
observed.
56
28.11.2014/Mey

4. Kinetics of Clinker Burning

Physiochemical Burnability Model
Quartz and calcite grains
Whether a grain of material reacts fully under given

burning conditions depends on its diameter, structure

and chemical composition.
Too large calcite grains result in CaO not being

completely combined as also results from grains whose

lime saturation is over 100 %.
For the "Holderbank" burnability test conditions the

following grain diameters were found to be critical limits:

quartz 32 m
calcite 90 m

57
28.11.2014/Mey

4. Kinetics of Clinker Burning

Physiochemical Burnability Model
Influence of chemistry
and coarse grains on
burnability of raw mixes

58
28.11.2014/Mey

Overview
1. Introduction
2. Reaction Pathways Encountered During Clinker
Formation

Basic Sequence of Reactions

Mineralogical and Chemical Characteristics of Raw Mixes
Intermediate Products
Liquid Phase
The Overall Reaction Sequence

3. Reaction Mechanisms
4. Kinetics of Clinker Burning

Practical Considerations
Assessment of Raw Meal Burnability

5. Thermodynamics of Clinker Formation

59
28.11.2014/Mey

5. Thermodynamics of Clinker Formation

During clinker production, heat is both absorbed

(endothermic heat changes) and produced

(exothermic heat changes).
Temp. (C)
20 - 100
100 - 300
400 - 900

Type of Reaction
Evaporation of free H2 O
Loss of physically adsorbed H2O
Removal of structural H2O (H2O, OH groups from
clay minerals)
600 - 900
Dissociation of CO2 from carbonate
> 800
Formation of intermediate products, belite,
aluminate and ferrite
> 1250
Formation of liquid phase (aluminate and ferrite melt)
Formation of alite
1300 - 1240
Crystallization of liquid phase into mainly
(cooling cycle) aluminate and ferrite

Heat Change
Endothermic
Endothermic
Endothermic
Endothermic
Exothermic
Endothermic
Exothermic
Exothermic
60
28.11.2014/Mey

5. Thermodynamics of Clinker Formation

Examples for exothermic reactions (heat liberated)

Coal (C) + O2
Lime (CaO) + H2O
Cement + H2O
Liquid K2SO4

CO2
Ca(OH)2
Cement Hydrates
Solid K2SO4

Examples for endothermic reactions (heat absorbed)

H2O (liquid)
CaCO3

H2O (steam)
CaO + CO2

61
28.11.2014/Mey

5. Thermodynamics of Clinker Formation

DTA curves of typical cement raw meals
The greatest heat
requirement occurs
between 850 - 900 C,
i.e. for the
decomposition of the
carbonate
minerals.The total heat
requirements for
dehydration,
decarbonisation and
melting exceed the
heat liberated by the
formation of belite and
the intermediate and
final products.
62
28.11.2014/Mey

5. Thermodynamics of Clinker Formation

Endothermic processes
dehydration of clays
decarbonisation of calcite
heat of melting
heating of raw materials 0 - 1450 C

kJ/kg clinker

170

1990

105

2050

Total endothermic

Exothermic processes
crystallization of dehydrated clay
heat of formation of clinker minerals
crystallization of melt
cooling of clinker
cooling of CO2 (ex calcite)
cooling of H2O (ex clays)

kJ/kg clinker

-40

-420

-105
-1400

-500

-85

Total exothermic

-2550

Net theoretical heat of clinker formation

+ 1765

4315

63
28.11.2014/Mey

5. Thermodynamics of Clinker Formation

Heat balance of wet and dry kiln, kJ/kg clinker
( HFW Taylor: Cement Chemistry, 1998 )

Dry kiln
Evaporation of H2O

Wet kiln

13 (0.4%)

2,364 (41.5%)

1,807 (54.6%)

1,741 (30.5%)

Heat losses through

gas, clinker, dust, etc.

711 (21.5%)

812 (12.3%)

Heat lost in air from cooler

427 (13.0%)

100 (1.7%)

Heat losses by radiation

and convection

348 (10.5%)

682 (12.0%)

3,306 kJ/kg

5,699 kJ/kg

Heat of reaction

64
28.11.2014/Mey