Refractories For The Lime Kiln Industries
Refractories For The Lime Kiln Industries
Refractories For The Lime Kiln Industries
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H.-J. Klischat, H. Merker
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The lining of lime shaft and lime rotary kilns is quite complex, although the lime burning process consists mainly of the decarbonization
reaction of natural limestone to achieve calcium oxide. However, the construction of a lime shaft kiln can be rather complicated to realize
a reasonable thermal efficiency when a coarse-grained material is processed. On the other hand, in case of a fine-grained material with
a small particle size, a lime rotary kiln has to be used.
Every kiln system, whether shaft or rotary kiln, requires an especially tailored refractory lining design to achieve an optimum performance
Dr. Hans-Jürgen Klischat (41) and production behaviour. The various zones of each kiln system, preheating zone, burning zone, and cooling zone each have to be
studied Pit and Quarry lined with suitable refractories. Preheating and cooling zone are lined with refractories from the binary system Al2O3–SiO2, while the
between 1979–1986 at the burning zone is progressively more lined with basic bricks at the cost of andalusite and bauxite bricks due to increasing temperatures
Institut für Nichtmetallische and thermal load.
Werkstoffe of the Techni-
cal University Clausthal. He To achieve a satisfactory thermal insulation, shaft kilns are insulated by a multilayered wall consisting of silicate plates, lightweight bricks,
subsequently received his fireclay or insulating fireclay bricks and the working lining. Rotary kilns are insulated by a two-layer-lining or a lining with so-called clog
Ph.D at the Institut für bricks comprising a recess on the cold side. With an individual lining concept consisting of adjusted refractory grades, the lime kiln can
Nichtmetallische Werkstoffe, be operated satisfactorily and smoothly.
AG Keramik-Email in 1989. CN SPECIAL REFRACTORIES · (2000) (2)
Since 1989, he has been
employed at REFRATECHNIK
GmbH in Göttingen, and paring and upgrading natural carbonate rocks. The main
focusses on the field of
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developing refractory bricks
component of limestone rocks is calcium carbonate. The
for the cement industry. In
Limestone is one of the few minerals present in almost limestone is called dolomitic or dolomite as the amount of
1997, he was named Head unlimited quantity throughout the world. About 7 % of the magnesium increases.
of the R&D Department of Earth’s crust consists of this material. The earliest traces of
REFRATECHNIK GmbH (all calcined limestone are about 12,000 years old, and about Depending on the degree of upgrading, a distinction is made
Germany). 5,500 years ago the first professional lime kiln went into between:
operation in Mesopotamia [1]. N unburnt lime products
N burnt lime products
N slaked lime products.
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+'* =^Ûgbmbhg After the limestone has been extracted, crushed, washed,
and classified, the first unburnt end product is obtained, the
The term lime is frequently used to describe lime products raw lime stone. This can then be fed in the required particle
such as quicklime and slaked lime. Often however “lime” size to a shaft or rotary kiln, resulting in the burnt product
Harald Merker (38) stud- is also incorrectly used to mean limestone products such quicklime. In the hydration plant the calcined lime is crushed
ied Mining Engineering at as lime fertilizer. This confusion of terms frequently leads to and ground, the end product being slaked lime. “Lime” in the
the Institute of Mining of misunderstandings. Lime products are produced by pre- following paper always means quicklime.
the Technical University
Clausthal between 1982
and 1988. Since 1989,
he has been employed at
REFRATECHNIK as a Sales
Engineer for the cement in-
dustry. Since the beginning
of 1999 he is Manager of
the company’s new Lime
Department (all Germany).
Fig. 1
World production
of quicklime and
slaked lime
including dead
burnt dolomite in
1998 [3]
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The world output of limestone and other minerals contain-
ing calcium carbonate, such as dolomite, is estimated at
between 2000 and 4000 million t per year. In most coun-
tries limestone is used mainly as an aggregate in the build-
ing industry and as a raw material for cement production.
Some limestone deposits contain over 95 mass-% CaCO3.
This high-quality limestone is used for producing quicklime
and slaked lime [2]. The world output of quicklime in 1998
is estimated at 116 million t. Fig. 1 shows the countries pro-
ducing more than 2 million t of lime per year in 1998. These
figures are taken from published market surveys. However,
actual lime production must be considerably higher since, as
according to unconfirmed reports, the real lime production
in China alone is estimated at over 100 million t [4], and
the lime produced by in-house plants in the steel and sugar
industry are usually not included in statistics.
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It is not generally known that modern industrial production
would be inconceivable without lime. Although usually not
visible in the end product, it is a necessary component of a
variety of products or is needed for their production. Fig. 2
shows a summary of the main applications of lime products.
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Lime-burning means thermal decomposition of limestone to
56 mass-% quicklime and 44 mass-% carbon dioxide (CO2).
In practice this process is much more complex as there ex-
ists many different kinds of limestone containing different
amounts and kinds of impurities. The calcination process
is as well influenced by the calcination temperature, the
residence time in the kiln, and the particle-size distribution. kilns and other types, (Fig. 4). In view of their capacity and Fig. 2
Oates [2] divides the path of a limestone “particle” through heat consumption, no new kilns of some of the above types Uses of lime in
main industrial
a shaft kiln into five phases (Fig. 3): have been built for some time. Instead there is a trend towards
processes
double-shaft kilns, of the QualiCal, Cimprogetti or Maerz
N In the preheating zone of the kiln, considered to be (PFR principle) type or single-shaft kilns with or without side Fig. 3
phase I, the limestone is heated by the kiln gases from burners, type SIC or Fercalx. The five phases of
ambient temperature to approx. 800 °C. limestone burning
N At about 800 °C the partial pressure of CO2 resulting Differences in the kiln systems and the selection criteria are
from dissociation of the limestone equals the partial pres- due to the different limestone deposits, the particle size of the
sure of the CO2 in the kiln gases. If the temperature con- kiln feed, the desired end product, the desired kiln capacity
Fig. 4
tinues to rise, the limestone begins to decompose into and particularly the specific energy consumption of individual Classification of
CaO and CO2. When the temperature reaches 900 °C, kilns. In general, vertical lime shaft kilns can burn limestone of kiln types for
the decomposed layer is about 0.5 mm thick. a particle size from about 20 mm. The Maerz fine lime kiln is burning lime
N If the temperature is increased further, the partial pres-
sure exceeds 101.3 kPa and decomposition of the par-
ticle can proceed further inwards.
N If all the CaCO3 (calcium carbonate) dissociates before
the particle leaves the combustion zone, the lime will
begin to sinter.
N Lime particles, which still may contain small portions of
CaCO3, leave the burning zone at about 900 °C and
are cooled by the inflowing air for combustion.
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The decomposition of limestone as previously described oc-
curs in all kinds of lime kilns. Modern lime kilns can be di-
vided basically into three main categories: shaft kilns, rotary
an exception, for which the minimum particle size is said to be of corundum. Their Al2O3-content is 70 mass-%. Bauxite
10 mm. Rotary kilns, depending on their type, can process par- bricks have to be distinguished between products based on
ticle sizes from 0–60 mm. This advantage, however, is unfor- diaspore, boehmite and gibbsite respectively. Although they
tunately compensated by the much higher heat consumption posses a comparable chemical composition, bricks based
of this kiln type. On average, the heat consumption of a rotary on gibbsitic bauxite form higher contents of mullite on fir-
lime kiln is about twice that of a modern lime shaft kiln. ing, thus providing a higher refractoriness and hot strength,
a higher density and lower porosity.
. <
aZkZ\m^kblZmbhgh_K^_kZ\mhkrFZm^kbZel Fireclay and high-alumina bricks can either be ceramically
_hkEbf^Dbegl bonded (by ceramic sintering) or phosphate bonded (by ad-
dition of phospharic acid and a subsequent ceramic firing at
In the following a classification of refractory brick grades 1000–1500 °C). Phosphate bonded bricks are character-
for various lime burning systems and zones for lime kilns is ized by an increased resistance to slags, melts, and dust, as
shown. A good survey regarding classification and proper- their porosity is significantly decreased due to the formation
ties of refractories is given in [5]. of highly refractory aluminium phosphate during firing.
The refractoriness of alumina containing bricks is lowered in
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the presence of further compounds (e.g. Fe2O3, TiO2 and al-
Especially for kiln zones with lower temperatures, which are kalies from the raw materials or CaO from the kiln feed). The
thermochemically lower loaded areas of lime burning systems, reaction with CaO, which can take place during lime burning
products from the binary systems SiO2–Al2O3 are still suc- especially at higher temperatures, led to a substitution of the
cessfully used, Fig. 5. All compositions are refractory, i.e. they alumina-containing lining in the hot kiln zones by a basic lining,
show a Seger cone of at least 18 (corresponding 1500 °C). a process which already took place in the cement industry.
A distinction is made between fireclay products containing
below or equal 45 mass-% Al2O3, and high alumina products .'+ ;Zlb\;kb\dl
containing more than 45 mass-% Al2O3. The main mineral
phases in this system are corundum (B-Al2O3) and mullite Due to the increasing loads in lime shaft and rotary kilns, a
(3Al2O3· 2SiO2, 2Al2O3·SiO2 respectively, as mullite is always transition from alumina bricks to basic bricks was observed.
a mixed crystal of varying composition). At first, cheap dolomite bricks were used, but due to their poor
thermal shock resistance and comparably low hot strength of
Fireclay bricks (sometimes also named chamotte bricks) are these installations several premature failures were observed.
made from fired clays or kaolinites. Acidic fireclay bricks con- Furthermore, because of their high hygroscopicity, each kiln
tain between 10 and 35 mass-% Al2O3. Although they show the stop gave problems because of the water pick-up of the dolo-
lowest melting temperatures in the system, they still exhibit an ad- mite lining and the subsequent brick destruction. In a period of
vantageous high alkali resistance. Fireclay bricks with alumina time, dolomitic linings of lime kilns will be a thing of the past.
contents between 35 and 45 mass-% are characterized as alu-
mina rich fireclay bricks, due to their higher Al2O3-content their Magnesia is an interesting material for all high-temperature ap-
refractoriness is increased, compared to acidic fireclay brick plications involving basic products and by-products, like lime
grades. Between 45 and 55 mass-% Al2O3, alumina enriched burning, cement burning, magnesia and dolomite burning, or
fireclay bricks with further increased refractoriness are located. steel production, because of a high refractoriness (melting tem-
perature 2800 °C). To increase the elasticity and the fracture
Bricks on the basis of andalusite (an equimolar natural alumi- toughness and thus the thermal shock resistance and the stress
nosilicate) contain a further increased alumina content of ap- resistivity of basic magnesia bricks, a second compound is add-
prox. 60–63 mass-% Al2O3. Bricks based on sillimanite and ed to the brick material. For many years this second compound
Fig. 5
kyanite, with the same chemical composition as andalusite, was chromite (chrome ore), and these magnesia chromite bricks
Brick grades in the
SiO2–Al2O3 system are used only subordinately. In the high alumina rich region, have become a standard lining in rotary kilns world-wide.
(according to bauxite and mullite bricks are located. They are used in abra-
Welch [6]) sive areas of shaft and rotary kilns due to their high content The bonding of the brick influences the performance of a
magnesia chromite brick refractory lining to a high degree.
In the so-called direct bonded magnesia bricks, often made
from seawater magnesia, the chrome ore grains are bonded
tightly to the surrounding matrix. These bricks were originally
developed for the use in the steel and nonferrous industry.
They distinguish themselves by a high hot strength, they show
only a low high temperature plasticity and a poor thermal
shock resistance. Anyhow, these bricks have been installed
in the hot zones of lime shaft kilns for a period of time.
As it is observed in several kilns, in the presence of alkalies in
oxidizing kiln atmosphere the chrome ore of magnesia chro-
mite bricks can degenerate. This reaction is accompanied
by the formation of presumably toxic hexavalent chromates.
Known from experience, MA-spinel (MgO · Al2O3) is very
suitable to increase the elasticity of basic refractory bricks.
Comparable investigations on the performance behaviour
showed that even an increase of the lining life time could be
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The choice of suitable refractory grades for the different zones
of a kiln is particularly important because of the various loads
from the kiln feed and the kiln atmosphere on the refractory
lining, [8]. Fig. 8 shows the basic wall structure of a lime shaft
kiln divided into the working lining, permanent lining, and insu-
lating layers. In a lime shaft kiln the working lining, i.e. the layer
which is in direct contact with the charge, has to withstand the
following loads in order to ensure a maximum service life:
N abrasion by kiln charge
N mechanical forces, e.g. by expansion of the lining
N thermal shocks
N chemical corrosion.
The permanent lining must have sufficient strength not to be
destroyed by the static pressure of the limestone column, and
to absorb the expansion stresses of the working lining which
are not compensated by the expansion allowance. It should
also have certain “emergency running properties”, so when
the working lining is worn the kiln can operate at least for a
short time without a complete burn-through of the refractory
lining down to the kiln shell.
The kiln operator will quickly realize what the situation is,
owing to the increased temperature of a limited region of the
kiln shell, and will plan the required repair. The insulation be-
hind the permanent lining – usually two or three layers – must
be calculated in a way to adjust the kiln shell temperature to
a preset value without heat accumulating in the individual
layers and adversely affecting the layers in front. Using the
wall structure of a burning zone as an example, two different
possible methods of insulation are described.
The main difference between the two alternatives relates
Fig. 8 to the permanent lining. In the conventional wall structure on
Wall structure and important loads of a typical lime shaft kiln the left side of the diagram, a fireclay brick containing about
30 mass-% Al2O3, (e.g. KRONEX® 30) is used behind the
Fig. 9 working lining. As an alternative, an insulating fireclay brick
Comparison of heat transfer through a conventional lining and a lining with an
insulating brick (as an example in this case REFRATHERM® 150) in the burning zone when
with a porosity of 25–35 mass-% (here REFRATHERM® 150) as
installed with a basic magnesia spinel working lining (as an example REFRAMAG® 85) the first layer behind the working lining can be installed, as
shown on the right side in Fig. 9.
Fig. 12
Installation of
various refractory
grades in a rotary
lime kiln
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As a second example of a detailed solution the ring channel
Fig. 13 N shaft kiln with side burners (type SIC) ceiling of a Maerz shaft kiln is shown. Fig. 14 shows two possi-
Detail of a vertical N Maerz-PFR kiln with ring channel. ble constructions of the ring channel ceiling. On the left, large
allowance for special shapes form a horizontal ceiling. Various constructions
expansion
1'* LaZ_mDbeglpbmaLb]^;nkg^kl are possible, thus requiring a variable number of shapes. The
Fig. 14 right-hand side shows an alternative ceiling construction in the
Detail of ring- At first, the shaft-kiln type with side burners (SIC construction) form of an arch. Similarly, the construction can vary by chang-
channel ceiling of is discussed. In this kiln, in the burner sector (a certain number ing the shapes and the radius of the arch. A common feature
a Maerz-GGR kiln
of burners are uniformly distributed around the periphery on for both solutions is the need for a support of the ceiling con-
one level) the inside diameter of the lining is changed from struction on both the inner and the outer cylindrical brickwork.
2200 mm below the burner level to 2038 mm above the burn- Varying expansions of the inner and outer brickwork may re-
er level. Since the stepping between the individual layers is sult in a tilting of the ceiling construction so that gaps may
open, through which the hot gases can reach the insulating
layers and damage them by overheating.
A new proposed construction for a ring-channel ceiling is il-
lustrated in Fig. 15. To illustrate the idea underlying this pro-
posal, a spherical dish which is limited by an outer cylinder
is considered. The cylinder axis passes through the centre of
the spherical dish. Furthermore, a second, smaller cylinder is
inserted into the first cylinder through the spherical dish. As-
suming that the outer cylinder is the outer boundary of a ring
channel and the inner cylinder is the inner cylindrical lining of
a Maerz-PFR kiln, the remaining part of the spherical-shape
portion is the ring-channel ceiling (Fig. 16). The lining is pro-
vided in concentric rings, using shapes with edges pointing
towards the centre of the sphere. Under these conditions a
ring is intrinsically stable as soon as it is closed, i.e. it does not
need a second internal support in addition to the external one.
Another advantage of this solution is the lining of the complete
ring-channel ceiling with only 2 different shapes.
2 <hg\enlbhg
Limestone or quicklime and the various products manufac-
tured therefrom (slaked lime, milk of lime etc.) have for thou-
sands of years been used by human beings in various sectors
and industrial processes. Limestone deposits of relatively high
quality are available throughout the world, and consequently
the lime industry has also developed world-wide. The leading
lime-producing countries today are China, the USA and the
European countries.
The main uses of lime are closely dependent on the epoch and
geographical conditions. In the past century, the iron and steel
industry was the main customer of the lime industry, with an in-
creasing requirement for lime by the chemical industry, particu-
larly for environmental protection, which has almost overtaken
the iron and steel industry with regard to lime consumption [11]
in the USA. The basically simple calcining process for produc- tory lining of shaft kilns, the working lining, the permanent lin- Fig. 15
ing lime from limestone has become a highly-developed high- ing and the insulation have to be distinguished. The shaft kiln Proposed lining of
the ring-channel
tech process as a result of various impurities in the raw material, is divided into the preheating zone, the burning zone and the
ceiling in a Maerz
variations in the fuel, different kiln systems and the increasingly cooling zone. Generally, with regard to the working lining, kiln
stricter environmental requirements on lime producers. Modern this area should be lined with fireclay brick grades containing
lime producers can choose from a number of kiln systems. One 40 mass-% Al2O3 or, at higher temperatures, 50 mass-% Al2O3 Fig. 16
A new construction
criterion is the specific energy consumption (both of fuel and in the preheating zone. For the burning zone, a lining with ba-
of a ring-channel
electric energy). However, the raw materials, their particle size, sic brick grades (magnesia spinel bricks or magnesia zirconia ceiling proposed by
the kiln capacity and the desired end product properties are bricks) has to be considered with special regard to an increase REFRATECHNIK®
also decisive in the selection of the kiln system. Every lime kiln of the thermal load in all kiln types. In the cooling area, fireclay
requires a special lining design to achieve its optimum produc- brick grades can be used. With this conceptional design, an
tion and performance behaviour. With regard to the refrac- advantageous price-/performance ratio can be achieved.
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