Objectives :

Significance of pyroprocessing.
Burnability of Rawmix
Effect of Raw mix in burning process.
Formation of clinker and Granulation
Effect of S, Cl, Na, K in burning process

Pyro processing
Heating of the raw
meal to the required
temperature so as to
produce the desired
clinker compounds in
an economic way at
higher productivity in
the preheater & kiln.

Production of Good quality clinker from the kiln

depends on :
Good raw mix design which in turn depends on
1. Desired clinker minerals
2. Allowable free lime
3. Nature of the raw material
Liquid ratio & Residence time in the kiln
Fuel quality & Combustion
Fineness of the raw meal to the desired level

Reactions involved in Pyro processing

Sl Reactions taking place
Required minimum
no
temperature, Deg C
Evaporation of free water from
1
100
the feed
Evolution of chemically bonded
2
550
water
Evolution of CO2 from CaCO3 and
3
805
MgCO3
4 Formation of C2S, C3A
1200
5

Formation of liquid phase

1250

Completion of reaction &

Equilibrium

1400

BURNABILITY OF RAWMIX

The readiness with which a rawmix is transformed into

clinker minerals in the course of high temperature
treatment

Determined by their chemical, mineralogical and

granular composition

Deciding factor for the temperature necessary for a

good clinker product

Different rawmix with the same chemical composition

and equal fineness may differ in their burnability due to
their different mineralogical composition

Poor burnability of rawmix may be caused by coarse

grains of Calcite (rich in CaCO3) or Quartz (rich in SiO2)

COARSE GRAINS
Clinker consists of alite, belite, liquid phase, free
lime and pores
The effect of coarse grains is studied with optical
microscope
Coarse quartz and calcite results in poor burnability,
high free lime and too little C3S in the clinker
Critical size of particle for residual free lime after 30
minutes
Quartz - 45 microns
Calcite - 125 microns
1% increase of
Quartz +45mic ----> 0.93% Free CaO
Calcite +125mic ----> 0.93% Free CaO

FREE LIME
Free CaO1400 =

0.33 (LSF 95)

(30minutes)

+ 1.8 (SM-2)
+ 0.93 SiO2 +45 micron
+ 0.56 CaCO3

+125 micron

Kuehls Burnability Index

BI = C3S / (C4AF+ C3A)
Example :
BI = 45 / (14.5 + 7.5 )
= 2.045

 For the desired free lime, the required fineness

can be found out to improve the burnability.
The burnability can also be improved by
reducing the LSF and Silica Modulus
A mineraliser like flouride or sulfate (gypsum)
can also be added to reduce the temperature at
which liquid phase is formed
mineraliser modifies the viscosity and surface
tension of the clinker liquid to promote the
formation of clinker minerals.

Chemical Composition
Parameter
LSF
AR
SR

Variation

Burnability

Parameter
C3S
C4AF + C3A

Variation

Burnability

Effect of Raw mix in burning

% Liquid
Flux & Mineraliser
Fineness
Chemical Composition
Mineralogy of Raw meal
Desired Clinker Quality

FLUX & MINERALISER

Flux : Reduce the temperature of liquid
formation.
Examples : Fe2O3, Al2O3
Mineraliser : Reduce the temperature for
the Alite formation
Examples :TiO2, P2O5

LIQUID CONTENT
Raw meal melts at more than 1200 deg C
depending on the amount of fluxing material
Liquid formation is important for
Effective Granulation
Stable coating
Protecting the refractory

% Liquid =

2.92 Al2O3
+ 2.25 Fe2O3
+ Mgo
+ Alkali

CLINKER FORMATION
Poor granulometry and Dusty Clinker leads to.
More wear rate in cooler and more maintenance
Formation of unstable, porous coating instead
of dense, stable coating
Poor grindability of clinker
Problematic clinker handling and dust nuisance
Unstable kiln operation

NODULISATION
Particles are held together by capillary forces of the
liquid
Nodulisation depends on the amount of liquid,
particle size and the speed of the kiln
In the kiln, the liquid is formed in a narrow temp
interval at aprox 1300 degC
Formed C3S crystals sinter together to form coarse
C3S particles and slow down the nodulisation process
Nodulisation is enhanced by liquid phase and
counteracted by large C3S particles.
At higher BZ temp, the formation of C3S particles is
faster and hence smaller will be the nodule size

CHANGES IN CHEMISTRY &

CLINKER NODULISATION
Reducing the Alumina / Iron ratio (to 1.6) will
improve the nodulisation as the formation of
liquid phase starts at lower temperature
Lowering of the silica modulus increases the
amount of liquid and thereby improves the
nodulisation
Reducing the LSF reduce the potential C 3S
and thus increase the nodulisation

Nodulisation
% Liquid

Amount of
C3S

Particle
size

Length of
burning
zone

Temperature

Residence
time

Common Morphological features of Clinker Phases

Characteristic Optical Properties of Clinker Phases

Sl
No
1

Clinker
Phases
Alite C3S
(3CaO.SiO2)

Belite C2S
(2CaO.SiO2)

Free lime
CaO

Colour

Shape

Microstructures

Straw yellow,
brown,
yellowish
brown,
brownish yellow
Blue, Bluish
yellow,
yellowish blue,
greenish yellow,
yellowish green

Hexagonal,
Pseudohexagonal, Lath,
Subhedral,
Anhedral etc.
Rounded, Subrounded,
Elliptical,
Subhedral,
Anhedral etc.

Fused grains,
Stretched, Twinned,
Granulated, Broken
out line grain

Multiple high
order
interference
colours of pink,
green, yellow,
blue etc.

Rounded,
Sub-rounded,
Subhedral,
Anhedrtal etc.

Clusters of various
size, Fused grains,
Twinned grains,
Corroded grain
margins, Striations
on belite grain
surface as
inclusions
Clusters, Striations
on the grain surface
as inclusions.

Major Clinker minerals

Bouges Formulae:
when A.R > 0.64

C3S = 4.071 C - 7.6 S - 6.718 A- 1.43 F - 2.852 SO3

C2S = 2.867 S - 0.754 C3S
C3A = 2.650 A - 1.692 F
C4AF = 3.04F

VOLATILE
MATTER

Volatile Matters present

SO3

Na2O

Cl

K2O

OH

Circulation of volatile matter

A fraction of the volatile components evaporates in
the kiln burning zone and condense in the back end or
rawmeal and re-enter the burning zone
The repeated evaporation and condensation results in
an Internal circulation where the concentration can
go up to fifty times the input concentration
At equilibrium state, the output of volatiles along with
clinker is equal to the total input from rawmeal and
fuel
Higher degree of volatiles concentration exists either
due to more input or due to a high degree of volatility

External circulation
Volatile matter in rawmeal like sulfur, is burnt to
SO2 gas in the preheater upper cyclones at around
400 - 600 degC and expelled out from preheater but
effectively precipitated in ESP

Condensation in Preheater
Volatile matter with low melting point condenses in
preheater walls and rawmeal particles causing build
ups on cyclone
SO2 gas combines with calcined rawmeal and
condenses as CaSO4

CaO + SO2 + 1/2 O2 --------> CaSO4

INTERNAL CIRCULATION
SO3 thro Clinker
(c)

S in Raw meal a3

S
PC firing
a1

Raiser Duct
&
4 Cyclone

SO3 (b)

Through Raw meal

Recycled SO3 (e)

Kiln

S
Kiln firing
a2

EXTERNAL CIRCULATION
SO3 thro stack

S in Raw meal

SO3
LOWER
STAGES

PREHEATER
FIRST STAGE

SO3
IN HOTGAS

Recycled Raw meal

ESP

ESP

Raw meal

External Circulation
Types of
Circulation

3
4

Internal Circulation
PC
Kiln Coal

kiln

Melting Pt & Boiling Pt of Volatile Matter

Compound

Na

Ca

MPt

BPt

MPt

BPt

MPt

BPt

Oxide

dec

350

sub

1275 2850

Carbonate

894

dec

850

dec

Sulphate

1074 1689

884

1190

Chloride

768

1411

801

1440

772

1600

Hydroxide

360

1320

328

1390

580

dec 825

MPt : Melting Point, BPt : Boiling Pt,dec : Decompose, Sub:Sublimate

Affinity between the Volatile

Components
Chloride reacts first with alkalis to form NaCl and
KCL
Excess chloride reacts with Calcium to form CaCl 2
Alkalis in excess of chloride combine with sulphur to
form Na2SO4 and K2SO4
Alkalis not combined with chloride or sulphur will be
present as Na2O or K2O
Sulfur in excess of alkali combines with CaO to form
CaSO4

VOLATILITY
Volatility is expressed in terms of evaporation factor
% within clinker
Evap. Factor E = 1 - ------------------------% at kiln inlet LOI free basis
Chloride compounds KCl, NaCl and CaCl2 are having
an E of 0.99 to 0.996. At 800 degC they are melted and
at 1200 - 1300 degC they are almost entirely evaporated
Sulphate compounds with alkalis K2SO4, Na2SO4 are
more stable ( E = 0.30 - 0.90), which is very desirable

Molecular Ratio of Sulfur and Alkali

Sulfur and alkali overall concentration and their
proportion is very important
Individually they are more damaging than their
sulphate compounds(K2SO4, Na2SO4) as K2SO4
has such a very high evaporation temp and they
come out along with clinker
Only half of Na2SO4 comes out as it begins to split
into Na2O and SO3 at around 900 degC
Sulfur in excess of alkali will form a more volatile
CaSO4, which has a high evaporation factor
An optimum molecular ratio is a must to avoid the
presence of the damaging individual components

Optimum (SO3 / Alkali) Ratio

SO3
Alk

SO3 / 80
K2O + 0.5 * Na2O
------------94
62

Operational Aspects of VC
Formation of build-ups in preheater riser
pipes and cyclones reduces the air volume
Reduced kiln production and increased
circulation of sulfur compounds due to
less availability of excess oxygen
Higher heat consumption
Dusty clinker formation

CONTROL LIMITS
Limits On Volatile Components In Bottom Cyclone
Stage in a SP kiln system on LOI free Basis

N or mal
Li mi ts
K

=
K

O+
1 . 5Na2 O

M ax
Li mi ts

3. 70%

6%

C hl or i ne as C l -

0. 80%

2. 00%

Sul f ur as SO3

2. 50%

5%

eq

CONTROL LIMITS
Max Allowable Input of Volatile Components for a
SP kiln system Without bypass on LOI free Basis
N or mal
L i mi ts
K

O+
0. 65*N a2 O

C hl or i ne as C l
Sul f ur as SO 3

M ax
Li mi ts

1 . 00%

1 . 5%

0. 02%

0. 02%

1 . 00%

1 . 6%

CONTROL LIMITS
Max Allowable Input of VC for a CALCINER Kiln
system Without bypass on LOI free Basis
N or mal
Li mi ts
K

M ax
Li mi ts

O+
0. 65*Na2 O

1 . 00%

1 . 5%

C hl or i ne as C l -

0. 01 5%

0. 01 5%

0. 80%

1 . 2%

Sul f ur as SO 3

Control
Methods

Reducing
Evop factor

Raw mix control

Flame adjustments
Excess air
Discard the filter dust
Kiln by pass
SO3 / Alkali ratio

Kiln Inlet Coating

PROBLEMS

CO formation in kiln inlet

reduced atmosphere
increased kiln inlet draught
reduction in kiln inlet Nox content
reduced kiln feed
blockage of meal chute and riser duct
premature refractory failure
dusty clinker formation and poor clinker quality
less intake of secondary air
kiln hood positive

Kiln Inlet Coating

Remedial Measures
increased oxygen content in kiln inlet ( to be
maintained around 2 %)
higher fineness of fine coal
smooth surface of kiln inlet lining
maintaining the alkali sulfur ratio near unity
using air blasters in kiln inlet and riser duct
using coating repellant refractory castable at kiln
inlet like silicon carbide castable
periodical cleaning of kiln inlet using compressed air
lance during plant running condition

Solving the Problem with Sulfur

Reducing the volatility- especially of CaSO4, by
lowering the BZ temp
By making the rawmeal easy to burn by means of
higher fineness / lower silica ratio
Maintaining optimum molecular ratio of sulphur to
alkali to avoid excess sulfur circulation
Reducing thermal load in the kiln
Increasing the availability of oxygen in kiln to shift
the equilibrium towards Alkali Sulphate
In the Case of reducing atmosphere, free carbon in
fuel reacts with alkali sulphates to liberate alkali
oxides which increases the VC circulation

Kiln burning zone

SO2 Formation :
Fuel S + 02 SO2
Alk SO4 <=> Alk-O + SO2 + O2
SO2 absorption :
Na2O + SO2 + O2 <=> Na2S04
K2O + SO2 + O2 <=> K2SO4
CaO + SO2 + O2 <=> CaSO4
During Reducing Atmosphere in Kiln
Ca SO + C => CaO + SO + CO

Calcining zone
SO2 Formation :
Fuel S + 02 S02
CaSO4+ C <=> CaO + SO2 + CO
SO2 absorption :
CaO + SO2 <=> CaSo3
CaCO3 + SO2 <=> CaS03 + CO2

PREHEATER
SO2 Formation :
Sulphides(FeS) + O2 Oxides +
SO2
Pyrite

Organic S + O2 SO2
SO2 absorption :
CaCO3 + SO2 <=> CaS03 + CO2

Solving the Problems with Chloride

As the evaporation factor of chloride is very high,
it is very difficult to reduce volatility.
Avoiding the chlorine rich raw material
Avoiding the peaks of chlorine content in rawmeal
by pre homogenization of raw material with
respect to chlorine
Discarding the ESP dust
Installation of alkali by pass system

Solving the Problems with Alkali

Maintaining the optimum the alkali sulfur ratio
Addition of sulfur in the system in the form of
gypsum