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Alkalis and chloridic compounds are mainly taken into the kiln
by the kiln feed and the sulfur and vanadic compounds by the
fuel
The combustion of alternate fuels and especially waste fuels
Increases the concentrations of volatile and further harmful
compounds within the kiln system accelerating shell corrosion.
Wear of oxidised kiln shell during longer kiln shut downs caused
by small blackflies eating iron compounds ( so-called
Ferrum Pedis syndrome)
1. Fe2O3 ( haematite )
2. Fe3O4 ( magnetite )
3. FeS2 ( pyrite )
4. FeS ( pyrrhotite )
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Corrosion scale
morphology and
composition
Scales containing chloride without alkalis
High sulphur layers alternate with high oxygen
layers
With presence of chloride
Quantitative microanalysis of corrosion powder
( % w/w ) : Iron : 74 , Sulphur : 15 , Chloride :
2.5,
Potassium : 0.5
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Corrosion scale morphology and
composition
1. Oxidation
2. Sulphidization
3. Hot corrosion
Oxidation
In an oxidising atmosphere the iron from the
steel shell will react with oxygen to form
an oxide scale. Compound with highest oxygen
content , Fe2O3 being found at the scale-brick
interface , and the compound with highest iron
content , FeO at the metal-scale interface .
Sulphidization
Where no oxygen is present , SO2 takes over
as the oxygen donor and a different reaction
occurs as follows :
4 Fe + 2 SO2 ( g ) = Fe3O4 + FeS2
Suphidization is enhanced by the presence of
chlorides , mainly because they affect the morphology
of corrosion scale ,hindering the formation of a strong
, protective oxide layer.
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Mechanisms important to kiln shell
corrosion
Sulphidization
1. High temperature hydrolysis of the thermally unstable alkali
chlorides to form the more stable sulphates.
2. Followed by re-oxidation of hydrogen chloride gas ( by oxygen
or SO2 ) at lower temperatures to elemental chlorine which
attacks the metal.
2 KCl ( g) + H2O ( g ) + SO2 ( g ) + O2 (g ) =
K2SO4 + 2 HCl ( g ) ( T < 900 0C )
2 HCl ( g ) + O2 ( g ) = Cl2 ( g ) + H2O ( T< 400 0C )
Sulphidization
1. In preheater kilns , chlorides evaporates during
or shortly after calcination without substantial
formation of hydrogen chloride gas.
2. Kilns with tertiary air duct, show delayed alkali
chloride evaporation and, consequently,
evaporation will be followed by more extensive
hydrolysis of chlorides.
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Mechanisms important to kiln shell
corrosion
Sulphidization
Once Cl2 ( g ) is formed, it can reach the kiln shell
through the protective refractory bricks or through
cracks and fissures in the lining, and will react with
either the oxide-sulphide layers or, most likely,
directly with the kiln shell according to the following
reactions :
- reaction with the oxide-sulphide layers
FeS + Fe3O4 + 4 Cl2 = 4 FeCl2 + SO2 +
O2
- reaction with the kiln shell
Cl2 + Fe = FeCl2
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Mechanisms important to kiln shell
corrosion
Hot corrosion
Alkalis can probably only penetrate the lining
as part of a liquid potassium and/or sodium salt
melt.
If corrosion products therefore contain
substantial quantities of potassium or sodium
the form of corrosion is termed as Hot
corrosion, indicating that a liquid phase takes
part in the corrosion reactions.
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Measures to prevent kiln shell corrosion