Wear of refractories, particularly when using waste fuels

and their influence on the brick life

Dr. Johannes Sdje

Influences on the part of the cement producer

Refractory
installation

thermal

storage
Lifetime
of
refractories

chemical
kiln
burning
conditions
mechanical

Refractory
selection

Installation
draw

Productionquality

Raw
material
quality
Influences on the part of the producer

Stresses on the Refractory Lining in Rotary Cement Kilns

loads on
refractory linings

Thermal influences

Typical burning conditions

Clinker melt infiltrations
Concave/sloping erosion
Thermal shocks

Typical burning conditions

Clinker melt infiltration

Densification of the bricks hot face caused by clinker melt infiltration
increased thermal influences
- variations of the kiln feed composition
-

Concave/sloping erosion
(brickwork erosion)
constant thermal overloading of the brickwork
direct flame impact
coating free operating conditions with standard bricks with low refractoriness

Thermal shock influences

Too fast heating up or cooling down
Loss of coating
Optimizing:
Taking heating procedure into consideration/
cooling down slowly

Chemical influences
Salt infiltration
Corrosion of chrome spinel
Silicate corrosion
Redox burning conditions
Alkali Spalling
Corrosion of the kiln shell
Hydration of basic bricks

Salt infiltration:
Volatile elements and their principal compounds
(without heavy metals)
Sulphur compound
SO2, SO3, S2Potassium oxide
K2O
Sodium oxide
Na2O
Chlorine
Cl2, Cl-

Salt infiltration: alkali sources

Kiln feed raw material

Clay and mica minerals
Feldspar (Na,K)AlSi3O8
Plagioclase (Na,Ca) (Si,Al) Al2Si2O8
Additives (ashes, bentonite, etc.)
Alternative combustibles

Salt infiltration: chlorine sources

Coal

0.01 - 0.3 % Cl

Lignite

0.1 - 0.13 % Cl

Animal meal

0.6 - 1.6 % Cl

Plastics PVC
20 % of the worldwide production ofplastics
CH2=CHCl

30 % Cl

Salt infiltration: sulphur sources

Kiln feed raw material:

FeS2, PbS, ZnS, CaSO4, CaSO4H2O

Oil

0.2 - 2.5 %

Pitch/Tar

1-6%

Coal

0.1 - 12 % SO3 in the ash

Petrol coke

5-8%

Lignite

0.2 - 15 % SO3 in the ash

Concentrations of salts in the cement kiln system

Circulation of volatile compounds
alkalis + Cl-

alkalis + SO2/SO3

Calculation of the alkali-sulphate modulus (ASM)

in the cement clinker

K 2O Na2O Cl
+

62
71
ASM = 94
SO3
80

<1

KCl +
K2SO4 +
SO3 free

KCl +
K2SO4

>1

KCl +
K2SO4 +
K2O free

Salt infiltration, balanced alkali-sulphate modulus (ASM ~1)

Densification of different brick horizons
Infiltration of gaseous alkali chloride and/or sulfate components,
condensation and densification of the brick texture
Sulfate salts mostly in the lower transition zone and burning zone together
with alkali chlorides in the upper transition zone

Salt infiltration, balanced alkali-sulphate modulus (ASM ~1)

Chrome spinel corrosion, surplus of alkalis in kiln atmosphere (ASM >1)

Corrosion of chrome spinel in the presence of free alkalis
at higher temperature
Formation of toxic, hexavalent alkali chromate sulfate
(yellow efflorescences = water soluble)
Contamination of ground water, mason eczema

Silicate corrosion, surplus of sulphur in kiln atmosphere (ASM <1)

Silicate corrosion reduces the refractoriness
and the structural flexibility
2 C2S + MgO + SO3

CaSO4 + C3MS2

C3MS2 + MgO + SO3

CaSO4 + 2 CMS

CMS + MgO + SO3

CaSO4 + M2S

Possibly operational difficulties in the kiln system and to the clinker

composition caused by the high sulphur content in the kiln gas
atmosphere and/or surplus of sulphur in kiln atmosphere (ASM <1)
Formation of coating rings
and/or build-ups in the calcining
zone, inlet section, cyclones etc.
caused by the formation of
anhydrite (CaSO4), double sulfate salts
(calcium langbeinite, syngenite),
and spurrite phases (sulfate spurrite).

Possibly operational difficulties in the kiln system and to the clinker

composition caused by the high sulphur content in the kiln gas
atmosphere and/or surplus of sulphur in kiln atmosphere (ASM <1)
Sulphur will be retained as sulfates in the clinker (approach or exceed 2 %),
reducing the add of gypsum at the clinker grinding stage. The retarding of
hydration and setting of cement will be changed.
Formation of dusty clinker
Excess of sulphur in the clinker reduces the viscosity of clinker melt and the surface
tension of the liquid phases, which results in clinker structure loosening, and a
greater proportion of clinker dust is formed.

Redox burning conditions

Local reduction and/or redox burning conditions caused by
incomplete combustion of fuels (coarse coal, ashes on the linings surface)
Basic brick grades with alpine magnesia (crystalline magnesia) are sensitive
to the high Fe2O3 content

Alkali Spalling
Thin hot face spallings due to brittleness of the brick texture
Alkalis react with the brick components from fireclay and high alumina bricks
forming alkali alumina silicates (feldspar, feldspathoids). This formation is
accompanied by volume increase.

wear by alkalis

alkali spalling due to the formation

of new minerals

ng
palli
s
i
l
alka

alumina content, refractoriness, mechanical resistance

Kiln shell corrosion

Migration and efflorescences of salts between brickwork and kiln shell
Chemical attack of salts under kiln operating conditions (high thermal corrosion)
Depending on the alkali-SO3-ratio and oxygen partial pressure bi- and trivalent iron
oxides and/or iron sulphides are formed.

Hydration
Cracks from the brick surface into the bricks internal texture
Basic bricks are sensitive to humidity and must be stored and protected against
humidity, rain and sea water.
MgO reacts with water to brucite (Mg(OH)2) which is accompanied by
volume increase (~ 53%).
Tropical/sub-tropical climate conditions accelerate this reaction.

Hydration

Mechanical influences
Thermal expansion
Loosenings of the lining
Kiln shell deformation (ovality)
Grooves in the lining
Pressure loads on the kiln retaining ring

Thermal expansion

Convex spallings on the longitudinal joints

Too little allowance for expansion leads
to higher pressure within the brickwork.
Convex spallings finally occur.
Insufficient expansion space
Frequent kiln stops after the burnout of
the cardboards

Loosenings of the lining

Loosenings of the brickwork due to brickwork movements
Spiral twisting, tilting of bricks, shearing cracks, abrasion marks
on the bricks cold face
Wrong installation, frequent kiln stoppages, kiln shell deformations and ovalities

Kiln shell deformation (ovality)

Local strong spallings in the tire section, the surrounding brickwork is intact.
Increased ovality in the tire section causes tensions and loosenings of the
lining.
The bricks hot face is more loaded (spallings).

Groove formation
Increased wear parallel to the kiln axis caused by groove formation, the other
brickwork is intact (spallings of 2 - 3 brickwork width)
Brickwork rings are closed too tightly, damage of the key bricks using a wrong
hammer
More than one iron plate within the brickwork rings

High pressure on the retaining ring section

Increased pressure of the brickwork onto the retaining ring. Shearing tensions
occur within the brickwork leading to cracks and spallings of brick parts.
Instable, deformed kiln shell or ovality increase this wear.

Wear influences onto the monolitic lining

vapour explosion

mechanical
influences

monolithic
wear

thermal
influences

chemical
influences

Wear influences onto the monolitic lining

Vapour explosion (100 C to ~600 C)
Too fast heating up during setting/hardening and
after heating up of the monolithic lining
Thermal influences
Thermal shocks, thermal overloading, thermal spots
Chemical influences
Reaction with the kiln feed (clinker dust), thermochemical
attack by harmful components (alkali and sulfur compounds)
Mechanical influences
Abrasion, dust erosion (clinker dust), influences due to anchor, kiln shell
and metallic construction

Vapour explosion (100 C to ~600 C)

Riser shaft to calcinator/inlet chamber

Cooler banks

Thermal influences
Cooler banks (tension cracks caused by thermal shock)

Chemical influence
Kiln hood back wall (alkali attack -> alkali spalling)

Chemical influence
Corrosion of metallic anchors

Mechanical influence
Damper in the tertiary air duct (high abrasion caused by strong air stream)

Thermal, chemical and mechanical influence

Burner lance

A change of refractory wear, particularly when using

alternative or waste fuels in the cement rotary kiln

A change of refractory wear, particularly when using

alternative or waste fuels in the cement rotary kiln

Fuel oil and gas as primary energy since approx. 1960

Changeover to coal after the petroleum crisis in 1973/74
Use of alternative fuels since mid eighties

Lining and coating zone of kilns using fuel oil and gas

outlet zone

burning zone

safety zone

Coating in the burning zone

The magnesia-chromite bricks used in the hot zones and the high alumina
and fireclay bricks in the other sections perform good regarding lifetime and
wear resistance

A change of refractory wear, particularly when using

alternative or waste fuels in the cement rotary kiln

Fuel oil and gas as primary energy since approx. 1960

Changeover to coal after the petroleum crisis in 1973/74
Use of alternative fuels since mid eighties

Lining and coating zone of kilns using coal and fuel oil

outlet
zone

lower
transition
zone

burning zone

upper
transition
zone

safety zone

Coating in the burning zone and particularly in the transition zones

Magnesia-chromite bricks in the burning zone showing a usual wear
Reduced service life of the magnesia-chromite lining in the transition zones (salt
infiltration, formation of alkali chromates, redox burning conditions)

Salt infiltrations, alkali chromate formation and reducing burning

conditions in case of magnesia-chromite bricks

Development of magnesia-spinel and magnesia-zirconia bricks

MAGPURE93/95

ALMAGA1

ALMAG SLC

REFRAMAG85

ALMAG85
FERROMAG90
MAGNUM95

MAGNUMS

Main properties:
high resistance to alkali attack (no corrosion of the MA spinel or the zirconia)
insensitive to reducing or redox conditions

A change of refractory wear, particularly when using

alternative or waste fuels in the cement rotary kiln

Fuel oil and gas as primary energy since approx. 1960

Changeover to coal after the petroleum crisis in 1973/74
Use of alternative fuels since mid eighties

Lining and coating zone using fuels with 50 % usual fuels

and 50 % alternative fuels

outlet
zone

lower transition
zone

burning
zone I

transition
zone

burning
zone II

transition
zone

safety
zone

Complex and instable coating situation and various flames

Lining lifetime clearly reduced, particularly in the transition zones
(massive salt infiltrations, local overheating, local redox burning conditions)

Influence of secondary fuels on the refractory lining and kiln system

Stronger chemical and physical attack against the basic bricks

Risk of irregular temperature profile in the kiln (local thermal overload)
Risk of formation of local reducing atmosphere
Stronger chemical attack against the aluminous and fireclay bricks
Stronger attack against the kiln/cyclone shell and the anchor system

Percentage of the different wear types

Up-to-date studies show that more than 60 % of the wear cases are caused by
salt infiltrations (alone or in combination with other attacks)

23 % thermochemical influences and salts

23 % mechanical/thermomechanical influences and salts
17 % salts
23 % overheating
8 % mechanical/thermomechanical influences
1 % redox conditions
5 % other

> 60 %

Increase of salt infiltrations and accumulation of other harmful substances

in the structure, balanced alkali-sulphate modulus (ASM ~1)

Increase of salt infiltrations and accumulation of other harmful substances

in the structure, balanced alkali-sulphate modulus (ASM ~1)
Use of alternative additives with the kiln feed
(e. g.: condensation of lead sulfide (PbS))

Silicate corrosion, surplus of sulphur in kiln atmosphere (ASM <1)

refractoriness and the structural flexibility
are reduced
2 C2S + MgO + SO3

CaSO4 + C3MS2

C3MS2 + MgO + SO3

CaSO4 + 2 CMS

CMS + MgO + SO3

CaSO4 + M2S

K2O + 3 SO3 + 2 MgO

K2Mg2[SO4]3

Influence of secondary fuels on the refractory lining and kiln system

Stronger chemical and physical attack against the basic bricks

Risk of irregular temperature profile in the kiln (local thermal overload)
Risk of formation of local reducing atmosphere
Stronger chemical attack against the aluminous and fireclay bricks
Stronger attack against the kiln/cyclone shell and the anchor system

Local overheating and redox burning conditions

Redox burning conditions and salt infiltrations

Formation of oldhamite (CaS),

K2S, K2S3, KFeS2 under
reducing atmosphere
Sulfate salts reform in oxidizing
atmosphere, and lead to the
bricks destruction.
Typical smell of H2S during kiln
stop (smell of foul eggs)

Strong reducing and redox burning conditions

carbon disintegration, Boudouard reaction (CO2 + C <-> 2CO)

carbon horizon
16

Influence of secondary fuels on the refractory lining and kiln system

Stronger chemical and physical attack against the basic bricks

Risk of irregular temperature profile in the kiln (local thermal overload)
Risk of formation of local reducing atmosphere
Stronger chemical attack against the aluminous and fireclay bricks
Stronger attack against the kiln/cyclone shell and the anchor system

Alkali Spalling in the aluminous bricks

Structural embrittlement and spalling of thin layers.
The alkalis react with the components of fireclay and aluminous bricks under
formation of alkali containing alumina silicates (feldspars, feldspathoids).
This formation is accompanied by a volume increase.

Influence of secondary fuels on the refractory lining and kiln system

Stronger chemical and physical attack against the basic bricks

Risk of irregular temperature profile in the kiln (local thermal overload)
Risk of formation of local reducing atmosphere
Stronger chemical attack against the aluminous and fireclay bricks
Stronger attack against the kiln/cylcone shell and the anchor system

Effect of kiln shell corrosion and cyclone steel shell

Corrosion of metallic anchors (refractory areas installed with castables),

formation of alkali chromate (K2CrO4), surplus of alkalis
in kiln atmosphere (ASM >1)

Alkali chromate condensation in magnesia spinel lining

arcanite (blue efflorescences)

arcanite (green efflorescences)

alkali chromate

Requirements to refractory material and its installation

in Cement Rotary Kilns fired with secondary fuels
Minimization of infiltration and corrosion of refractory components
Optimization of the structural texture by higher flexibility
and high structural strength
Renewable sealing of the refractorys hot face
Optimization of installation technology, especially in the static area of cement
kiln system including a flexible and fast installation of high grade refractory
concretes and bricks
Innovative insulating and protection options for the anchoring system and steel
shell to reduce or even prevent different corrosion mechanism of shell and anchor
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Refratechnik Cements refractory solution

Basic refractory brick grades
established concept
AF-series: ALMAG AF, REFRAMAG AF, TOPMAG AF
new developments
TOPMAG A1, FERROMAG F1, FORMAG 88
Non-basic material
brick grades
established concept
new development
refractory concretes
high grades
high grade and
fast application
Installation technology

AR-series: KRONAL 50 AR, KRONAL 63 AR

KRONAL 60 AR
LCC, and LCC-AR product range
JC- and MCG-technology
AR-lining concept with integrated refractory design
including wear lining, insulating concept,
and anchor system

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