Report No.

61
Degradation of refractories
in cement rotary kilns
fired with waste fuels
P. Bartha
J. Södje
Published by:
Refratechnik Cement GmbH,
Göttingen

All rights reserved. Reproduction

in any form – including extracts –
only with publisher’s permission.
Degradation of refractories
in cement rotary kilns
fired with waste fuels
P. Bartha
J. Södje

©Refratechnik Cement GmbH 1

Abstract

In modern, waste-fired cement kilns, harmful atmospheric particles in the kiln

gases are primarily responsible for the degradation of the refractory lining. The new
formation of mineral phases is based on infiltration and chemical interaction with
the primary mineral phases. This leads to a differentiation of the physical properties
towards temperature gradients in the direction of the kiln shell.

Suitable new product developments need to be chemically inert to alkali and sulphur
and demonstrate a maximized infiltration resistance. It is self evident that adequate
thermochemical resistance to the cement clinker must be present in each zone of
use. Some modified and new products are described in brief form.

1. Introduction

Following the two major energy crises, the cement industry has undergone a radical
change in the use of fuel. This was accompanied by a changeover from oil and
natural gas to low-grade coal and the combustion of waste materials including rubber
tyres, plastics, solvents, etc. Parallel to this development, the precalciner kiln was
introduced in which the decarbonisation takes place outside the rotary kiln.

These developments have led to a change of the stress acting upon the affected
refractory lining in the entire kiln system. The burning zone has been thermally
discharged. Short lifetimes of the refractory lining caused by thermal overload have
become less frequent.

The most common reason for the degeneration of the refractory lining is now the
massive, complex influence of alkalis, metal compounds, SO 2 /SO 3, Cl, CO/CO 2 ,
etc. A distinction has to be made between infiltration processes with and without
interaction of the primary mineral phases of the refractory lining. As a consequence
of these processes, the physical properties of the refractory lining are changed in an
undesired manner. These are mainly a rise of the heat conductivity of the refractory
lining with increasing kiln shell temperatures, and an increase of the moduli of
elasticity resulting in brittleness and spalling.

This article is based on the results of comprehensive ”post mortem“ analyses of

refractory materials carried out in the various zones of modern cement kilns using
waste materials for firing. It also provides information on new refractory materials
fulfilling better the changed requirements.

©Refratechnik Cement GmbH 2

 2. Changes in Cement Burning Technology
and Sources of Energy

Changes in cement burning technology over the past 10-20 years are primarily
related to two key objectives of the cement industry:

• Reduction of the specific heat consumption by more efficient production

technologies
• Reduction of fuel costs

In technological terms, the replacement of the long wet and dry kilns by grate
and cyclone preheater kilns, and finally by precalciner kilns, and the continuous
optimization of burning and cooling systems could significantly reduce the specific
energy and heat consumption [1]. A cement plant with a six-stage preheater and
precalciner system requires 3,000 MJ of heat or less to produce a ton of clinker
while a wet kiln system requires more than 6,000 MJ. At the same time, kiln
capacity has been increased over recent decades from around 800 t/d in 1960 to
8,000 t/d and above by the end of the 20 th century. The process of precalcination
has enhanced this increase.

The availability and prices of fossil fuels led to a reduction in the use of coal from
the early sixties to the mid-seventies with oil and gas becoming the primary sources
of energy. The oil crisis of 1973/74 reversed this situation, and the use of coal once
again became more widespread. At the same time, the use of low-cost, low-grade
coal (lignite) and other alternative fuels including used tyres, petroleum coke,
podsol, wood, used oil, plastics, solvents, household and industrial waste, etc.,
increasingly became common sources of energy for the production of cement [2].

Following the dramatic price increases for imported coal in the mid-nineties,
secondary fuels became increasingly important. Along with increasing environmental
awareness (preservation of fossil fuels, reduction in the amount of landfill, reduction
of CO 2 emissions), the significant economic advantages (e.g. disposal fees) became
significant factors in favour of using these fuel sources.

Table 1 outlines a list of solid, liquid and gaseous alternative fuels. Since both the
variety and the quantity of secondary fuels are constantly increasing, this list is by
no means complete. The current BSE crisis in Europe and the resulting use of bone
meal is mentioned here as an example of an additional source of energy.

Solid Liquid Gaseous

Secondary Fuels Secondary Fuels Secondary Fuels
Petroleum coke oil shale used oil landfill gas
Graphite dust wood waste tar pyrolysis gas
Charcoal olive kernels acid sludge
Plastics residues coconut shells wastes from the paint
industry (varnish residues)
Rubber residues rice chaff chemical wastes
Tyres shreddings asphalt slurry
Battery residues oil-bearing earths oil sludge
Podsol sewage sludge petrochemical wastes
Paper wastes household refuse distillation residues
Activated bentonite refuse-derived fuel

Table 1: List of solid, liquid and gaseous alternative fuels [3 – 4].

©Refratechnik Cement GmbH 3

Depending on the composition of the alternative fuels, compounds containing
alkalis, chlorine and sulphur, as well as heavy metals and trace elements (lead,
cadmium, chrome, cobalt, copper, nickel, mercury, selenium, thallium, vanadium,
zinc), are introduced into the kiln system. Table 2 shows typical concentrations of
heavy metals and trace elements in alternative fuels.

components [mg/MJ]
Beryllium < 0.01 – 0.1
Cadmium 0.01 – 0.7
Mercury 0.01 – 0.1
Thallium < 0.01 – 0.1
Arsenic 0.003 – 1
Cobalt 0.02 – 8
Nickel 0.1 – 25
Selenium 0.03 – 0.4
Tellurium < 0.01 – 0.01
Antimony 0.03 – 0.05
Lead 0.09 – 25
Chrome 0.09 – 21
Copper < 0.01 – 67
Vanadium 0.03 – 16
Tin 0.03 – 0.7
Zinc 0.5 – 6.25

Table 2: Typical concentrations of heavy

metals and trace elements in alternative fuels [5].

As a result of the physical and chemical characteristics of these substances, internal

and external circulations of substances can build up in the kiln system. Depending
on the level of volatility of these substances, they are either bonded in the cement
or can enrich in the gaseous atmosphere in various kiln system zones leading to a
considerable circulation load in the kiln system. Fig. 1 shows a schematic diagram
of the behaviour and the transfer of the most important substances introduced into
the kiln system.

This cannot only lead to changes in the quality of the cement end product and to
disruptions of the process as a result of coating and ring formations, but also result
in impairments of the refractory lining due to premature wear.

Therefore, there are limits to the use of alternative fuels. These differ from case to
case, so that the following requirements must be taken into account when using
these fuel sources [4].

• T he structural properties and environmental compatibility of the cement must

not be impaired.
• The cement manufacturing process must not be adversely affected.
• A dditional environmental pollution must be avoided (compliance with local
emission restrictions).

©Refratechnik Cement GmbH 4

 filter
halogenides
semi-volatile elements
Tl, Cd, Bi alkalis
volatile elements

alkali chlorides

non-volatile elements reaction with

sulphur and
halogens

Fe, Ni, V, Ti, Cu, Zn, Pb,

As, Sb, Be, Mg, Sr, Ba
Fig. 1: The behaviour and transfer of the
key substances introduced into the kiln system [5]

3. Currently Available Refractory

Linings – a Retrospective Look at the
Various Kiln Zones

Over the 100-year history of rotary kiln operation, refractory brick linings have
undergone continuous modifications as a result of the changes in burning
technologies. Up until the 1940s, fireclay refractories and high alumina products
were used throughout the entire kiln. Afterwards, basic brick products including
magnesia bricks and magnesia-chromite bricks were used for the first time in the
burning zone of rotary kilns [6-7]. Due to their poor structural flexibility, magnesia
bricks could not compete with the performance of magnesia-chromite bricks in
rotary cement kilns. At the same time, dolomite bricks were used in the burning
zone, but this brick grade reveals a significant degree of sensitivity to CO 2 and H 2 O
as well as to excess sulphur in the kiln gas atmospheres [8, 9]. The development
of high performance rotary kilns with increased kiln capacity and higher specific
thermal cross-sectional stressing meant that magnesia-chromite bricks, e.g.
PERILEX ® 80, now became essential throughout the entire basic kiln section
(burning zone, transition zones). In the mid-seventies, Japanese rotary cement kilns
started using chromite-free magnesia-spinel bricks, primarily in the coating-free
transition zones. Use of magnesia-spinel bricks in these kiln zones was introduced
in Germany in the early eighties [10]. In this connection, the brick grade ALMAG ® 85
became the most popular magnesia-spinel brick.

©Refratechnik Cement GmbH 5

Although coating-forming magnesia-chromite bricks and dolomite bricks are
still used in the burnung zone, the environmental problems caused by refractory
products containing chromite (alkali chromate formation and negative impact on
the environment) resulted in an increasing demand for chromite-free basic bricks
in the cement industry.

In the nineties, the refractory industry introduced new chromite-free basic brick
grades with modified structural properties and enhanced physical characteristics.
Some of these were optimized for specific kiln zones, e.g. the tire section, extremely
thermally stressed zones, and the burning zone [11-13].

In the other thermochemically lower loaded kiln sections (outlet zone, preheating
zone, safety zone, chain zone in long wet and dry kilns, inlet zone) lightweight
refractory bricks, fireclay refractories, and high alumina brick grades are used
partially in combination with refractory castables based on fireclay, andalusite and
bauxite. The same applies to the cyclone heat exchanger, calcinator, kiln hood, and
cooler systems where a combined lining design consisting of brick and castable
has proved to be the ideal solution [14]. The lining with refractory castables was
originally restricted to few zones in the cement kiln (kiln inlet and outlet, chain
zone, burner pipe, some areas of the cooler (bullnose, cooler shaft, elbow inlets of
the satellite cooler, etc.)). The introduction of preheater and precalciner kilns led to
a significant increase in the use of unshaped refractory products in the seventies,
eighties, and nineties, particularly for lining the stationary zones of the cyclone heat
exchanger, calcinator, and cooler [14, 15].

A modern refractory lining concept for rotary cement kilns is presented in [16].

©Refratechnik Cement GmbH 6

 4. New Formation of Mineral Phases and Their
Influence on the Degradation of the Refractory Lining

A comprehensive range of case studies on used bricks and castables from various
zones of the rotary cement kiln system provides ample evidence of a change in
the causes of wear of refractory linings following the introduction of solid fossil
energy sources (coal, lignite) and increased use of secondary fuels. Significant salt
infiltrations without, or in combination with other wear factors, have come to the
fore, apart from mechanical/thermomechanical loads, thermochemical influences,
thermal overload and redox burning conditions (Fig. 2).

thermochemical influences + salts

17% thermal overloaded
23% redox-conditions
other
mechanical/thermomechanical
mechanical/thermomechanical + salts
salts

23%

23%

8%
5% 1%

Fig. 2: Percentages of the various wear factors in rotary cement kiln systems,
based on numerous investigations of basic brick grades as well as brick and
castables grades from the system Al 2 O 3 –SiO 2 in recent years.

In addition to infiltrations without chemical interactions, thermochemical reactions

between the infiltrates and the brick and/or castable components can occur under
certain circumstances. These result in the formation of new mineral phases with
consequential structural changes in the affected brick and/or castable horizons.
Table 3 lists the salt compounds and the newly formed minerals with their
melting and vaporization points, density and mineral names, which have been
mineralogically determined in the refractory lining of coal and waste-burned rotary
cement kilns based on case studies. The physical data have been sourced and
compiled from [17-19].

©Refratechnik Cement GmbH 7

Compounds Mineralogical Chemical Formula Melting Point [°C] Boiling Point Density
Name [decomposition or [°C] [g/cm3]
transformation
point]
Sylvine KCl 772 1500 1.98
Halite NaCl 801 1413 2.17
Potash K2CO3 897 decomposes 2.43
Soda Na2CO3 852 decomposes 2.55
K2CO3·1.5H2O 2.16
Arcanite K2SO4 1074 1689 2.66
Na2SO4 884 1429 2.70
Anhydrite CaSO4 1397 decomposes 2.96
Alkali/
alkaline Aphthitalite 3K2SO4·Na2SO4 stable below 2.70
earth salts 400/500 °C
K2SO4·CaSO4 867 (eutetic)
Calcium K2SO4·2CaSO4 936
langbeinite
Glauberite Na2SO4·2CaSO4 2.81
Langbeinite K2SO4·2MgSO4 930 2.83
Syngenite CaSO4·K2SO4·H2O 1004 2.60
K2 (Cr6+,S)O 4

K2 Cr6+O 4 968 2.73

K 2S 840 1.81
Alkali/
alkaline K 2S 3 252
earth KFeS2 2.56
sulphides
Oldhamite CaS 2450 decomposes 2.56
Magnetite Fe3O4 1594 5.13
Iron Hematite Fe2O3 1385 5.26
oxides/
Troilite FeS 1193-1199 decomposes 4.74
Iron
sulphides Pyrrhotine Fe1-xS
Pyrite FeS2 1171 5.00
Heavy metal Galenite PbS 1114 7.50
sulphides Cd9.5Zn0.5S10

Alkaline Merwinite C3MS2 [1575] 3.15

earth Monticellite CMS [1490] 3.20
silicates Forsterite M 2S 1890 3.13
Mayenite C12A7 1455 2.69
Alkaline
earth Ye’elimite C4A3·SO3 1590
aluminates/ Melilite C4AMS3 1390 2.95
Alkaline
earth C3MA2
aluminate Anorthite CAS2 1550 2.77
silicates
Gehlenite C2AS 1590 3.04
Sanidine KAS6 [1150] 2.58
Alkali Leucite KAS4 1150 2.51
aluminate
silicates Kalsilite KAS2 923 2.59
ß-Al2O3 (K,N)A11 1565 3.17

Table 3: Salt compounds and newly-formed minerals determined by mineralogical

analysis in the refractory lining of coal and waste-fired rotary cement kilns.
©Refratechnik Cement GmbH 8
 4.1. Infiltrations by Alkali and
Alkaline-Earth Salts and Trace Elements

The influence and interaction of salt components with the refractory lining depend
on the prevailing temperatures, the oxygen partial pressure, and especially the
alkali/chlorine/sulphur ratio in the various zones of the kiln.

The alkali/chlorine/sulphur ratio can be determined using the alkali sulphate

modulus (ASM), defined by HOLDERBANK Management and Consulting Ltd. as
shown in Fig. 3.

Calculation of the Alkali-Sulfate-Modulus (ASM)

in Cement Clinker

K2O Na2O CI
+ –
94 62 71
ASM=
SO3
80

<1 1 >1

KCI+ KCI+ KCI+

K2SO4+ K2SO4 K2SO4+
SO3free K2Ofree

Fig. 3: The alkali sulphate modulus (ASM), in accordance

with a proposal by HOLDERBANK Management and Consulting Ltd.

The following criteria have to be distinguished, which can result in various

degradation effects in the refractory lining:

• A lkali salts in a balanced ratio, i.e. ASM = 1 (recommended: 0.8 – 1.2)

• Excess of alkali, i.e. ASM > 1
• SO 2 /SO 3 excess i.e. ASM < 1

The relationships of the degradation effects on the refractory lining are mentioned
and in some cases discussed in detail in [20–23], providing a summary of the
essential details of the three various cases.

4.1.1. A Balanced Ratio of Alkali Salts

in the Kiln Atmosphere (ASM = 1)

In the case of a balanced alkali sulphate modulus (ASM = 0.8 – 1.2), all alkalis,
sulphates, and chlorides react in the kiln gas atmosphere to form alkali chloride and
alkali sulphate salts, and are bonded in the clinker or infiltrate into the brickwork. The
salt compounds migrate into the brick stucture until they reach their condensation
temperatures (K 2 SO 4 ≈ 1070 °C, KCl ≈ 800 °C) (Figs. 4, 5). The crystallization of the
salts leads to a densification of the brick structure with frequently sharply limited
infiltration horizons, accompanied by a reduction of the elasticity and the thermal
shock resistance of the affected parts. In this case, changes in the properties of the
refractory lining by chemical influences are rather unlikely.

©Refratechnik Cement GmbH 9

 Though these salt compounds were also found in coal-fired cement kilns, the use
of alternative fuels resulted in increased salt concentrations in the structure of the
refractory lining within shorter time intervals. In addition, significant concentrations
of heavy metal compounds (e.g. PbS) can occur in the structure of the refractory
material, primarily in the upper transition zone, due to the temperatures prevailing
there (Fig. 6). Under the influence of thermal shock and/or mechanical stress,
premature wear frequently occurs as a result of deep spalling.

During longer kiln shutdowns, and in the presence of air humidity, a transformation of
the infiltrated alkali salts by H 2 O-adsorption can occur. For example, from the sulphate
salt calcium langbeinite (K 2 SO 4·2CaSO 4) the salt syngenite (CaSO 4·K 2 SO 4·H 2 O) is
formed, K 2 CO 3 reacts with the absorption of H 2 O to form K 2 CO 3·1.5H 2 O.

These reactions are associated with progressive structural weakening, which can lead
to a more rapid degradation of the refractory lining following a recommissioning.

4 5 6

Figs. 4 – 6: Infiltration of magnesia-spinel bricks by sulphate salt (on the left),

alkali chloride salt (centre), and sulphate salts, alkali chloride salts and galenite
(PbS) (on the right)

©Refratechnik Cement GmbH 10

 4.1.2 Excessive Alkalis in
the Kiln Atmosphere (ASM > 1)

Under oxidizing kiln gas atmosphere, an excess of alkalis leads to oxidation of the

(ASM) (ASM)
chromium ore contained in the magnesia-chromite bricks, forming alkali chromates
and/or alkali chromate sulphates. The formation of toxic chromate salts can be

of the Alkali-Sulfate-Modulus
identified by yellowish efflorescences (Fig. 7). This same yellow efflorescence can

K2SO4+ K2SO4+K2SO4 K2SO4 K2SO4+ K2SO4+

K2Ofree K2Ofree
>1

KCI+ KCI+ KCI+ KCI+ KCI+ KCI+

be observed in the area of metallic anchoring of castable linings or in the case of

71
CI O CI
of the Alkali-Sulfate-Modulus
castables with integrated metal fibres (Fig. 8). This is also due to the formation of

+ 2 2 +– 2 –
ClinkerClinker

>1
alkali chromates as a result of alkali attack, whereby the chrome originates from

71
SO3 SO3
62

80
O O Na
the alloyed anchoring steel or from the steel fibres to strengthen the structure. The
in Cement

1
chromate formation can be described as follows (Table 4):

9462

80
K2O KNa
in Cement

1
ASM= ASM=
94

SO3free SO3free
Cr 2 3 + O 3 + 2K 2 O + 3 / 2 O 2 2K 2 Cr 6+ O 4

<1
Calculation

2K 2 SO 4 + 2K 2 O + Cr 2 3+ O 3 + 3 / 2 O 2 2(K 2 SO 4 /K 2 Cr 6+ O 4)

<1
Calculation

Table 4: Reaction Equations

7 8

Figs. 7 and 8: Yellow efflorescences of chromate sulphate salts in a m ­ agnesia-

chromite brick (on the left), and in a used castable with steel fibres, removed from
the burner pipe (on the right)

©Refratechnik Cement GmbH 11

 In both cases, the chromate formation can lead to premature wear of the affected
brick or castable lining as a result of spalling of embrittled brick hot faces or by
dropping of castable sections due to the corrosion of the metal anchors.

Brick grades from the system Al 2 O 3 –SiO 2 react with excessive alkalis to form

(ASM) (ASM) (ASM) (ASM)

ß–Al 2 O 3, feldspathoids (leucite (KAS 4), kalsilite (KAS 2)) and feldspars (KAS 6),
depending on the Al 2 O 3 content.

of the Alkali-Sulfate-Modulus

4 K2SO4+ K2SO4+
SO3free SO3free SO3free SO3freeK2Ofree K2Ofree K2Ofree K2Ofree
>1

KCI+ KCI+ KCI+

71
CI O CI
Formation of these minerals is accompanied by a significant volume increase

of the Alkali-Sulfate-Modulus

+ 2 2 + – 2 2 +– 2 2 + – 2 –
ClinkerClinker
(up to 30%), which leads to a stuctural weakening of the brick hot face (Fig. 9).

>1
71
SO3 SO3 SO3 SO3
62
Finally, thermomechanical and/or mechanical influences cause spallings of the

80
O O Na
the Alkali-Sulfate-Modulus

4+
thermochemically altered horizons – referred to as alkali spalling. The following is

in Cement

2SO
>11

KCI+ KCI+
2SO
71 946271
a selection of reaction equations (Table 5):

CI

80
O O KNa

4 KK
the Alkali-Sulfate-Modulus
Clinker

4+
in Cement

2SO
1<1 >11

KCI+KCI+
K2SO
ASM= ASM= ASM= ASM=
9462 9462
CI

80
O O KNa

4 4K+
Clinker

2SO
A 3 S 2 + 16S + 3K -> 3 KAS 6 (feldspar)
in Cement

KCI+ KCI+
KK2SO
ofCalculation

80
K2O KNa

4 4+
1<1

2SO
A 3 S 2 + 10S + 3K -> 3KAS 4 (leucite)
in Cement

KCI+ KCI+ KCI+

K2SO4+ K2SO4+KK2SO
ofCalculation

94

<1
2A 3 S 2 + 8S + 6K -> 6KAS 2 (kalsilite)
Calculation

11A + K + N -> <1 (K,N)A11 (ß-Al 2 O 3)

Calculation

Table 5: Reaction Equations

Fig. 9: High alumina brick spalling sample exposed

to thermochemical reaction with alkalis

4.1.3 Excessive Sulphur Oxides in the Kiln

Atmosphere (ASM < 1)

If there is an excess of sulphates, alkali sulphate and alkali chloride salt infiltration
may also occur, but the remaining free sulphate oxides can react either with the
clinker melt or the components of the brick and castable lining.

In the case of dolomite bricks, the CaO, one main component of this brick grade, is
reformed into CaSO 4 or CaS. In accordance with the Boudouardian equilibrium, the
organic impregnation substances in dolomite bricks can release carbon monoxide
(CO) under operating conditions, which reacts with CaSO 4 to form CaS and CO 2 .
CO 2 can then effect a recarbonization of the CaO. These mineral formations are
accompanied with an increase in volume, leading to a weakening of the physical
properties of the affected brick horizons, and finally to a destruction of the brick
texture.

©Refratechnik Cement GmbH 12

The CaO-containing silicates (e.g. belite (C 2 S)), occurring in low concentrations
in basic brick grades, react with SO 2 /SO 3 to form lower melting silicates, such
as merwinite (C 3MS 2) and monticellite (CMS). By this, the magnesia of the brick
is also corroded. Under the influence of continued SO 2 /SO 3 attack, the formation
of forsterite (M 2 S) can additionally occur. As a result, the sulphate salt CaSO 4
is formed, densifying the brick structure in deeper brick horizons. The silicate
corrosion leads to a weakening of the refractoriness and structural flexibility.
Magnesia-chromite bricks containing high levels of silicates are more susceptible
in their reaction to this degradation mechanism than magnesia-spinel bricks or
magnesia-zirconia bricks.

The CaO stabilized ZrO 2 or calcium zirconate (CZ), added to magnesia-zirconia bricks
for elastification, can also be corroded by severe SO 2 /SO 3 attack, forming CaSO 4 .
The elastifier becomes destabilized. Temperature influences lead to reversible
crystal lattice transformations of the destabilized ZrO 2 from cubic to tetragonal
to monoclinic, which may finally result in destruction of the structure, since these
lattice transformations involve significant changes of volume.

In cement-containing, and in particular, cement-rich castables, the formation of

C 4 A 3·SO 3 has been observed, accompanied by a corrosion of calcium aluminate
from the cement phase. The C 4 A 3·SO 3 -formation leads to a loosening of the
structure of the affected parts of the castable, allowing sulphur oxides and other
volatile components (alkalis, etc.) to migrate easier and deeper into the compound
structure, triggering off further structural changes.

The above-described degradation mechanisms and their newly formed mineral

phases can be described by the following reaction equations (Table 6):

Refractory Grade Reaction Equations

4CaO + 4SO 2 3CaSO 4 + CaS
CaSO 4 + 4CO CaS + 4CO 2 (locally reducing
Dolomite bricks
atmosphere due to tar residues in the dolomite)
CaO + CO 2 CaCO 3
2C 2 S + MgO + SO 3 CaSO 4 + merwinite (C 3MS 2)
Basic bricks containing
C 3MS 2 + MgO + SO 3 CaSO 4 + 2 monticellite (CMS)
calcium silicates
CMS + MgO + SO 3 CaSO 4 + forsterite (M 2 S)
Basic bricks containing ZrO 2 CaO-stab. + SO 3 CaSO 4 + ZrO 2
zirconium oxide CZ + SO 3 CaSO 4 + ZrO 2
Castables containing 4CA 2 + SO 3 C 4 A 3·SO 3 + 5A
calcium aluminate cement 4CA + SO 3 C 4 A 3· SO 3 + A

Table 6: Degradation mechanisms

©Refratechnik Cement GmbH 13

4.2. Thermochemical
and/or Thermal Influences

High thermochemical and thermal stresses are mostly caused by abnormal burning
conditions with increased temperature load. Due to fluctuations in the fuel
composition and feed rates, the use of low grade coal and especially alternative
fuels can lead to a change in the flame shape, and therefore to local occurrences
of overheating. In addition to the burning zone, significant thermal impingement
on the brickwork can also occur in other areas of the cement kiln system. This also
applies to other aggregates in which supplementary burning systems are fitted (e.g.
the calcinator).

When subjected to stress of this kind, a thermochemical reaction occurs between

the cement clinker or the infiltrated clinker melt and the brick or castable
components.

In the case of basic bricks, the elastifier (chrome ore, MA-spinel, hercynite) is
primarily corroded, resulting in the formation of low melting mineral phases. In
the presence of chrome ore, the formation of C 2F and/or C 4 (A,Cr)F occurs (Fig. 10).
Mayenite (C12 A 7 ) or C 4 A 3·SO 3 (in the presence of sulphur oxides) are the corrosion
products in the case of MA-spinel (Fig. 11).

Hercynite (fA) is degenerated to C 4 AF/C 2F and/or mayenite (Fig. 12). Under

extremely high temperature loads, the brick’s resistor (magnesia) is also attacked
and partially dissolved by formation of the mineral phases melilite (C 4 AMS 3) and/or
C 3MA 2 (Fig. 13).

Fig. 10: Chrome ore corrosion

Fig. 11: MA-spinel corrosion

©Refratechnik Cement GmbH 14

Fig. 12: Hercynite corrosion

Fig. 13: Magnesia corrosion

Figs. 10 –13: Corrosion of various elastifiers and of the magnesia

by clinker melt

In this respect, magnesia-zirconia bricks behave differently. The zirconium oxide

(added as an elastifier) reacts with cement clinker, forming the highly refractory
mineral phase, calcium zirconate (CZ, melting temperature: 2340 °C). There is no
brick corrosion accompanied by the formation of low melting phases observed.

The infiltration of clinker melt and the corrosion of the elastifier reduce the flexibility
of the structure of the affected brick zones. This can result in discontinuous wear
by spallings of brick hot faces, if increased thermomechanical and/or mechanical
influences act upon the masonry.

In the case of brick and castable products from the system Al 2 O 3 –SiO 2 , melts
containing calcium aluminate silicates with an anorthite and/or gehlenite
composition are formed at elevated temperature with relatively low ternary eutectic
melting points in the system CaO–Al 2 O 3 –SiO 2 (Fig. 14). The eutectic melting
temperature is further reduced by the presence of alkali halogenides, so that initial
melting can occur at lower temperatures.

Increased temperatures rapidly lead to an erosion of the refractory lining (erosion of

the brickwork). Typical visual appearances of this type of stress are wavy, sloping,
and concave hot surfaces (Figs. 15, 16).

©Refratechnik Cement GmbH 15

 Fig. 14: The ternary system CaO-Al 2 O 3 -SiO 2 is subdivided by a line with low
melting compounds between the kiln feed and the brick and castable products
from the system Al 2 O 3 -SiO 2 (red line) [24]

15 16

Figs. 15 and 16: Sloping and concave brick hot faces due to sustained
thermochemical overload (basic brick grade, left; fireclay brick grade, right)

©Refratechnik Cement GmbH 16

 4.3. Redox Burning Conditions

Redox burning conditions represent a low proportion of the overall volume of cases
of wear, but can occur more frequently and in some cases determine the course of
degradation causing by inhomogeneous combustion of low grade and alternative fuels.

Basic refractory brick grades with increased iron oxide contents in the magnesia
(alpine magnesia), e.g. magnesia-chromite bricks, have a higher susceptibility
to these burning conditions. In a reducing atmosphere, the magnesioferrite
(MgFe 3+2 O 4), contained in the alpine magnesia, is reduced to magnesiowustite
((Mg,Fe 2+)O) (reduction of the trivalent iron to bivalent iron), and this involves a
significant reduction of volume (≈ 20%).

This is macroscopically indicated by bleaching of the reduced hot face of the

brick (Fig. 17). Figs. 18 and 19 show the microstructure of an unchanged high-iron
magnesia with segregations of magnesioferrite and a high-iron magnesia after the
influence of a reducing atmosphere.

Fig. 17: Structure of an overheated and redox-subjected magnesia-chromite brick

Figs. 18 and 19: Microscopic structural changes under redox burning conditions,
(left: unchanged high-iron sinter magnesia with MF (MgFe 3+2 O 4) segregations;
right: high-iron sinter magnesia after the influence of a reducing atmosphere)

©Refratechnik Cement GmbH 17

If redox burning cycles occur, there are frequent changes between magnesioferrite
and magnesiowustite, resulting in the structural weakening of the affected brick
horizons. This can lead to a premature wear as a result of spallings of the redox-
subjected brick zones.
If additional infiltrated sulphate salts are present in the structure of the refractory
lining, and particularly under the influence of sulphur excess, sulphide compounds
can form from these under strongly reducing conditions. The sulphides K 2 S,
oldhamite (CaS), K 2 S 3, KFeS 2 were determined in analyzed used brick samples.
Macroscopically, the presence of the sulphides is visible by a greyish to blackish
colour of the brick structure (Fig. 20). The micrograph in Fig. 21 shows the sulphide
KFeS 2 , which partially fills the pore space. When oxidizing conditions predominate
again, an oxidation of the sulphides takes place, accompanied by a significant
volume increase. This leads to expansion of the brick structure resulting in the
destruction of the brick [21, 25] (Figs. 22 and 23).

Fig. 20: grey-blackened brick structure,

indicating sulphides in the brick.

Fig. 21: brick microstructure with KFeS 2 ,

which partially fills the pore space of the brick

©Refratechnik Cement GmbH 18

 22 23

Figs. 22 and 23: On the left: a used magnesia-spinel brick with sulphides in the hot
face area and sulphate salts in deeper brick horizons. On the right: expansion effect
due to oxidization of sulphides in the hot face part of the brick

Table 7 shows examples of reaction equations under reducing and oxidising

conditions. During kiln shutdowns, and particularly during removal of the refractory
lining, an intensive H 2 S odour is frequently discernible, due to the hygroscopic
character of these sulphides. Table 8 shows examples of reaction equations.

Burning Reaction Equations

Conditions
Reducing MgFe 2 O 4 + CO 3(Mg,Fe)O + CO 2
Oxidizing 3(Mg,Fe)O + 1/
2 O2 MgFe 2 O 4
(ASM)(ASM)

Reducing K 2 SO 4 + 4CO K 2 S + 4CO 2

the Alkali-Sulfate-Modulus

K2SO4+K2SO4+K2SO4 K2SO4 K2SO4+K2SO4+

K2Ofree K2Ofree
>1

Reducing K 2 SO 4 + 8CO + 2SO 2 K 2 S 3 + 8CO 2

KCI+ KCI+ KCI+ KCI+ KCI+ KCI+
71
NaCIO CI
Alkali-Sulfate-Modulus

Reducing MgFe 2 O 4 + K 2 SO 4 + 13CO + 3SO 2 2KFeS 2 + MgO + 13CO 2

– 2 –
ClinkerClinker

>1
6271

Oxidizing 2KFeS 2 + 8O 2 K 2 SO 4 + Fe 2 (SO 4) 3

SO3
80
in Cement

+
O 2O

Table 7: Examples of reaction equations

SO3
9462

80
K2O K2Na
in Cement

1
ASM= ASM=
94

SO3free SO3free
of the of

<1

CaS + 2H 2 O Ca(OH) 2 + H 2 S
Calculation

<1

KFeS 2 + 4H 2 O K(OH) + Fe(OH) 3 + 2H 2 S

Calculation

Table 8: Reaction Equations

©Refratechnik Cement GmbH 19

4.4 Corrosion of the Kiln Shell and Other
Metal Components (Anchors etc.)

Occurrences of corrosion of the kiln shell are well known in the cement industry
and are undoubtedly related to the composition of the kiln gas atmosphere. The
increased use of alternative and waste fuels increases the rate of deterioration
of the kiln shell and also corrosion of the metal anchoring of castable linings by
chemical corrosion under the influence of temperature (scaling) (Fig. 24).

Fig. 24: Corroded kiln shell

Scaling is caused by contact reactions between the metal components (kiln shell,
anchoring, etc.) and hot gases and/or vapours of volatile components from the kiln
gas atmosphere (K 2 O, Na 2 O, SO 3, Cl -, H 2 O, O 2). These elements and compounds
migrate through open joints and pores of the refractory lining and condense
as salt compounds in cooler zones, mostly in the area of the metallic units and
components.

Depending on the alkali/sulphate ratio and the oxygen partial pressure, reaction
products, such as magnetite (Fe 3 O 4), hematite (Fe 2 O 3), pyrrhotite (Fe1-x S), troilite
(FeS) and pyrite (FeS 2), presented in the ternary system Fe–S–O, form under the
prevailing temperature conditions (Fig. 25).

Fig. 25: Ternary system Fe–S–O

As a consequence of the corrosion, the scaled metal plates become brittle and flake
off. The presence of alkali chlorides accelerates the corrosion process. Due to the
hygroscopic effect of the alkali chlorides, rusting can also occur during longer kiln
downtimes.

©Refratechnik Cement GmbH 20

 5. Conclusions and Prospects

The post-mortem analyses of refractory lining of waste-fired rotary cement kilns

clearly demonstrate that more than 60% of the degradation of the refractory
material is due to the high load by harmful atmospheric particles of the kiln gases.

Our development objectives therefore concentrate on shaped and unshaped

refractory products, which on the one hand provide increased resistance to
infiltration and diffusion processes and on the other hand are mineralogically
structured in such a way that they do not react with the infiltrates to form harmful
secondary phases. The latest state of materials development and the available
materials grades has already been dealt with in detail elsewhere [14, 26, 27]. The
research confirms that due to the individual modes of operating cement plants,
taking into account the regional conditions, no harmonization and standardization
of refractory materials will be achieved, but instead coordinated lining concepts
from an extended range of new or modified grades of material have to be used.
However, this excludes the possibility of the refractory materials becoming
commodity products, readily accessible on the Internet.

For this reason, refractory products will, in the future, continue to be purchased as
branded products and not on the basis of material numbers, if positive operational
results are to be achieved. Instead of an all-round brick capable of being used in
all zones of a cement kiln, a balanced lining will be used with fine graduations,
depending on the area of application.

©Refratechnik Cement GmbH 21

6. The Future of Waste-Fired
Cement Burning Kilns

In the upper cyclones, high alumina bricks and standard refractory castables will
continue to be used. However, as a result of the preferred condensation range of
the complex alkali salts between 700 and 1100 °C, the use of refractory castables
with autogeneous ”surface sealing“ or special bricks from the Al 2 O 3 –SiO 2 system
with a comparable ”sealing“ of the entire brick structure, is recommended in the
calcinator, the riser duct, and the kiln inlet.

Dense basic bricks, with open porosity approaching zero and inert behaviour in
relation to alkalis, sulphur and CO, are another future alternative to standard high
alumina bricks in the preheating and safety zones.

In cases of high SO 2 /SO 3 charging of the kiln gas atmosphere, the use of calcium
cement-free monolithic refractory materials is recommended. This particularly
applies to the kiln hood, bullnose, cooler sidewalls, and cooler banks.

Special bricks based on Al 2 O 3 –SiO 2 with internal structural sealing are currently
being tested in zones outside the burning zone. Based on the same material
system, basic bricks, inert to alkalis and sulphur, have been developed for
thermal insulation. Internal and external process testing is still in progress. Basic
lightweight refractories are being designed for the thermal back insulation of the
working lining, and with a higher bulk density, these can also be installed as a
working lining. An innovation is the use of ”gas-impermeable“ magnesia-spinel
bricks for the burning zone. These can be further optimized by the presence of
secondary phases with a high resistance to sulphates and CO. In comparison with
standard fired brick grades, their open porosity has been reduced from 16–19%
to 8–10%. The bricks should not be installed by the clench method, to avoid the
alkali salt condensates penetrating through the joints to the kiln shell, corroding it.
Instead, special ”self-sealing“ mortars have to be used (Table 9).

Refractory castables and mortar with ”post-forming surface sealing“

during use

Special Al 2 O 3 -SiO 2 bricks with prefabricated ”internal sealing“

of the structure

Dense basic special bricks, chemically inert to alkali and sulphur,

with closed porosity approaching zero

Thermally insulating bricks, chemically inert to alkali and sulphur,

with a bulk density of 1.0g/cm 3 or 1.4g/cm 3

”Gas-impermeable“ magnesia-spinel bricks with a minimized

open porosity of 8 – 10%

Table 9: Some product developments for cement kilns

using secondary waste fuels

©Refratechnik Cement GmbH 22

 References

[1] W. Bittner: Trends in the cement industry. REFRA-Kolloquium 2000, Berlin,
Published by Refratechnik Cement GmbH, Göttingen, 25-38

[2]  H. Krogbeumker: Practical use of secondary fuels at the Phoenix Cement
Works. REFRA-Kolloquium 2000, Berlin, Published by Refratechnik Cement
GmbH, Göttingen, 169-183

[3]  W. Kreft: Betriebskostensenkung beim Zementklinkerbrand durch rationelle

Energieanwendung und Einsatz von Ersatz- und Abfallbrennstoffen.
REFRA-Kolloquium 1989, Malmö, Published by Refratechnik Cement GmbH,
Göttingen, 77-94

[4] P. Liebl, W. Gerger: Nutzen und Grenzen beim Einsatz von Sekundärbrenn­
stoffen. ZKG International 46 (1993) [10] 632-638; Benefits and limitations
when using secondary materials, ZKG International 46 (1993) [12]
E 327-E 332

[5] R . Gaebel, W. Nachtwey: Alternative fuels in the cement industry. REFRA-

Kolloquium 2000, Berlin, Published by Refratechnik Cement GmbH, Göttingen,
151-168

[6]  G . Hotz: Entwicklung der Zementbrenntechnologie im Drehofen und dessen

feuerfeste Ausmauerung. REFRA-Kolloquium 1979, Göttingen, Published by
Refratechnik Cement GmbH, Göttingen, 80-93

[7]  G . Hotz, P. Bartha: Stand der feuerfesten Zustellung von Drehofenanlagen.

ZKG International 28 (1975) [6] 236-240

[8]  P. Bartha: Mineralogisch-chemische Veränderung an Dolomitsteinen während

ihres Einsatzes in Zementdrehöfen. ZKG International 25 (1972) [8] 359-364

[9] W. Münchberg, J.G.M. De Jong: Verhalten von keramisch gebundenen

Dolomitsteinen in Zementdrehrohröfen bei Infiltrationen von Ofengasen.
Ber. Dt. Keram. Ges. 52 (1975) [5] 108-117

[10] P . Bartha: Direktgebundene Periklasspinellsteine und ihr Einsatz

in der Zementindustrie. ZKG International 35 (1982) [9] 500-506

[11] H.-J. Klischat, G. Weibel: Magnesia-spinel bricks with differentiated

properties for the sintering and transition zones of rotary cement kilns.
Refra Symposium 1993, Munich, Published by Refratechnik Cement GmbH,
Göttingen, 33-64

[12] P . Bartha, H.-J. Klischat: Klassifikation von Magnesia-Steinen nach

Spezifikation und Gebrauchswert im Zementdrehrohrofen. ZKG International
47 (1994) [8] 474-478; Classification of magnesia bricks in rotary cement kilns
according to specification and serviceability, ZKG International 47 (1994) [10]
E 277-E 280

[13] H
 .-J. Klischat, G. Weibel, P. Bartha: Entwicklungsstand chromerzfreier
Magnesiasteinsorten für die Zementindustrie. ZKG International 50 (1997) [8]
418-428

©Refratechnik Cement GmbH 23

[14] K . Beimdiek, H.-J. Klischat: REFRA-Line – an update of monolithic refractory
lining system for rotary cement kilns. REFRA-Kolloquium 2000, Berlin,
Published by Refratechnik Cement GmbH, Göttingen, 74-89

[15] M. Häwecker, J. Tiemann, E. Schmitt: Monolithische Feuerfestzustellung

von Zementbrennanlagen. ZKG International 53 (2000) [11] 614-620

[16] P . Bartha, H.-J. Klischat: Present State of the Refractory Lining

for Cement Kilns. CN-REFRACTORIES 6 (1999) [3] 31-38

[17] R .C. Weast: CRC Handbook of Chemistry and Physics. 66 th edition

(1985-1986), CRC Press, Inc., Boca Raton, Florida, U.S.A.

[18] E . Lax: D’Ans-Lax Taschenbuch für Chemiker und Physiker. 3rd edition (1967),
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[19] G
 . Routschka (Hrsg): Taschenbuch FEUERFESTE WERKSTOFFE, 3rd edition
(2001), Vulkan Verlag, Essen

[20] P . Bartha: Probleme und Entwicklung bei feuerfesten Steinen für mit Feststoff
beheizte Drehöfen. ZKG International 35 (1982) [5] 274-277

[21] H
 . Barthel, I. Müller: The Influence of Alkali Oxide, Sulphur and Chlorine on
the Wear of Magnesia Chrome Bricks in Rotary Cement Kilns. Interceram
Special Issue (1984) 18-21

[22] H. Naefe, M. Naziri, H. Walk: Optimale chromfreie Brennzonenauskleidung

von Zementdrehöfen. ZKG International 46 (1993) [4] 204-210: Optimum
chrome-free burning zone lining for rotary cement kilns. ZKG International 46
(1993) [6] E 159-E 165

[23] L . Kilb, J. Södje: Salt infiltrations in refractory linings due to the application
of alternative fuels. REFRA-Kolloquium 2000, Berlin, Published by
Refratechnik Cement GmbH, Göttingen, 186-198

[24] P . Bartha, E. Hobrecht, H.-J. Klischat, G. Weibel: The use of basic and high
alumina bricks in highly thermally and chemically stressed lime recovery kilns
with special regard to thermal insulation considerations. Refratechnik Report
No. 56, Published by Refratechnik Cement GmbH, Göttingen

[25] F . Trojer: Futterzerstörung durch Alkalisulfid- und -Sulphatphasen

im Zement-Rotierofen. Radex-Rundschau (1961) [2] 546-552

[26] H.-J. Klischat, H. Wirsing: Development of chrome ore-free structural

flexibility systems for basic bricks. REFRA-Kolloquium 2000, Berlin,
Published by Refratechnik Cement GmbH, Göttingen, 41-58

[27] H
 . Liever: Application and performance of Refratechnik’s advanced
basic refractories. REFRA-Kolloquium 2000, Berlin, Published by
Refratechnik Cement GmbH, Göttingen, 60-72

©Refratechnik Cement GmbH 24

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