Alkali Corrosion of Refractories in Cement Kilns

Alkali Corrosion of Refractories in Cement Kilns
1
Alkali Corrosion
Topics
1. Introduction to alkali corrosion of refractories
2. Characterization of corroded industrial refractory materials
3. Behavior of alkali salts and alkali salt mixtures
4. Mechanisms of alkali corrosion
5. Investigation methods
6. Conclusions
2
Alkali Corrosion
raw material preparation clinker burning clinker storage cement mill
Corrosion attack
in cement rotary kilns
clinker burning
high temperature thermal

insulation material
heat exchanger electrostatic filter
combustion of fuels
rotary kiln
grate cooler
refractory lining
high temperature thermal insulation material
Deuna Zement GmbH, Informationsmaterial 2005 metallic components
Introduction to Alkali Corrosion of Refractories
3
Alkali Corrosion
Reason of alkali accumulation in the cement rotary kilns
• cement dust returns into the burning process

• implementation of raw meal preheating first with the Lepol grate
• improved preheating of cement raw meal in Humboldt air-suspension preheater and
intensified due to alkali circulation
• use of secondary fuels, i.e. use of combustible waste instead of
powdered coal ore oil
Sources of corrosive substances
• alkali: included in natural raw materials, coal, secondary fuels

• chlorine: included in secondary fuels
• sulfur: included in natural raw materials, coal, oil, secundary fuels
E. Schlegel, C.G. Aneziris, U. Fischer: Alkali Corrosion Resistance High-Temperature Insulation Materials

4
Alkali Corrosion
The use of secondary fuels
P. Scur, Mitverbrennung von Sekundärbrennstoffen wie heizwertreiche Abfälle und Tiermehl in der Zementindustrie am
Beispiel Zementwerk Rüdersdorf. VDI-Berichte Nr. 1708, 2002, S. 189 - 20

5
Alkali Corrosion
Combustion of secundary fuels

• The chlorine is particularly inserting in burning process:
 chlorine containing compounds, not pure gas
• The chlorine is mainly included in:  polyvinylchlorid (PVC)
 used tires
 common salts of domestic waste
• The chlorine appearance tends to result:  changing of the reaction process
 intensification of the refractory corrosion
• Reasons for this behavior:  formation of low viscous and aggressive fused salts
at relatively low temperatures
 high amount of the corrosive compound is gaseous
 gases an melts can simply pass trought pores and
cracks of working refractory material to the metallic bars
 attack by chemical reaction and dissolution the
fire-proof material behind
 condensate on the metallic components leads to
excessive corrosion phenomena

6
Alkali Corrosion
Effect of the combustion of secundary fuels in cement rotary kilns
Secondary fuels Organic Compounds

solid alkalis
(plastic, rubber, battery, animal
residues; tyres, domestic waste...) sulfates
liquid chlorides
..
(used oil, tar, chemical wastes...) .
gaseous and other corrosive
(landfill, pyrolysis gas)
compounds
Alkalibursting and
chemical spalling of the
refractories
Gas corrosion
(condensation) of the
fireclay insulating brick after 3 years in use in a
metal components
cement rotary kiln (feed end)

7
Alkali Corrosion
Post mortem investigations
• Roof of kiln hood of the DOPOL-kiln:
Cool side (metal jacket)
Calcium silicate
basic abrasion Insulating brick

lining
Hot side (refractory bricks or concrets)
Characterization of corroded industrial refractory materials

8
Alkali Corrosion
Post mortem investigation
• Alkali corroded calcium silicate thermal Hot side (refractory concrete)

insulating material in the chamber
at 600 – 700 °C:
 X-ray analysis
• Hot side area:

 based on KCl and CaSO4
Cool side (metal jacket)
 residual NaCl,
futher chlorides,
Cr- and Fe-sulfates Calcium silicate thermal insulating material
(thickness 25 mm) after 18 month in use in the
chamber between the preheater and the
rotary cement kiln.

9
Alkali Corrosion
• Alkali corroded fireclay brick in the hot zone Hot side Cool side
at 800 °C:
 X-ray analysis
• Area around the crack:

 based mainly on leucit (K2OAl2O34SiO2)
 residual silica (SiO2),
mullite (3Al2O32SiO2)
corundum (Al2O3)
Fireclay brick from the chamber between the
preheater and the rotary tube of the cement
kiln after use (18 month), left heat site with a
temperature between 800 to 900 °C.

10
Alkali Corrosion
Cool side
• Alkali corroded fireclay insulating brick in
the hot zone at > 1000 °C:
Infiltration zone
 X-ray analysis
• Hot side area:

 based mainly on leucit (K2OAl2O34SiO2),
mullite (3Al2O32SiO2)
 residual silica (SiO2),
kalsilit (K2OAl2O32SiO2) Hot side
larnit (2CaOSiO2) Fireclay insulating brick after 3 years in use in
a cement rotary kiln (feed end), front heat site
with a temperature > 1000 °C.

11
Alkali Corrosion
Hot side
• Alkali corroded magnesia brick in
the sinter zone at > 1100 °C:
 X-ray analysis
• Hot side area:

 based mainly on leucit (K2OAl2O34SiO2),
mullite (3Al2O32SiO2) Cool side
 residual silica (SiO2), Magnesia brick after 2 years in use in a

kalsilit (K2OAl2O32SiO2) cement rotary kiln (sinter zone), above on the
heat site with a temperature > 1000 °C.
larnit (2CaOSiO2)

12
Alkali Corrosion
• Alkali corroded refractory concrete from the

wall of a bottom cyclone of cement: A
 SEM-Analysis
(pore size 100 to 200 µm)
• In pores and reacted layers: B

 “A” and “B” present deposit KCl
 bubbly microstructure of KCl-layer is an
evidence for its primary liquid state
 “B” present cracks in the KCl-layer as a
indication for differences of the thermal Industrial refractory brick from the wall of a bottom
linear expansion coeffizients cyclone of cement kiln after 1 year usage.

13
Alkali Corrosion
Validation of the industrial refractory materials by alkali attack

• Refractories based on aluminum silicate:
 formation of feldspar
 volume increase
 alkali bursting
• Refractories based on calcium silicate

 not stable in the exhaust
 disintegration to CaCO3, CaSO4, SiO2 without volume change
• Refractory bricks and concretes (based on alumina or magnesia)

 deposit of substances in pores
 spalling (spall in layers)
 The formation of feldspar, the alkali bursting, the cracks and the fractional dropout
are caused due to alkali corrosion attack.

14
Alkali Corrosion
Alkali compounds in corroded refractory bricks and concretes
• The most of analyzed samples contained:

Feldspar,
KCl,
Alkali sulfate,
NaCl,
Other chlorides
Other sulfates
 In summery, K and K-compounds are more “common” than Na and Na-compounds.

15
Alkali Corrosion
High temperature behavior of alkali salts and alkali salt mixtures

• Salts after heating at 1100°C in crucibles:
Solid salt after 1100°C

Na2SO4, K2SO4  molten
Na2CO3, K2CO3  molten
NaCl, KCl  evaporated
CaSO4  sintered
• The solid salts as most reactive and corrosive mixtures after heating at 1100°C
in crucibles:
Salt mixtures after 1100°C

SM 1 K2SO4 / K2CO3  melting
SM 2 K2SO4 / K2CO3 / KCl  gas
SM 3 K2SO4 / K2CO3 / KCl / CaSO4  solid
Behavior of alkali salts and alkali salt mixtures

16
Alkali Corrosion
• Thermal linear expansion lin lin

coefficient (lin) of solid salts and measured literature
Solid salt
salt mixtures: 10-61/K 10-61/K
(20/600 °C) (0 °C)
 highest value: K2SO4
KCl 52 66,2
 lowest value: CaSO4
 is reflected in the value of the K2SO4 90 44,6
salt mixtures
K2CO3 58 43,3
CaSO4 16
SM 1 (K2SO4/K2CO3) 58
SM 2 (K2SO4/K2CO3/KCl) 50
SM 3 (K2SO4/K2CO3/KCl/CaSO4) 34
Thermal linear expansion coefficient (lin) of solid salts and

salt mixtures

17
Alkali Corrosion
• Density of solid and molten salts (literature):

 density difference between liquid and solid salts
 volume increase during heating up
Density of Density of Volume

• Hygroscopicity: Solid salt solid melt increase Hygroscopicity
g/cm³ g/cm³ %
 K2CO3 are hygroscopic
KCl 1,99 1,52 31 no
 KCl, K2SO4, CaSO4 are
not hygroscopic K2SO4 2,66 1,89 41 no
K2CO3 2,43 1,96 24 hygroscopic*
CaSO4 2,96 no
*weight increase app. 15 % after 4 days on normal area
(24 °C, 60 % rel. humidity)
 The volume expansion during heating up combined with the hygroscopicity (K2CO3)
leads to the destruction of the refractory in humid atmospheres.

18
Alkali Corrosion
Behavior of satured water based solutions of alkali salts and alkali salt mixtures
• pH-values of satured water based pH-value

salt solutions: Salt solution after
 K2CO3-solution is high alkaline directly
8 days
 KCl-, K2SO4-, CaSO4-solutions KCl 7,99 7,69
are neutral to alkaline
 solutions of salt mixtures are K2SO4 7,27 8,34
mainly high alkaline
K2CO3 13,83 13,74
CaSO4 9,69 7,92

 The acid effect is not identifiable of the
corrosion products of sheet-matall jacket SM 1 (K2SO4/K2CO3) 12,10 12,23
of rotary kiln too.
SM 2 (K2SO4/K2CO3/KCl) 12,09 12,14
SM 3 (K2SO4/K2CO3/KCl/CaSO4) 12,08 12,14
pH-values of satured water based salt solutions as a function

of time at 21 °C.

19
Alkali Corrosion
Behavior of satured water based solutions of alkali salts and alkali salt mixtures
• Electrical conductivity of satured Electrical

water based salt solutions: conductivity
Salt solution
 K2SO4 is more soluble than CaSO4 after
directly
8 days
 the value of electrical conductivity
of CaSO4 is increased by a factor 16 KCl 378 381
K2SO4 91 90
 The corrosion due several micro K2CO3 173 172
processes is supported by Cl- and SO42-.
CaSO4 1560 1655
 One of the corrosion mechanisms is
based on electrochemical corrosion. SM 1 (K2SO4/K2CO3) 161 161
SM 2 (K2SO4/K2CO3/KCl) 184 184
SM 3 (K2SO4/K2CO3/KCl/CaSO4) 178 178

Electrical conductivity in µS/cm of satured water based salt
solutions as a function of time at 21 °C.

20
Alkali Corrosion
Melt formation
Change of
4 main alkali Expansion as a
density and
corrosion result of salt
volume of the
mechanisms stored in pores
solid phase
Corrosion due to water

condensation
Mechanisms of alkali corrosion

21
Alkali Corrosion
Refractory oxid / Temperature of
Alkali compound 1. melting [°C]
melting point [°C]
1. Melt formation K2SO4 1067
K2CO3 895
MgO / 2840
Na2O No miscibility
K2O No miscibility
• Alkali salt + refractory material: KCl + NaCl 645
CaSO4 1365
 formation of melts at 750 – 1450 °C CaO / 2580
Na2O No miscibility
(from literature) K2O No miscibility
KCl + K2O 366
Cr2O3 / 2200
K2O 669
Na2O 1410
Al2O3 / 2050
• Alkali salt mixtures + refractory material: K2O 1450
K2SO4 + K2O 804
 partially melt formation at 600 – 950 °C TiO2 / 1830 Na2O 986
K2O 950
 completely melt formation at 700 – 1000 °C Na2O 789
(from phase diagrams) SiO2 / 1713
K2O 742
MgO + Al2O3 / 1925 No dates
 In addition: presence of K2O and Na2O as Al2O3 + SiO2 / 1595
Na2O 732
K2O 695
reactive and corrosive substances at high
Na2O 713
temperature and water vapour MgO + SiO2 / 1543
K2O 685
Na2O 725
CaO + SiO2 / 1436
K2O 720
Temperature from the 1. melting for refractory oxids or oxids
mixturs with compounds of alkalis from the phase diagrams. CaO + Al2O3 / 1395 No dates

22
Alkali Corrosion
1. Melt formation
Magnesia
• Phase diagram of the system K2SO4 – MgO: 3000
2850o
 melt formation of eutectic at 1067 °C
2500 Liquid
• Phase diagram of the system K2CO3 – MgO:

 melt formation of eutectic at 895 °C 2000 MgO + Liq.
T, C
o
• similar behavior is due of the system 1500
KCl - MgO
1069o (2%) 1067o
1000
 MgO based refractory materials Hex-K2 SO4 + MgO
are not alkali resistant because melt formation 588o
at 895 °C. 500
Ortho-K2 SO4 + MgO
0 20 40 60 80 100
Mol % MgO
K2 SO4

23
Alkali Corrosion
1. Melt formation
SiO2-based refractories
• Phase diagram of the system Na2O – SiO2:
 melt formation at 782 °C resp. 789 °C
 complete melt of by 26 % Na2O
 no strength of solid structure (25 % melt)
by 4 % Na2O at 1300 °C
• Phase diagram of the system K2O – SiO2:

 melt formation at 769 °C
 complete melt of eutectic by 27 % K2O
 no strength of solid structure (25 % melt)
by 4 % K2O at 1300 °C
 25 % eutectic melt by 6,5 % Na2O or K2O at 800 °C

 Strong effect of flux of the alkalis leads to damage of SiO2-based refractories
at 700 and 800 °C by a melt formation

24
Alkali Corrosion
1. Melt formation
Calcium silicate
• Phase diagram of the system Na2O – CaO – SiO2:

 lower volume expansion of reaction products
• Phase diagram of the system K2O – CaO – SiO2:

 melt formation of eutectic at < 720 °C
 Refractory materials based on wollastonite

no alkali resistant, because melt formation
at 700 °C.
Alkali Corrosion of Therml Insulating Material Based of Calcium Silicates

25
Alkali Corrosion
1. Melt formation
• Applied Temperatures in presence of alkali < 1300 °C,

because of melt formation below 1100 °C:
 refractory oxides MgO, CaO, Cr2O3, TiO2 and SiO2
 binary combinations Al2O3/SiO2, CaO/SiO2, MgO/SiO2
• Applied Temperatures in presence of alkali > 1300 °C:

 refractory oxid Al2O3
 binary combinations Al2O3/MgO, Al2O3/CaO could be „suitable“
(no dates of melt formation)

26
Alkali Corrosion
2. Change of density and specific volume of the solid phase
Volume
Refractory Density New formed Density
• Alkali compounds unknown: oxide g/cm³ alkali compounds g/cm³
change
%
 MgO, CaO
Al2O3 3,99 (N,K)1…6A1…11 2,63…3,42 +17…+52
• Densities of refractory oxids:
 > 3 g/cm³ Cr2O3 5,25 NC 4,36 +20
(except SiO2, CaOSiO2)
SiO2 2,65 (N, K)1…3S1…4 2,26…2,96 -10…+17
• Densities of new formed alkali 3Al2O32SiO2 3,17

(N,K)1…3AS1…6
2,40…2,62 +21…+32
N3CA3S6(SO4)
compounds:
 < 3 g/cm³ (most frequently) CaO6Al2O3 3,69 (N,K)C0…14A4…11 3,03…3,31 +11…+22
3,55…
MgOAl2O3 NM0,8…4A5…15 3,28…3,33 +7…+13
3,70
 The volume increase of solid phase
of the refractory oxides containing 2MgOSiO2 3,22 (N,K)1…2M1…5S3…12 2,56… 3,28 -2…+23
alkali compounds leads to an
CaOSiO2 2,92 (N,K)1…2C1…23S1...12 2,72…3,36 -13…+7
attrition of microstructure and
the damage of refractory lining. Refractory oxids, possible alkali compounds (cement chemistry notation)
from the phase diagrams, whose densities and change of volume
(„+“ expansion, „-“ shrinkage).

27
Alkali Corrosion
• Phase diagram of system

MgO – SiO2 – K2O with forsterite:
 formation of solids at 1100 – 1300 °C
2MgOSiO2, MgO, K2OMgOSiO2, K2O
• Change of densities e.g. specific volume

by chemical reaction of forsterite with K2O:
Density Specific volume
Solid
g/cm³ cm³/g
2MgOSiO2 3,22 0,311
MgO 3,59 0,279 K2OMgOSiO2
K2OMgOSiO2 2,76 0,362

K2O 2,33 0,429
 expansion and shrinkage

 Refractory materials based on forsterite no alkali resistant, because volume
increase leads to destruction of the structure

28
Alkali Corrosion

K2O – Al2O3 – SiO2 with mullite and fireclay:
 formation of solids with lower densities
at < 1556 °C
mullite react to corundum
fireclay react to alkali feldspar Fireclay
 first eutectic melts appear at 1556 °C

1556 °C
• similar behavior is due of the system

Na2O – Al2O3 – SiO2 Mullite
 Lower density of products by reactions of

K2O and Na2O with mullite and fireclay
leads to:  high volume expansion
 “alkali bursting”
 damage of refractories

29
Alkali Corrosion
• Calculated volume expansion

of mullite and fireclay depend
on the content of K2O or Na2O
(from phase components and
Mullite + K2O
densities)
Mullite + Na2O
Volume expansion in %
• Mullit: Fireclay + K2O
22 % volume increase with Fireclay + Na2O

8 % linear expansion
by formation of corundum
• Fireclay:
volume expansion decrease at a
K2O/Na2O-content of > 20 % Content of K2O or Na2O in % by weight
Volume expansion of mullite and fireclay by reaction with K2O or Na2O

30
Alkali Corrosion

K2O – CaO – Al2O3 with hibonite:
 formation of solids at 1100 °C
with high volume expansion

Na2O – CaO – Al2O3 with hibonite:
 more expansion of volume than with K2O
 Refractory materials based on hibonite

are not alkali resistant, because the volume
expansion at 1100 °C leads to a damage of
the structure (contrary to literature opinion)

31
Alkali Corrosion

Na2O – Al2O3 with alumina:
 formation of solids at < 1300 °C

K2O – Al2O3 with alumina:
 formation of solids at < 1300 °C
 Refractory materials based on alumina

are not alkali resistant, because the volume
expansion up to 1000 °C leads to a damage of
the structure
 up to 1400 °C destruction of the aluminates (NaAlO2, KAlO2) and evaporation of alkalis
 Exception: -alumina with “alkali resistant considerations”

32
Alkali Corrosion
• The increased volume of the solid phases to 52% is leading to bursting of solid
structures. Less known and in contrast to the general opinion are the following topics:
 Alumina Al2O3 reacts to alkali aluminates with a volume increase to 52 % and leads to a
destruction of the products.
 Cr2O3 leads to expansion by reaction with alkalis.
 The density modifications of SiO2 and calcium silicates taking place by melting. The
volume increase of solid parts by melting is not a problem, but the melt formation and the
deformation of the products.
 Fireclay reacts to feldspars and shows a volume increase between 21 to 32 %. This
corrosion process is known as “alkali bursting”.
 Hibonite, known as alkali-resistant, reacts to β-alumina, and presents a volume increase
of about 22 %.
 Spinel reacts to (Na2O⋅MgO⋅Al2O3)-compounds, like β-alumina, and leads to volume
increase of approximately 13 %.
 Forsterite reacts to alkali compounds and shows a volume increase to 23 %. Forsterite is
also,( contrary to literature opinion), not alkali corrosion resistant.

33
Alkali Corrosion
3. Expansion phenomena
• Salt storage in pores of refractories:

 evaporation of salt at high temperatures A
 condensation of salt in cooler range of
refractory materials
 pores are filled entirely with liquid or
solid salts B
• Destruction mechanisms:
 thermal linear expansion of salts
5- to 10-fold more than refractory materials
 thermal shock sensibility of refractory Industrial refractory brick from the wall of a bottom
material is increased cyclone of cement kiln after 1 year usage.
 volume increase between solid and

liquid salt (change of densities)
 hygroscopicity of salts and volume increase
(destruction in humid atmosphere)

34
Alkali Corrosion
4. Corrosion due to water condensation
• Satured water based salt solutions:

 pH-values are neutral to alkaline (no acid!!)
• Metal corrosion
 pH-value < 10
 electrochemical corrosion
 Investigations for the future
Alkali corrosion of a steel bar in a gradient furnace

after treatment at 1000°C.

35
Alkali Corrosion
Sumary of the alkali corrosion mechanisms
physical-chemical high temperature melting processes associated

with solution, sintering and shrinkage
chemical material conversion under solid conditions and so modification

of density of solid refractory phases causing bursting effects
mechanical stresses/bursting between solid salt in the pores and the refractory material
chemical material conversion followed by expansion and shrinkage due to

water condensation and removal of water condensation products

36
Alkali Corrosion
Investigations of the alkali resistance – “disc-test”
layer of solid salt

• Disc-test: particles
pressed disc based on 70 % refractory powder

and 30 % salt mixture (K2SO4, KCl, K2CO3)
solid raw
mixture of solid raw material +
• Change of sample diameter, weight and material particle
alkali salts
visual features of refractory/salt heat treated
Coating of solid raw material with solid salt
discs under periodic heating and cooling particles
conditions
• Fireclay:
diameter increase from 50 to 53 mm
 linear expansion of 6 % due to
alkali bursting
unfired 1100 °C / 5 hours
Disc-test of fireclay salt briquette before and
after heat treatment at 1100 °C for 5 hours
U. Fischer, C.G. Aneziris, E. Schlegel: Corrosion Problems of Refractories due to the Use of Secondary fuels
Investigation methods
37
Alkali Corrosion

Salt mixtures
SM 1 K2SO4 / K2CO3
• Change of diameter after 1100 °C at 5 hours SM 2 K2SO4 / K2CO3 / KCl
SM 3 K2SO4 / K2CO3 / KCl / CaSO4
 high value of expansion
Zirconia mullite Z72
Spinel MA 76
Spinel AR 78
Hibonite SLA-12
Hibonite Bonite
Forsterite Olivin
Aluminium titanate
 high value of shrinkage

Zirconia 3Y-TZP
 suitable materials
Zirconia 3,5Mg-PSZ
Na-aluminate
-alumina
Betacalutherm (dried, fired)
Expansion and shrinkage of the different mixtures after treatment at 1100 °C and 5 h
38
Alkali Corrosion

Salt mixtures
SM 1 K2SO4 / K2CO3
Spinel AR 78
Hibonite SLA-12
Hibonite Bonite
Forsterite Olivin
Aluminium titanate

Zirconia 3Y-TZP
Zirconia 3,5Mg-PSZ
Na-aluminate
Spinel MA 76
-alumina
Betacalutherm (dried, fired) Expansion and shrinkage of the different mixtures after treatment at 1300 °C and 5 h
39
Alkali Corrosion

Salt mixtures
SM 1 K2SO4 / K2CO3
Spinel AR 78
Forsterite Olivin
-alumina
Spinel MA 76
Expansion and shrinkage of the different mixtures after treatment at 1300 °C

and 50 h
40
Alkali Corrosion
• Change of diameter after 1100 and 1300 °C, 5 and 50 hours hold time
Spinel MA 76
Spinel AR 78
Hibonite SLA-12
Hibonite Bonite
Forsterite Olivin
Aluminium titanate

Zirconia 3Y-TZP
Zirconia 3,5Mg-PSZ
Na-aluminate
Samples for change of disc diameter after heating at 1300 °C and 5 h
-alumina
 Betacalutherm and -alumina are long-time and alkali resistant after that as the only
fire-proof materials up to 1300 °C
41
Alkali Corrosion
Salt mixtures
• Influence of humidity of alkali-infiltrated SM 1 K2SO4 / K2CO3
used raw materials:
 increase of sample weight
30 – 70 %
 The sample weight had increased

because the humidity had condensed
in the pores of the sample structure.
Increase of sample weight after heat treatment and storage

time at 20 °C and 100 % rel. humidity.
42
Alkali Corrosion
• Influence of humidity of alkali-infiltrated

Salt mixtures
used raw materials: SM 1 K2SO4 / K2CO3
 volume increase
<1%
 volume decrease
<1%
 The water absorption of alkali infiltrated

samples took place with out or minor
changes in volume at high humidity
across month.
 The alkali infiltrated Betacalutherm

and -alumina take in humidity and
dehumidify without change in volume
again and no destruction of the structure.
Change of sample volume after heat treatment and 2 and 3
months storage time at 20 °C and 100 % rel. humidity.
43
Alkali Corrosion
Investigations of the alkali resistance – crucible test according DIN 51069
upper
alkali gas
• Crucibel test: crucible
DIN 51069
sealing
1000 °C for 5 hours
salt mixture K2SO4, K2CO3 bottom alkali salt
crucible mixtur
• Refractory concrete on the base of Fireclay:

 completely infiltration of the salt mixture
 alkali bursting lead to critical cracks
 damage of the crucible at low temperature
and short exposure time
Crucible test of castable gunning material

according to DIN 51069, after heat treatment
at 1000 °C for 5 hours
44
Alkali Corrosion
Investigations of the alkali resistance – crucible test according DIN 51069
• Crucibel test:
DIN 51069
700 °C / 800 °C for 5 hours
salt mixture K2SO4, K2CO3 and
salt mixture K2SO4, K2CO3, KCl, CaSO4
• Calcium silicate thermal insulating material:

Calcium silicate thermal insulating material with
 infiltration with partly fluid salt melt at 700 °C salt mixture K2SO4 and K2CO3 at 700 °C for 5 h
 damage the crucible at 800 °C
 partly dissolving of the calcium silicate
in the salt melt
• Melt formation at low temperature (720 °C)
Calcium silicate thermal insulating material with salt

mixture K2SO4, K2CO3, KCl and CaSO4 at 800 °C for 5 h
45
Alkali Corrosion
Investigations of the alkali resistance – test in a gradient furnace
• Gradient furnace:
 gradient of temperature
100 - 1300 °C
 alkali atmosphere
• Thermal insulation material:

 Betacalutherm
• Refractory material:
 refractory concrete
• Steel bar: Wall built-up for corrosion test in gradient furnace

 austenitic steel 1.48.28 with
scaling resistance to 1000 °C
• Salt mixtures:
 K2SO4 / K2CO3 / KCl
46
Alkali Corrosion
Investigations of the alkali resistance – test in a gradient furnace
• Thermal insulation material:

 Betacalutherm with out
corrosion effects
• Refractory material:
 refractory concrete with cracks,
volume increase (2-3%),
formation of feldspar in the
hot zone
Wall built-up after corrosion test in gradient furnace:
left – scaling of the steel bar in the alkali corroded refractory material;
right – Betacalutherm without corrosion effects
• Steel bar:
 scaling with volume increase
(33-56 %) in the hot zone
 Verification of the post mortem investigations of the industrial refractory materials
47
Alkali Corrosion
Conclusions of alkali corrosion of the refractory materials

• Worst corrosion – bursting effect: Refractory Alkali
Damage by
 salt mixture of K2SO4 / K2CO3 oxide oxid
Na2O Melt up to 782 °C
• No alkali resistant: SiO2
K2O Melt up to 769 °C
 all refractory oxides Na2O Melt up to 720 °C
Calcium
 all refractory mixtures silicate K2O Melt up to 700 °C
Na2O 10% volume expansion by 3% Na2O
• “alkali resistant considerations”: Al2O3
K2O 10% volume expansion by 4% K2O
 low alumina content materials
(-alumina doped material) Na2O 10% volume expansion by 14% Na2O
Mullite
• -alumina:
 alkali aluminate Fireclay
(5 to 11 mol Al2O3, 1 mol Na2O or K2O)
Forsterite K2O 10% volume expansion by 34% K2O
 melting point 1580 – 2053 °C Spinel Na2O 10% volume expansion by 7% Na2O
 -alumina does not melt ore react Hibonite
with higher content of alkalis at K2O 10% volume expansion by 6% K2O
temperatures below 1580 °C Sumary of phase diagrams
Conclusions
48
Refractories for gasification process
49
Wear mechanisms of refractories in slagging gasifiers
J.P. Bennett, Refractory liner materials used in slagging gasifiers
Introduction to Refractories for Gasification Processes

50
Potential Refractory Problems in Coal Gasification
1 alkali attack
2 carbon monoxide disintegration
3 silica volatilization dry ash
4 steam-related reactions gasifiers
5 thermoelastic stresses slagging
gasifiers
6 erosion due to solid particulates
7 corrosion and erosion due to molten coal slag and/ or iron

8 iron oxide bursting
C.R. Kennedy and P.E. Schlett, Refractories for Coal Gasification

51

Corrosion and Erosion by Molten Coal Slag and/or Iron
• High-purity alumina, chrome-magnesia, alumina-zirconia-silica, zirconia, SiC

 Grand Forks Energy Technology Center (GFETC)  less than 10 h at 1550 °C lifetime
 Ruhrchemie Texaco gasifier  hundreds of hours at 1600 °C lifetime
 lifetime depends on conditions (unique for single gasifier) and coal/ slag (e.g. CaO/SiO2 < 1
or CaO/SiO2 > 1)
• major mechanisms of the corrosion process: dissolution, penetration and disruption, and
erosion
• higher velocity slag  rate of corrosion ↑  dissolution and/or erosion ↑

52

Corrosion and Erosion by Molten Coal Slag and/or Iron
• dense high-chromia content refractories  superior corrosion resistance to CaO/SiO2 =

0.2-1.7
• high-iron oxide acidic coal slag at 1575  chrome-spinel (MgCr2O4)

 low solubility of Cr2O3 and MgCr2O4 in SiO2-Al2O3-CaO liquids
• refractories containing > 30 % Cr2O3

 reaction with all types of coal slags to form complex spinels (slowly dissolution)
 problems: poor thermal-shock resistance and susceptible to iron oxide bursting
• high alumina refractory intermediate in performance in acidic slags and poor in basic slags
• SiC + FexOy → ferrosilicon alloy (low melting)
• magnesia-chromite refractories better in basic slags than in acidic slags (dissolution of

MgO in all cases)

53

Thermal Shock Resistance of Brick Linings
• only few data available (Fig.)

• dense high-chromia (~ 80 wt%) have
significantly lower thermal shock
resistance than sintered low-chromia
bricks (e.g. 90 wt% Al2O3-10 wt% Cr2O3)
• improvement of the thermal shock
resistance by microstructural alteration
• heating and cooling rates have to be
carefully controlled to avoid spalling

54

Iron Oxide Bursting
• absorbed iron oxides leads to failures in spinel

containing refractories
• ferrite spinels have larger unit-cell sizes than
chromites or aluminates (Fig.)
 reactions with FexOy leads to internal
stresses  spalling
• Fe+2/Fe+3 ratio depends on partial O2-pressure
(unit cell size alters)
• low porosity limits the penetration of iron
oxides from the slag  spalling occurs only in
a thin surface layer (problem: cracks due to
thermal shock

55

Alkali Attack
• formation of low-melting low-viscosity liquids or dry alkali-alumino-silicate compounds

• problems occurs in the non-slagging regions of gasifiers
• most coal slags contain significant amounts of alkali (1-10%)
Na(g) + atmosphere → NaOH
NaOH + refractory (mullite) → NaAlSiO4 + NaAl11O17 (~ 30% volume expansion)
• minimizing the alkali attack by:

 use of low-alkali coals
 lower process temperatures (decrease efficiency)
 higher density of refractories (limitation of the penetration)
 use of high-silica refractories (60 wt%)  react with alkali to produce glass  sealing off
of the surface

56

Carbon Monoxide Induced Disintegration
2 CO = C + CO2 (400-700°C, red. atm.)
 deposition of carbon  refractory failure caused by internal
stresses
• accelerated by metallic iron, free iron oxides, iron carbides

• no reported failures but laboratory experiments (Fig.)
• rate of attack increases rapidly as the pressure increases
• small amounts of iron (0.25 wt%) affect the rate  alumina
castables loose strength in pure CO
• alkali compounds increase the attack rate
• H2S retard attack

57

Reduction of Silica by H2
SiO2 (s) +H2 → SiO(g) + H2O
(reducing and steam-containing atmosphere)
• loss of silica due to formation of volatile compounds
• e.g. 50% loss of silicate refractory in a secondary ammonia reformer after several years
• no changes of silica content at a depth of ~10 mm from the hot face
 indicates extremely slow diffusion rate of SiO below 1200 °C

58

Steam-Related Reactions
• coal gasification atmosphere

containing high partial pressures of
steam:
 SiC disintegration
 strength loss in phosphate-
bonded refractories
 no degradation of cement-
bonded castables
Results applicable to low-temperature sections

of most gasifiers. (1000-1100 °C)

59
Refractory problems in coal gasification

C – Physical wear – “spalling”
J.P. Bennett, Refractory liner materials used in

slagging gasifiers

60

Thermomechanical Degradation of Monolithic Linings
• cracking during initial dryout and heat-up of monolithic refractory lining
• mechanical reliability of the lining can be improved by:
(1) minimizing the amount of linear shrinkage of the refractory
(2) continuous, slow heat-up rate
(3) elimination of long hold periods during the heating and cooldown
(4) maintaining the vessel shell temperature as close to ambient as possible
(5) using incompressible bond barriers
(6) using anchor spacings greater than 1.5 times the lining thickness

61

Erosion of Refractory Materials
Testing methods:
• direct-impingement: (dolomite and sand particles vs. refractory)
 chrome castable more erosion resistant than high-alumina and lightweight castable
• fluidized-bed: (ambient temperature and 810 °C with dead-burned dolomite)

 high- and intermediate-alumina castables more erosion resistant than chrome
castable
• impingement-tube: (simulates hot-gas transfer lines with dolomite)

 high- and intermediate-alumina castables performed well
 erosion occurs primarily in the softer matrix

62
Corrosion Mechanisms
dissolution formation of an solid solution

intermediate compound
Kwong, et al., Wear Mechanisms of Chromia Refractories in Slagging Gasifiers

63
• oxygen partial pressure in a gasifier range from 10-7 to 10-9
• oxygen potential affects:
(1) valence state of transition oxides such as iron and vanadium oxides
(2) oxide basicity
(3) basicity of slags formed from iron and vanadium oxides
(4) melting point of the slags
 oxygen potential influences slag – refractory reactions and the compounds
formed

64
Thermodynamic calculations - HSC Chemistry®
• V3O5 should be stable phase in • FeO with some Fe3O4 may be

gasifiers environments stable phase formed at oxygen
partial pressure of 10-7 to 10-9

65
Material development from the 1970’s until today
R. Dürrfeld, Refractories in Coal Gasification Plants

66
Evaluated materials in the 1970’s and 1980’s
• alumina-silicate
• high alumina
• chromia-alumina-magnesia spinels
• alumina and magnesia
• alumina and chrome
• SiC
• chrome materials with phosphate
 only materials with high chrome oxide

content (min. 75 wt.-%)
(reaction between chromia and FeO)
J.P. Bennett, Low chrome/ chrome free refractories for slagging gasifiers

67
today’s researches – low /no chrome oxide
• alumina with ZrO2, MgO and additives

• alumina-zirconia with MgO, SiC and additives
• HfO2, HfSiO4
• ZrSiO4
• NiAl2O4
 researches still in progress

J.P. Bennett, Low chrome/ chrome free refractories for slagging gasifiers
M. Müller et al., Corrosion behaviour of chromium-free ceramics for liquid slag removal in pressurized pulverized coal combustion

68
Thank you for your attention!
69

Alkali Corrosion of Refractories in Cement Kilns

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Alkali Corrosion of Refractories in Cement Kilns

1. Introduction to alkali corrosion of refractories

2. Characterization of corroded industrial refractory materials

3. Behavior of alkali salts and alkali salt mixtures

4. Mechanisms of alkali corrosion

high temperature thermal

Reason of alkali accumulation in the cement rotary kilns

• cement dust returns into the burning process

Sources of corrosive substances

• alkali: included in natural raw materials, coal, secondary fuels

Introduction to Alkali Corrosion of Refractories

The use of secondary fuels

Introduction to Alkali Corrosion of Refractories

Combustion of secundary fuels

Introduction to Alkali Corrosion of Refractories

Effect of the combustion of secundary fuels in cement rotary kilns

Secondary fuels Organic Compounds

Introduction to Alkali Corrosion of Refractories

Post mortem investigations

• Roof of kiln hood of the DOPOL-kiln:

Cool side (metal jacket)

basic abrasion Insulating brick

Hot side (refractory bricks or concrets)

Characterization of corroded industrial refractory materials

Post mortem investigation

• Alkali corroded calcium silicate thermal Hot side (refractory concrete)

• Hot side area:

Characterization of corroded industrial refractory materials

Post mortem investigation

• Area around the crack:

Characterization of corroded industrial refractory materials

Post mortem investigation

• Hot side area:

Characterization of corroded industrial refractory materials

Post mortem investigation

• Hot side area:

 residual silica (SiO2), Magnesia brick after 2 years in use in a

Characterization of corroded industrial refractory materials

Post mortem investigation

• Alkali corroded refractory concrete from the

• In pores and reacted layers: B

Characterization of corroded industrial refractory materials

Validation of the industrial refractory materials by alkali attack

• Refractories based on calcium silicate

• Refractory bricks and concretes (based on alumina or magnesia)

Characterization of corroded industrial refractory materials

Alkali compounds in corroded refractory bricks and concretes

• The most of analyzed samples contained:

 In summery, K and K-compounds are more “common” than Na and Na-compounds.

Characterization of corroded industrial refractory materials

High temperature behavior of alkali salts and alkali salt mixtures

Solid salt after 1100°C

Salt mixtures after 1100°C

Behavior of alkali salts and alkali salt mixtures

High temperature behavior of alkali salts and alkali salt mixtures

• Thermal linear expansion lin lin

Thermal linear expansion coefficient (lin) of solid salts and

Behavior of alkali salts and alkali salt mixtures

High temperature behavior of alkali salts and alkali salt mixtures

• Density of solid and molten salts (literature):

Density of Density of Volume

K2CO3 2,43 1,96 24 hygroscopic*

Behavior of alkali salts and alkali salt mixtures