Mechanism of Clinker Coating Formation & Flame

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K.P.Pradeep kumar
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Clinker chemistry(related to Refractory) Burning mechanism
Mechanism of clinker coating formation and Flame

Clinker chemistry
Silica ratio = SiO2 / Al2O3+ Fe2O3 normally 1.9 - 3.2 (optimum: 2.2 - 2.6)
Silica ratio characterizes the ratio solid / liquid i.e., The amount of liquid phases in the clinker.
Alumina ratio = Al2O3 / Fe2O3 ,
normally
1.5 - 2.5
Alumina ratio characterizes the composition of the melt and its viscosity in the clinker. Low AR ( < 1.5 ) increases the Fe2O3 content, decreases the viscosity and increases the infiltration of liquid, deep into the brick
Silicic acid ratio, SAR = SiO2 / Al2O3, normally 2.5 -3.5
Optimization of rawmeal moduli for better refractory life .

c re as id ing ra 1.5 fo tio( rm S ati iO on 2/ 2 of Al2 2.5 coa O tin 3 3 g 4 5 8
SiO2
6 4
ica Si l O3 n) 2 ,M Fe ting + ( coa 1 3 l 2O tion /(A ma 2 for 1.5 SiO sing a io 2 rat Incre
3
Inc
Si lic
ic a
Al2O3
4 3 2.5 2 1.5 1 0.75 0.5 Increasing formation of coating Alumina ratio = Al2O3 / ( Fe,Mn)2O3
(Fe,Mn)2O3
Phase CaO-Al2O3-SiO2
C2S C3S
C3 A
CASF -Phase diagram
Fe2O3
CaO
SiO2
Al2O3
Liquid content According to Lea and Parker the % of liquid formed (S) S = 3 Al2O3 + 2.25 ( Fe2O3 + Mn2O3) + MgO + K2O + Na2O ( % by weight at 1450 deg) S = 30 % dense and firm coating S = 25 % good coating conditions S = 20 % loose and porous coating
If
Burnablity and coating index

Burnability index = C3S /( C3A + C4AF)
Minimum burning zone temp=13000C +4.51C3S+ 3.74C2S -12.64 C4AF Coating index , AW AR > 0.64, AW = C3A + C4AF + 0.2 C2S + 2F ( = normally 27 - 32 ) AR < 0.64, AW = C3A + C4AF + 0.2 C2S + 2F When AW < 20 , No coating or very less coating When AW > 30, Excessive but unstable coating with tendency to form thick ring formation.
Liquid percentage ( by Weight)

If AR > 1.38 , % L.P = 6.1 F+ M + K+ SO3 If AR < 1.38 , % L.P = 8.2 A - 5.22F+M+K+N+SO3 at 1338 deg C If AR< or = 0.64, L.P = 3.0A+2.25F+M+K+N+SO3 at 1450 deg C
Viscosity
Al2O3,K2O and Na2O increases the viscosity Fe2O3 and SO3 decreases the viscosity
Silica modulus vs liquid content

AM= Al2O3/ Fe2O3 LSF= 96, AM=2 35
Liquid content by weight in % at 1450 deg C
30
25
20
15 1.5 2 2.5 3. SM= S/ (A=F)

3.5
4.0
Mechanism of clinker reaction
Liquid
silicate
lime
1) At 1200 deg c the material consists of C2S, CaO, C3A and C2A all as small crystal grains 2) Viscosity and surface tension of liquid decreases with increasing temperature 3) C2S and CaO continue to undergo size enlargement with prolonged soaking in the absence of contact with the liquid.
P.t.o
4) Prolonged tumbling of material with droplets of clinker liquid with high surface tension will promote the than coalescence of these droplets among themselves rather reaching and wetting of silicate and lime grains with slow drop in the viscosity and surface tension the and tiny droplets get enough to meet one another away. 5) With rapid drop in the viscosity and surface tension of clinker most of the silicates and lime grains are drawn into the liquid even the liquid droplets get enough opportunities to meet one another and grow.
enlarge their own size leaving most of the silicates and lime
Clinker nodule
Model of clinker reactions

The clinker reactions proceed in the following ways up to 700deg C : dehydration of the clay minerals with the associated lattice formations and increase in surface reactivity 700 - 900 deg c: calcination of CaCO3 ,partial reaction of the release of CaO with Al2O3 and Fe2O3 to C2(A,F) and C12A17 and with the active part of the silica to belite (C2S) 900 - 1200 deg c: Transformation of the calcium ferrites into liquid state and commencement of the formation of the alite (C3S) from the belite and the uncombined CaO ( free lime) Above 1350 deg c : almost complete reaction of the free lime to alite , together with further decomposition of the belite content.
Phase transformation
1. Evaporation of free water from the feed 2.Evolution of the chemically combined water 550 deg c ( required 363 Kcal / kg cl ) 3. Evolution of CO2 from CaCO3 and MgCO3 4. Formation of interim phase C2F 5. Formation of interim phase CF 6. Formation of interim phase C2S+C2AS+CF +C2F 7. Formation of interim phase C2S+C5A3+ C5A+ CF + C2F 8. Formation of interim phase C2S+C3A+ C5A3+C2F+C3S 100 deg c 500 deg c
805 deg c 800 deg c 900 deg c 1000 deg c 1100 deg c 1200 deg c
9. Formation of C3A + C3S + C2S + C2F 1300 deg c ( required 511 Kcal / Kg cl )
Clinkering process
1450 OC
Deg C
1400
1200
CaCO3
CaO
Alite Belite
1000 800 600 400
Beta quartz Pre heating zone
Gamma quartz
C12A7
C3A C2(A, F) C4AF
Liquid
200
Burning zone cooling zone
Calcining zone Transition zone
Clinker moduli and their influence on the burning properties of clinker
Chemical and minerologica processes during clinker burning
Quasi-quantitative variation of minerals with temperature
Reactions in preheater
Stage-1 Evaporation of free water 0.3% H2O = - 3 kcal / kg .cl Stage-2 Evaporation of chemically combined water 0.7 % H2O = - 18 kcal / Kg cl Oxidation of sulfides ( pyrites) Stage-3 Oxidation of sulfides, partial Decarbonation of CaCO3 and combustion of coal in the rawmix( organic matter) Stage-4 Oxidation of sulfides, partial Decarbonation and recarbonation Stage-5 Decarbonation or CaCO3 ( 30 -40 %) Calciner Decarbonation(90 - 95 % ). Lime reacts with 1400 deg c reactive silica
310 deg c
490 deg c 640deg c
750 deg c 820 deg c
900 deg c
1100 deg c
Clinker burning
1)Radiation of heat from flame to refractory 2)Conduction of 1400 deg c heat from refractory to charge 1900 3)Convection of 1350 deg c 1450 ded c heat from particle to particle while rotating.Higher rpm 1500 deg increases the rate of convection
Heat
Higher rpm improves the thermal distribution,better heat exchange between refractory and raw meal bed and so reduces the radiation losses
Ideal flame
Clinker burning
1400 deg c
Heat
1450 ded c
1900
1350 deg c
1500 deg
Higher rpm improves the thermal distribution,better heat
Short,intense and convergent flame is favourable for burning, favorable coating formation improves the refractory life. Burner pipe at center - this flame radiates the heat to the the refractory surface(evenly) in well distributed manner
Short and divergent flame burning Clinker

Heat
1550 degcc
1600 deg c 1500 deg c 1900
1650 deg c
Higher rpm improves the thermal distribution,better heat
Short and divergent flame is favorable for burning, unfavourable for coating formation and deteriorates the refractory life. This flame radiates intense heat on the refractory surface and causes more thermal stresses on the brick. Some times it impinges the refractory.
Long and loose flame
Long flame is neither good for burning nor for favorable coating. It releases heat over a long distance and hence relieve some thermal stresses on the refractory.It forms unstable long coating and so if coating dislodges refractory has thermal shocks.
Coating formation on magnesite bricks in cement rotary kilns 1 6

Coating drops off(too high stresses, irregularities in operation. Moving of kiln, C2S disintegration)
Chemisorption and adsorption on the brick surface
5
Solidifying of the infiltrated material in the brick at further formation of coating
2 formation
Infiltration of liquid phases of the clinker and the reaction with the brick
falling off
coating
adhesion 3
Mechanical anchoring of the coating in the brick (max 1200 deg c
Stress formation (increase coating weight,differences in contraction
Pores on the bricks

Open pores
Closed pores
Coating formation on the brick
Penetration of the liquid into the pores of the brick Mixing of the liquid with the liquid of the brick Reaction or dissolution the solid phase by the new liquid
Clinker coating
Thick coating
500 mm
optimum coating
300 mm
Thin coating
100 mm
Coating formation
Dicalcium silicate (C2S) Anorthite(CAS2) Gehlenite(C2AS)
Alumina brick
Magchrome brick
Merwinite (C3MAS)
Dolomite brick
CaO - C3S
Spinel brick
Merwinite(C3MAS) Monticellite(MCS) Forsterite(MS2)
Micro structure of clinker coating on dolomite
Clinker coating on magchrome bricks
Clinker coating on dolomite brick
Contact zone between clinker and spinel brick
Typical burning conditions Good coating formation
in R-63 brick
Constriction of the free cross section due to coating ring formation
Heavy and unwanted coating
Firm and optimum coating for good refractory life
Thank you for your kind attention

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Welcome to refractory seminar

Clinker chemistry(related to Refractory) Burning mechanism

Mechanism of clinker coating formation and Flame

Alumina ratio = Al2O3 / Fe2O3 ,

Silicic acid ratio, SAR = SiO2 / Al2O3, normally 2.5 -3.5

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Optimization of rawmeal moduli for better refractory life .

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CASF -Phase diagram

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Burnablity and coating index

Liquid percentage ( by Weight)

Silica modulus vs liquid content

Liquid content by weight in % at 1450 deg C

15 1.5 2 2.5 3. SM= S/ (A=F)

Mechanism of clinker reaction

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Model of clinker reactions

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1000 800 600 400

Beta quartz Pre heating zone

C3A C2(A, F) C4AF

Calcining zone Transition zone

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Clinker moduli and their influence on the burning properties of clinker

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Chemical and minerologica processes during clinker burning

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Quasi-quantitative variation of minerals with temperature

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490 deg c 640deg c

750 deg c 820 deg c

Higher rpm improves the thermal distribution,better heat

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Short and divergent flame burning Clinker

1600 deg c 1500 deg c 1900

Higher rpm improves the thermal distribution,better heat

Long and loose flame

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Coating formation on magnesite bricks in cement rotary kilns 1 6

Chemisorption and adsorption on the brick surface

Mechanical anchoring of the coating in the brick (max 1200 deg c

Stress formation (increase coating weight,differences in contraction

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Pores on the bricks

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Coating formation on the brick

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Merwinite(C3MAS) Monticellite(MCS) Forsterite(MS2)

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Micro structure of clinker coating on dolomite

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Clinker coating on magchrome bricks

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Clinker coating on dolomite brick

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Contact zone between clinker and spinel brick

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Typical burning conditions Good coating formation

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Constriction of the free cross section due to coating ring formation