Chemical and thermal requirements for optimal refractory lining lifetime

Dr. Ing. Lothar Kilb

Refractory life time determining aspects
• Chemical aspects
Composition of raw material
Composition of fuel

• Thermal aspects
Thermal shock
Specific heat load

• Mechanical aspects
Ovality
Kiln alignment
 Critical areas in stationary and
rotating units of a modern cement kiln
Cyclone

Precalciner

Safety & Upper Lower Transition

Transition main Zone/Outlet/Nosering
Inlet chamber & burning zone Burner,
Riser duct Kiln hood,
Hot parts of cooler
Critical areas in stationary and rotating units of a modern cement kiln
thermal load
thermal shock
clinker infiltration
salt infiltration
redox
7 mechanical stress
3 ring formation

10
4
3
6 2
6 3
2 5
5 2
5 4
3 9 7
4 2
5 3

• Cyclone • Safety zone • Main burning zone • Lower transition zone • Cooler side walls
• Calciner • Upper transition zone • Kiln outlet • bull nose
• Inlet housing • Nose ring • Kiln hood
Chemical aspects

• feed and fuel

• the kiln atmosphere

 S03 / SO2
H2O
Cl
Cl O2

Na2O
Na2O

K2O S03 / SO2 K2O

Secondary phases entering the kiln firing unit by alternative fuels and or raw mixes
Tools
Tools – determining chemical conditions cement moduli

cement modulus typical values statement

Lime standards 85-95 (Portland cement) content of CaO, which can technically be
(KSt III) 95-100 (high-grade cem.) bond to SiO2, Al2O3 and Fe2O3

Hydraulic Modulus 1.7 – 2.3 ratio of CaO to the hydraulic factors SiO2,
(HM) Al2O3 and Fe2O3

Silica Ratio 1.9 – 3.2 characterizes the ratio solid/liquid, i.e.

(SR) (opt.: 2.2 – 2.6 !) the amount of liquid phases in the
clinker

Alumina Ratio 1.5 – 2.5 characterizes the composition of the melt

(AR) (possibly: < 1.5; >2.5) and ist viscosity

Alkali-Sulphate-Ratio 0.8 – 1.2 characterizes the ratio alkali versus

(ASR) sulphate
Silica modulus versus content of liquid phases at 1450°C
Al 2 O 3
AM = = 2 .2
Fe 2 O 3
Lime standard = 96
35
Liquid phase at 1450 °C in %

30
by weight

25

20

15
1,5 2 2,5 3 3,5 4
SiO 2
SM =
Al 2 O 3 + Fe 2 O 3
Coating – liquid phase
Coating

20 % 28 %
Liquid phase
Calculation of the Alkali-Sulphate-Ratio (ASR) in Cement Clinker

Na 2 O K O Cl
+ 2 −
Alkali /94Chlorides
62 71
ASR =
ASR =
Sulphates
SO 3
80

<1 1 >1

KCl / NaCl + KCl / NaCl + K2SO4 / KCl / NaCl +

K2SO4 / Na2SO4 + Na2SO4 K2SO4 / Na2SO4 +
SO3 free K2O free / Na2Ofree
ASR < 1
ASR > 1
ASR = 1
 ASR < 1

Corrosion, surplus of sulphur in kiln atmosphere

Corrosion reduces the refractoriness

and the structural flexibility

2C2S + MgO + SO3 CaSO4 + C3MS

C3MS2 + MgO + SO3 CaSO4 + 2CMS

CMS + MgO + SO3 CaSO4 + M2S

ASR < 1
ASR > 1
ASR = 1
Corrosion of basic Mg-Chrome bricks

ASR > 1

Na2, K2 (CrO4)

MgCr2O4 Na2, K2 (CrO4)

III VI
MgCr2O4 + Na, K Na2, K2 (CrO4)
Corrosion of chrome ore

Deposit of alkali-chromate

ASR > 1
Alkali attack on alumina bricks and concretes
Formation of new minerals
unaffected microstructure destruction of grains
i.e. feldspar, leucite, calsilite

Volume expansion of up
to 30% causes:

“alkali-bursting”

Al2O3 + K2O + SiO2 K2O Al2O32 SiO2 + ( 2,5 % Vol )

3Al2O32SiO2 + 3K2O + 4 SiO2 3K2OAl2O32SiO2 + ( 29 % Vol )
Calciner expanded due to alkali bursting alumina – alkali reaction
Reaction path / formation of salt compounds affinities

formula salts

I. Na,K + Cl2 NaCl, KCl

Na,K SO3 K2SO4 Na2SO4

II. + SO2 double salts

III. Na,K + CO K2CO3 Na2CO3

SO3 CaO CaSO4

IV. SO2
+
Build - up Problems
Sulphur Reactions in the Calcining Zone – Ring Formation
50 adhesion strength of alkali-
sulphate melt in kp/cm²

40

30

20

10

800 1000 1200 1400

Temperature °C

adhesion strength of clogging on refractory lining

ASR < 1
ASR > 1
ASR = 1
Physical Properties

• Bulk density ρ g/cm³

• Apparent porosity Φ %
• Cold chrushing strength s N/mm²
• Thermal expansion a lin. %
• Thermal conductivity l W/mK
• Elasticity E N/mm²
Infiltration of alkali/sulphate melts

ρ1 , %1 , N/m²1 , lin. % 1 , W/mK 1

ρ2 , %2 , N/m²2 , lin. % 2 , W/mK 2

ρ3 , %3 , N/m²3 , lin. % 3 , W/mK 3

Salt infiltration, mechanical load
The favourable ranges of cement clinker modules

AR 0 .4 1 .6 2 .0 2 .4 2 .8

SR 1 .4 2 .2 2 .4 2 .6 3 .8

HM 1 .4 1 .7 2 .0 2 .3 2 .6

ASR 0 .6 0 .8 1 .0 1 .2 1 .4

LSF 85 90 94 98 103

LP 19 22 25 28 31

A c c e p t a b le F a v o u r a b le R a n g e A c c e p t a b le
Range Range

A R = A lu m in a R a t io H M = H y d r a u lic M o d u l L S F = L im e S a t u r a tio n F a c t o r
S R = S ilic a R a t io A S R = A lk a li- S u lp h a te - R a t io L P = L iq u id P h a s e
Clinker analysis reports
Plant A Plant B Plant C

SiO 2 20.33 22.34 22.68

Fe 2 O 3 3.03 3.44 5.65
Al 2 O 3 5.05 5.01 4.33
CaO 65.14 67.20 63.07
MgO 4.07 0.83 1.34
K 2O 0.26 0.54 0.27
Na 2 O 0.38 0.24 0.31
SO 3 1.49 0.34 1.04
Cl 0.02 0.20 0.00

AR 1.64 1.45 0.72

SR 2.50 2.65 2.27
ASR 0.33 1.40 0.61
K 2 O+Na 2 O free 0,00 0,37 0,00
SO 3 free 1,00 0,00 0,41
LP 27,00 25,10 29,10
Caution: sulphate surplus alkali surplus sulphate surplus
spurrite clogging corrosion of Mg.Cr. aggressive LP
chem. therm. attack
PX CF, PX 83 PX CF, AG 85,
AG 85, AG AF, RG AF, TG AF, MG E , AG AF
AG A1 TG A1
ASR in rotary kiln

ASR ASR
clinker raw mix
Thermal aspects
Burning zone heat input net burning zone cross section

Max. thermal burning zone load:

5.8 x 106 kcal/m2h
24,28 GJ/m²h

max. specific burning zone load

1. SP preheater system:

Plant production: 1000 tpd 41tph

Heat consumptionn 800 kcal/kg clinker
Kiln diameter 3,8 m inside shell
Brick thickness 200 mm
Cross section: ( 3,4/2 )2 x π = 9,07 m2

Heat load:41000 kg x 800 kcal = 33 x 106 kcal h

Specific Heat load: 33 x 10 6 / 9,07 = 3,66 x 106 kcal / m2 h

2. SP preheater system:

Plant production: 3000 tpd 125 tph

Heat consumption 800 kcal/kg clinker
Kiln diameter 5,4 m inside shell
Brick thickness 250 mm
Cross section: ( 4,9/2 )2 x π = 18,85 m2

Heat load:125000 kg x 800 kcal = 100 x 106 kcal h

Specific Heat load: 100 x 10 6 / 18,85 = 5,3 x 106 kcal / m2 h

Limiting specific heat load for refractory material

KRONEX 85 high alumina 2 - 3 G cal./m2 h

PERILEX 83 magnesia-chromite 3 - 4 G cal./m2 h
ALMAG 85 magnesia-spinel 4 - 5 G cal./m2 h
ALMAG AF premium spinel > 5 G cal / m2 h
MAGNUM premium magnesia > 6 G cal./m2 h
Temperatures in kiln cross section of unstable coating area

2000 °C

∆ 600 °C

1450 °C
Heating up in 8 hours
up to 1000°C
Essential control steps for optimal kiln operation

1. Control your chemical parameters

2. Observe your specific heat load

3. Control your mechanical conditions