Chap. 2.1-Raw Materials Selection PDF
Chap. 2.1-Raw Materials Selection PDF
Chap. 2.1-Raw Materials Selection PDF
by A. K. Chatterjee*
Dispersed and homogenized raw mixes for the manufacture of portland cement clinker consist
basically of two generically different natural raw materials calcium carbonate (or limestone) and
aluminosilicates (or argillaceous substances) that are complementary in nature in meeting the
stoichiometric needs of forming the clinker phase assemblage. At times, when such stoichiometric
needs cannot be met by the above two primary components, certain corrective materials such as
bauxite, laterite, iron ore or blue dust, sand or sandstone, etc. are used to compensate the specific
chemical shortfalls in the raw mix composition. For certain processing advantages a few chemical
reagents are used as slurry thinners in the wet process and raw grinding operation, as granulation
activators in the process of nodulization in semi-dry plants, as mineralizers in clinker formation,
and as grinding aids in the cement milling process. These are essentially surface-active materials and
are used in very small quantities, when required. Further, in the context of environmental amelioration and resource conservation, a large number of industrial wastes or byproducts are used as basic
or corrective raw materials in the cement industry.
37
38
Basic mechanism. It is widely believed that in order of abundance in the earths crust, calcium
holds the fifth position after oxygen, silicon, aluminum, and iron. On the other hand, carbon dioxide, according to Oates (1998) makes up about 0.03% by volume of the earths atmosphere. The
combination of dissolved calcium ions and carbon dioxide results in the sedimentary deposition of
calcium carbonate, which is subsequently converted into limestone rock.
39
The deposition takes place primarily in two different environments: marine and inland waters, the
descriptions of which have been given by Scoffin (1987) as well as by Tucker and Wright (1990).
The primary marine environment, of course, has its own variety that includes beaches, tidal, subtidal flats, lagoons, reefs, shelves, slopes, and deep basins. Whenever the physico-chemical conditions in the basins had been favorable in terms of concentration, temperature, salinity, water levels,
turbidity, etc. for deposition, thick carbonate deposits formed in shallow seas within a 30 band on
either side of the equator.
So far as the mechanism of deposition is concerned, two main types are recognized inorganic
and organic. The inorganic route involves the direct precipitation or crystallization of carbonate.
This mechanism had occurred in the environments of both marine and inland waters, and had
resulted in some commercially significant deposits.
But it has generally been observed that most of the commercially viable deposits of carbonate
rocks were formed by the organic route. This happened because of the fact that carbonate-secreting organisms such as bivalves, gastropods, brachiopods, corals, echinoderms, foraminifera, various algae, etc. had existed in seawaters quite extensively. A few illustrative scanning electron
micrographs of some fossils associated with limestones are given in Figures 2.1.2 to 2.1.7. Many
such organisms, such as algae, are known to remove carbon dioxide from water, causing precipitation of fine chemical carbonate. Certain other organisms directly remove calcium carbonate from
marine water to form their shells, the accumulation of which gives rise to carbonate deposits. The
carbonate sedimentation by the organic route also had taken place in inland waters but the resultant deposits are generally not as extensive nor commercially as important as those produced in
marine environments.
40
Simple compaction, cementation, neomorphism, microbial micritization, etc., are the specific variants of the diagenetic processes, some details of which have been furnished by Tucker (1991). For
example, compaction occurs during the burial process when the pebbles are crushed, the particles
are closely packed, and pressure-induced dissolution and recrystallization take place. In the cementation process, water supersaturated with calcite passes through porous carbonate layers resulting
in the growth of calcite crystals in pores. The most common cement in medium-to-coarse grained
limestone is sparite or calcite spar. Silica as quartz crystals also acts as a cement in some limestones. In microbial micritization many organisms bore into carbonate deposits and the holes
become filled with calcium carbonate, called micrite, that typically forms an envelope around the
skeletal grains. Neomorphism refers to the progressive transformation of aragonite to calcite or
recrystallization of calcite into coarser crystals.
41
washed from the land. It is evident, therefore, that those parts of the continental plate, which have
remained south of 30S generally, have little limestone. Conversely, those continents that drifted
into, and in some cases across the band 30S to 30N, are relatively rich in limestone deposits.
So far as the distribution of limestone deposits in time is concerned, despite very precise physicochemical and climatic prerequisites for the carbonate deposition as mentioned earlier, the limestone deposits are encountered almost in all the geological eras and periods that span over 600
million years as indicated below:
Quaternary era
up to 1 million years
(Recent times to Pleistocene period)
Tertiary era
up to 75 million years
(Pliocene, Miocene and Eocene periods)
Mesozoic era
Palaeozoic era
Precambrian era
Limestones are not common in the Precambrian shields, although where shallow seas had formed
some carbonate deposition took place. It is believed that such Precambrian limestones were deposited either as inorganic precipitates or as a result of the biochemical activity of very simple
organisms such as bacteria. It may also be mentioned here that most of the Precambrian carbonates have been subjected to metamorphism and dolomitization during the long post-deposition
period. The Palaeozoic to Quaternary Eras are all fossiliferous and have favored the deposition and
formation of carbonate rocks although, according to Strakhov and others (1954), rocks of certain
geological periods (Ordovician or Cretaceous) show predominance of carbonates, while those of
certain other periods (viz. Upper Carboniferous or Triassic) are relatively poor in carbonates.
Further, the limestone deposits in different geographical regions and geological ages had different
environments of deposition. For example, the Carboniferous limestone deposits in England were
formed in equatorial and subtropical conditions, while the later Jurassic limestones and the Cretaceous chalk deposits were formed in the warm temperate zone, apparently at progressively higher
latitudes. From geotectonic evidence it has been seen that where there was progressive subsidence
of the sea bed over prolonged periods, very thick deposits accumulated, an illustration of which
are the Triassic deposits in the Western Dolomites which have a thickness of more than 2000 m.
42
It is the general view of geologists that the sea levels were higher in the past than at present and the
area of shallow seas capable of sustaining carbonate-producing organisms was considerably greater
then. As a result, the environmental condusiveness for carbonate deposition apparently was more
extensive in the Mesozoic and Tertiary periods.
Mineral
group
Crystal
system
Common
substitution
Specific
gravity
Calcite,
CaCO3
Hexagonal
rhombohedral
Mn, Fe, Mg
Aragonite,
CaCO3
Orthorhombic
Dolomite,
CaMg(CO3)2
Hexagonal
rhombohedral
Dissociation temperature at
760 mm pressure and 100%
CO2 atmosphere
Initial
Final
2.72
898C
Sr, Pb, Zn
2.94
425C
(aragonite to calcite)
898C
2.86
725C (MgCO3)
890C
Aragonite is pseudo-stable with respect to calcite under ambient conditions and has a higher
solubility in water by about 7% at all temperatures. It has been reported that aragonite slowly
re-crystallizes into calcite in the presence of water. However, in the absence of water this transformation takes places at 400C to 500C. Calcite is metastable with respect to dolomite in seawater
that contains dissolved magnesium. The process of dolomitization is a slow geological process, and
it is slowly reversed in the presence of fresh water.
According to Ghosh (1983), rise in temperature of seawater in the proximity of shelf or equator
decreases the solubility of CO2 in water and favors precipitation of CaCO3. Agitation of water by
breakers releases CO2 and favors carbonate precipitation. The solubility of CO2 decreases with
decrease in atmospheric pressure. Evaporation in restricted basins results in a decrease in CO2 and
an increase of salinity, facilitating carbonate deposition.
Notwithstanding what has been stated above regarding the solubility of calcium carbonate minerals, it may be mentioned here that the high calcium and dolomitic limestones are among the most
chemically stable substances. Decomposition never occurs at ordinary temperatures and these
minerals are also unaffected by CO2 -free water, except for very negligible dissolution as mentioned
by Boynton (1980).
Classification of Limestones
Limestone is treated as an omnibus term and is often imprecisely used to represent any calcium
carbonate-bearing rock. However, it can be classified on the basis of various criteria, depending on
the purpose for which a given classification is deemed necessary. A fairly detailed treatise on the
classification of limestones has been furnished by Ghosh (1983). Most classifications obviously are
for geological needs. For the purposes of industrial applications like cement making, one may
derive ones own version from such classifications and distinguish one limestone from the other in
terms of their genesis, lithology, mineralogy, texture, and microstructure.
The major platform of distinction is the presence or absence of fossils related to the organic or
inorganic genesis. Having recognized this differentiation, one may further classify the types based
on broad lithology. This mode of distinction can be developed as follows:
1. Inorganic sedimentary limestones typical examples include travertine deposited from
natural hot springs; tufa, a soft porous rock also associated with natural springs; stalactites
or stalagmites, columnar calcitic deposits inside the caves; micrites originating from
calcitic mud or silt, etc.
2. Fossiliferous sedimentary limestones rocks of widely differing textural and microstructural
characteristics and fossil content broadly differentiated as biosparites or biomicrites. While
the former represent the more extensively occurring massive well-bedded limestones consisting of fossil skeletons or small shells in a recrystallised calcitic matrix, the latter refer to the
limestones having organic debris in a micrite matrix. Within this broad frame one may
further distinguish the following types:
i. Algal limestone resulting from the action of algae
ii. Oolitic or pisolitic limestone showing round calcitic grains
iii. Reef or coral limestone characterized by nonbedded large fossiliferous deposits
iv. Chalk representing a white soft rock with very little land-derived silty material, generally
thick (50 m to 400 m) in deposition
v. Marl designating an impure soft rock of marine origin in which varying amounts of clay
and sand are present in a loosely knit crystalline structure
vi. Sea sand, essentially of quaternary age, representing calcareous sand carried on to sea
beaches, occasionally with a mixed mineralogy of aragonite and calcite
43
44
3. Metamorphic carbonate rock marble which is highly crystalline and often highly
dolomitic, although marbles derived from pure limestones through metamorphism without
dolomitization, consist simply of coarse white calcite grains
4. Igneous carbonate rock Carbonatite, which is effusive in nature and rare in occurrence
All of the above limestones can be further classified on the basis of certain textural and compositional yardsticks, some illustrations of which are given in Table 2.1.2 and 2.1.3.
The micro-structural variations encountered in different limestones are illustrated in Figures 2.1.8
to 2.1.16.
Nomenclature of rock
95 97
Same as above
Calcite limestone
80 95
MgCO3 + others
Magnesian limestone
Arenaceous/argillaceous/siliceous
/cherty limestone
FeCO3
FeO(OH)
FeS2
40 80%
+ others
Ferruginous limestone
C + others
Carbonaceous limestone
P + others
Phosphatic limestone
MgCO3 + others
Dolomitic limestone
Crystallinity
< 0.01
Micro crystalline
0.10 0.01
0.25 0.10
Fine grained
0.06 0.004
0.50 0.25
Medium grained
0.20 0.06
1.00 0.50
Coarse grained
1.0 0.20
> 1.00
45
It may be relevant to recapitulate here a few of the classical approaches made in the past to differentiate the limestones. A classification often referred to by the geologists is by Pettijohm (1957)
which distinguishes calcirudite, calcarenite, and calcilulite based on gravel, sand, and silt-sized
carbonate particles respectively.The classifications based on calcite and dolomite content as
proposed by Carozzi (1960), based on Ca/Mg ratio as proposed by Chilingar (1957), or based on
calcite, dolomite, and clay content as reported by Bissell and Chilingar (1967) are often useful for
specific purposes. Fitting a given limestone resource to one or more classifications ultimately helps
in understanding its behavioral pattern by comparison with parallels.
46
47
lenticular, folded, or structurally disturbed deposits; or deposits in hilly terrains with a little structural disturbance. The intricate deposits include highly complicated, highly folded, faulted and
dislocated, and highly lenticular deposits or those deposits that are interbedded with clay or shale,
or show extreme variations in form, thickness, and assay values. Many Precambrian limestone
deposits belong to this category. A high degree of intensity of prospecting is required in assessing
deposits of this kind, particularly for mechanized mining.
It should be borne in mind that the adequacy of exploration and proving of a limestone deposit
for setting up a cement plant ultimately has to be judged by the optimum expenditure incurred in
the exploration program in order to avoid risky ventures of developing inadequately explored
deposits or unprofitable propositions of setting up a cement plant on over explored deposits.
The most judicious course to assess the adequacy of an exploration program of a limestone deposit
is to adopt the minimum risk factor method which is based on the reliability of reserves estimated
in terms of quality and quantity.
The tentative target of an exploration program for a given deposit is to ensure the estimate of its
reserves of appropriate reliability as indicated in Table 2.1.4. Arriving at the delineation of reserves
of the reliability level of the proved category is considered a prerequisite for the preparation of a
detailed project report and final investment decisions.
48
Table 2.1.4. Illustrative Targets of Limestone Reserves for Cement Plants at the
Resource Proving Stage
Category
of reserve
Reliability
indices*
Corresponding
stage of proving
Proved
Vg 1%
Vr 10%
Probable
Possible
5000 tpd
7500 tpd
Detailed
exploration
60
100
150
Vg 3%
Vr 30%
Subsurface
prospecting
45
75
110
Vg 4%
Vr 50%
Reconnaissance
prospecting
82
140
205
* Vg is the anticipated deviation of CaO content from the actual value as mined.
* Vr is the anticipated difference between the estimated and mined reser ves.
49
Constituents
CaO
MgO (max)
SiO2 + Al2O3 + Fe2O3
44 52
Minimum 40
3.5
Mn2O3
< 0.5
< 3.0
R2O(K2O + Na2O)
< 0.6
< 1.0
< 0.6
< 0.8
P2O5
< 0.6
< 1.0
< 0.015
< 0.05
< 8.0
< 10.0
Cl
Free SiO2
50
Chemical composition
Decomposition temperature, C
Dolomite
CaMg(CO3)2
700 750
Ankerite
Ca(Mg,Fe)2(CO3)2
700
MgCO3
660
(Fe,Mg)CO3
580
Mg(OH)2
375 490
Magnesite
Magnesian Siderite
Brucite
The presence of coarse grains of quartz or siliceous veins is undesirable as it may affect the grindability and reactivity of the limestone as explained later in this chapter. The presence of sulfur as
sulfate is undesirable as it is difficult to decompose.
Physico-Textural Features
The physical properties of limestones show wide variation, apparently related to the prior history
of rock formation and the resultant minerographic and textural features.
The color of limestones reflects the level and nature of associated minerals and impurities. High
purity calcite limestones are white in color and other shades in the less pure varieties are essentially
caused by carbonaceous and ferruginous materials.
Depending on the mineralogy and texture, the porosity of the limestones, according to
Schwarzkopf (1994), varies from almost zero to 30%, while the upper value for chalks and marls
often goes up to 40% and 50% respectively. For predominantly occurring compact limestones, it is
in the range of 2% to 5%. Similarly, dolomites normally show relatively low porosity level
(1% to 10%).
The water absorption in limestones follows the pattern of pores and level of porosity. While it may
be negligible in dense varieties, it may go up to 20% in porous chalky varieties.
The Mohs hardness of most limestones lie in the range of 2 to 4. The apparent density of limestones on drying at 110C ranges from 1.5 to 2.6 g/cm3.
In addition to the above basic physical properties, a few characteristics like crushability and grindability as well as the physical behavior of crushed and screened limestones are important for the
process of cement manufacture.
Crushability is a generalized parameter expressing the energy consumed in crushing a rock under a
dynamic load. The property takes into account the elastic, plastic, and strength behavior of a given
sample and is measured as a work index. Similarly, grindability is determined with the help of a
specially designed ball mill according to standard practice and is expressed as Bonds index. For
details, one may refer to the article by Bond. The Bond grindability index for commonly occurring
compact limestones lies in the range of 4 to 13 kWh/short ton.
Sometimes, for crusher selection purposes, the compressive strength of limestones, determined on
sized cylindrical samples, is used. The compressive strength of limestones, like other properties,
also shows wide variation from 10 to 200 MPa.
The bulk density largely depends on the apparent density of limestones, their particle size distribution, and particle shape. In general, the reported range of variation of bulk density of limestones is
1400 to 2700 kg/m3, although typical values fall in the range of 1400 to 1600 kg/m3.
The external angle of repose for screened limestone is generally 35 45 but is affected by size
distribution, fines level, and moisture content.
The abrasion resistance characteristic of crushed stone is often called for in the process of technological assessment.
A broad framework of sequential steps and scope of technological assessment of limestones has
been given by Ghosh and Chatterjee (1979). Some of the desirable characteristics are 1) the average
size of calcite crystals (not particle size) should preferably be less than 0.25 mm, 2) presence of
coarse grains of quartz and siliceous veins is undesirable, 3) limestone should have low moisture
content (<5%), and 4) limestone should have low compressive strength (below 100 MPa).
For a general appreciation of the extent of variability of physical properties encountered in limestones and difficulties of correlating the physical properties with their chemical characteristics, a
set of data for some limestone samples of different ages is furnished in Table 2.1.7.
The limestones shown here are all high in silica content. Reasons for the major differences in
grindability probably include differences in the mineralogy of the siliceous contaminant.
51
52
CaO (total), %
39.7
48.7
43.9
46.6
41.5
47.4
43.0
46.4
10
47.7
44.5
SiO2 (total), %
22.6
10.5
18.9
11.7
15.7
10.2
13.0
10.6
12.6
18.0
L.O.I., %
36.3
37.5
34.9
38.1
36.1
38.2
35.5
36.1
37.5
34.4
Calcite, %
70.9
87.0
78.4
80.5
63.9
82.1
72.5
76.3
85.2
77.7
Quartz, %
16.8
7.9
14.5
8.2
10.1
7.4
10.3
7.3
8.7
14.5
18.8
12.0
Dolomite, %
5.0
4.6
7.9
3.3
Sp. gravity
2.73
2.70
2.72
2.63
2.66
2.66
2.70
2.66
2.59
2.62
Bulk density,
g/cm3
1.63
1.65
1.67
1.41
1.44
1.46
1.46
1.45
1.53
1.45
Porosity, %
4.03
4.45
6.16
2.51
3.73
4.60
2.65
2.41
2.24
1.91
Abrasion, %
36.76
65.38
63.16
22.06
23.74
Compressive
strength, MPa
84.4
48.0
48.1
Bonds index,
kWh/short ton
4.60
4.64
10.28
28.16
123.0
5.20
30.64 30.65
140.0 157.6
6.82 11.36
22.96
110.2
10.1
110.3
9.64
94.9
12.61
18.45
113.6
12.35
53
Table 2.1.8. Effect of Calcite Crystal Size on the Decarbonation Rate of Limestones
Limestone A
Limestone B
Composition, wt. %
SiO2
Al2O3
Fe2O3
CaO
MgO
LOI
Na2O
K2O
SO3
Cl
T.C.
Free SiO2
12.2
1.70
0.80
46.40
1.20
36.60
0.16
0.32
0.30
0.01
83.40
2.90
11.20
2.30
1.10
45.90
2.00
36.10
0.42
0.43
0.10
0.001
83.20
2.20
Calcite, size m
Min
Max
Mean
8
20
12
750
2100
1000
10.43
28.05
36.42
36.49
9.61
17.90
33.22
33.68
ARGILLACEOUS MATERIALS
The expression argillaceous materials
refers to all fine-grained natural earthy
substances that are alternatively known as
clay. It includes shales and argillites.
Chemically, these materials are essentially
hydrous aluminum silicates, with magnesium or iron substitution wholly or in part
for the aluminum in certain minerals, and
with alkalies or alkaline earths also present
as essential constituents in a few others. A
shale deposit as a source of argillaceous
materials in cement manufacturing is
shown in Figure 2.1.17.
Some argillaceous materials are composed of a single clay mineral but in many there is a mixture of
them. In addition to the clay minerals, many argillaceous materials contain non-clay minerals like
quartz, calcite, feldspar, sulphidic species, etc. Many others may contain organic substances as well as
water-soluble salts. Some clay materials may contain phases that are amorphous.
54
Structurally, these clay minerals are part of the larger family of phyllosilicates and are characterized
by interlinked tetrahedral and octahedral sheets. The structural configuration of clay minerals has
been dealt with in fair detail by Grim (1962), Brindley and Brown (1989), and Velde (1992), a
summary of which is presented below.
The structural variations among the clay minerals can be understood by considering various physical combinations of tetrahedral and octahedral sheets and the electrostatic effect chemical substitution has on the structural units. The tetrahedral sheets are composed primarily of Si4+ and
oxygen, but minor amounts of Al3+ or Fe3+ may substitute for Si4+. The substitution of Mg2+ for
Si4+ leaves the tetrahedral sheet negatively charged. The cations of the octahedral sheet are
composed primarily of Al3+, Fe3+, Mg2+, and Fe2+, but all other transition elements, except Sc, may
be included. The anions of the octahedral sheet are O2-, OH1- and F 1-. The smallest unit of the
octahedral sheet contains three octahedra having an ideal net charge of negative six, i.e. three O2-.
If the negative charge is balanced by two trivalent cations, the layer is referred to as dioctahedral
layer; if balanced by three bivalent cations, the layer is referred to as a trioctahedral layer.
Substitution of bivalent cations for trivalent cations, and univalent cations (Li1+) for bivalent
cations or unfilled octahedral sites, leaves the octahedral layer a net negative charge. The tetrahedral apical oxygen is shared with the octahedral layer to join the two types of layers.
The least complicated clay minerals are the 1:1 clay minerals composed of one tetrahedral (T) layer
and one octahedral (O) layer. These 1:1 clay minerals are also referred to as TO minerals. The TO
package has a basal spacing (nominal thickness) of 0.7 nm (7), and the minerals are commonly
referred to as 7 minerals. Clay minerals that are composed of two tetrahedral layers and one octahedral layer are referred to as 2:1 clay minerals or TOT minerals. The apical oxygens of the two
tetrahedral sheets project into the octahedral sheet. The 2:1 structure has a basal spacing (nominal
thickness) of 1.0 nm (10). The multitude of variation in clay minerals is caused by substitution in
the octahedral and tetrahedral layers, resulting in charge deficits. The manner in which the charge
deficit is balanced leads to many of the useful and unique properties of clay minerals.
As a result of such diversity of constitution of argillaceous materials, their technical assessment for
specific applications is rather complex. Broadly speaking, the property controlling factors in
argillaceous materials are the following:
1. Clay minerals
2. Non-clay minerals
3. Organic substances
4. Exchangeable ions and soluble salts
5. Particle characteristics including shape, size, and orientation
6. Structural assembling formed by 1:1 or 2:1 linkage of tetrahedral and octahedral sheets as well
as neutralization of excess layer charge by various interlayer materials
55
Some relevant data regarding the structure and properties of clay minerals are furnished in
Table 2.1.9.
Name
Broad composition
Structural
features
Cationexchange
capacity,
(Meq/100)
1. Allophane
X-ray amorphous
2. Kaolinite
(OH)8Si4Al4O10
46.54%
SiO2
39.50%
Al2O3
H2O20
13.96%
3 15
3. Halloysite
Two forms:
(OH)8Si4Al4O10 or
(OH)8Si4Al4O104H2O
Halloysite minerals are made up of
successive layers with the same structural composition as those of kaolinite.
A little substitution seen.
5 40
80 150
5. Illite
Muscovite-like dioctahedral:
(OH) 4 K 2 (Si 6 Al 2 )Al 4 O 20 Biotitic type
is trioctahedral with incorporation of
Mg and Fe. Illites differ from mica in
having less replacement of Al for Si,
less K and less randomness of silicate
layers.
Structural character
istics same as the
micas, 2:1 layer type.
Small poorly defined
flake commonly
grouped in irregular
aggregates.
10 40
6. Chlorite
Alternate mica-like
(OH2)4(SiAl)8(MgFe)6O20 and brucitelike structure (MgAl)6(OH)12 Various
members of the chlorite group differ
from each other in the kind and amount
of substitutions within the brucite layer
and the tetrahedral and octahedral
positions of the mica layer.
10 40
7. Attapulgite
Sepiolite
Polygorskite
20 30
56
57
the wet and semi-dry processes. Clays with at least 7 to 15 plasticity index and having 10% particles of +0.2 mm size and cumulative 20% particles of 0.08 mm size with cation exchange capacity
of 11 to 12 meq/100g are reportedly considered suitable as cement-making variety in situations
where clay has a process role other than providing the stoichiometric requirements.
Thermochemical Reactivity
Experience has established that aluminosilicate, when present in raw mixes from the argillaceous
component, turns out to be significantly more reactive than fine-ground silica. It has been generally observed that the water vapor and hydroxyl group released from the argillaceous materials
shows some catalytic effect on the dissociation of calcium carbonate and the subsequent solid-state
oxidic reactions.
The trends of decomposition of a few clay minerals are shown in Table 2.1.10. It is evident that the
temperature ranges over which different clay minerals release water and hydroxyl ions as well as
transform into an amorphous state before stable phase formation are different. It is obvious, therefore, that their reactivity with lime and other oxides would not be identical in different situations.
However, still there is no unanimity in the views of different investigators regarding the order of
reactivity of different clay minerals. As reported by Volkonskii and others (1973), in accordance
with one investigation, the decreasing order of reactivity was as follows:
Montmorillonite
Halloysite
Kaolinite
Biolite
Hydromica
Pyrophyllite
Muscovite
Vermiculite
Halloysite
Montmorillonite
Kaolinite
Chlorite
Muscovite
Vermiculite
Notwithstanding such differences, it is evident that micaceous minerals have a tendency to show
relatively low reactivity.
It may also be borne in mind that the argillaceous materials have a high probability of containing
titania, alkalies, sulphides, sulfates, and phosphates. The reactivity may be strongly influenced by
the presence of the above constituents.
58
Dehydroxylation
Temperature of
initiation of
recrystallization, C
Allophane
550
900
Kaolinite
550
700
900
Halloysite
450
800
950
Chlorite
200
550
850
Biolite/muscovite
300
950
1150
Mineral
CORRECTIVE MATERIALS
When the primary components of a raw mix do not jointly permit achieving the desired range of
modulii values, a third or even a fourth component is added, known as corrective materials. It has
been a practice to recognize that a material with more than 70% silica, 40% iron oxide, or 30%
alumina can be termed as siliceous, ferruginous, or aluminous corrective materials.
Sand, sandstone, or quartzite acts as the source of siliceous corrective material. Other conditions
being equal, the grain size and specific surface of silica in free form (and particularly of the least
reactive forms like quartz and chalcedony), determine the rate of reaction in a kiln feed. According
to Makashev (1976), the reactivity of different types of silica, free or combined, increases in the
following order:
Quartz < chalcedony < opal < -cristobalite and -tridymite < silica from
feldspars < silica from mica and amphibole < silica from clay minerals < silica
from glassy slags.
On the whole, silica in amorphous state or derived from silicates or hydrosilicates is preferable to
silica in other forms.
The correction of iron oxide in a raw mix is generally done with iron ore, which may either be
magnetitic or haematitic. A haematite with colloidal texture or martitized magnetite is quite reactive with lime and alumina. Limonite (FeOOHH2O), often associated with laterite, is more reactive than the ferric oxide hydrate phases like goethite and lepidocrocite. It has been observed by
Makashev (1976) that the reactivity of raw material is often favorably influenced by the presence of
iron oxide in the ferrous state, the appearance of which is obviously dependent on the parent
mineral. For example, chlorite and glauconite may release FeO below 500C, while geothite and
lepidocrocite yields Fe2O3 at about 300C. The iron-bearing minerals thus play an important role
in shaping the reactivity of the kiln feed, although for alite formation the mineralogy is of little
import since most of the iron has entered the clinker melt by this point.
The correction of alumina is done with the help of bauxite or aluminous laterite. Mineralogically
these rocks contain such aluminous minerals as gibbsite (Al2O3 H2O), boehmite (Al2O3 H2O),
and diaspore (Al2O3 H2O). Generally these phases show low crystallinity and high energy in the
green state, dehydrate at 300C 500C, and give rise to different forms of alumina that ultimately
define their reactivity at higher temperatures.
59
60
The above examples show that the crusher selection strongly depends on full characterization of
raw materials. Similarly, the selection of a grinding system also involves proper understanding of
raw material characteristics, and particularly its
Grindability index
Moisture content as fed to the system
Abrasiveness, often inferred from free silica content.
The ultimate objective is to achieve the targeted particle size distribution, average particle size, and
specific surface with least consumption of energy and other operating costs. It has been reiterated
by Schnatz (1999) that ball mills are cost-effective only when a high degree of wear is expected due
to, say, high quartz content. High pressure grinding rolls can be profitably used for relatively dry
raw materials. Roller mills are generally preferred for raw grinding due to their low energy
consumption and the option of simultaneous drying.
Coming to the pyroprocessing, it may be mentioned that different raw mixes with more or less the
same chemical composition and equal fineness may have greatly differing burnabilities. The reason
for the differences lies in the variation off the mineral composition of the raw mix constituents,
their crystal size, and particle size. According to the F. L. Smidth training modules (1997), worldwide experience has shown that poor burnability is primarily caused by the presence of coarse
grains of calcite (+125 m) and quartz (+45 m). Deleterious effects of the presence of coarse
grains of dolomite (+125 m), feldspar (+63 m), and shale (+50 m) have also been reported.
The volatile matters, and more particularly alkalies and chlorides, present in the raw materials have
a very strong bearing on the process of clinkerization in the present-day preheater-precalciner
rotary kilns. The circulation of these volatiles in the system without any bypass imposes certain
upper input limits for these constituents in raw mixes. On a loss-free basis, these limits are
normally considered as follows:
K2O + 0.65 Na2O
Chlorine as Cl
Sulphur as SO3
1.0%
0.023%
1.0%
The study of alkalies, and sulfur- and chloride-bearing minerals in the raw materials becomes
essential in this context.
CONCLUDING OBSERVATIONS
Cement production is dependent on a wide spectrum of sedimentary and metamorphic rocks,
limestones being the most critical in terms of quality and quantity.
A limestone resource required for setting up a cement plant first needs to be examined from the
point of view of its prospectivity. The geological history defines the complexity of a deposit and an
appropriate exploration program is necessary for proving the deposit and arriving at a reliable estimate of the reserve in terms of quality and quantity. A rational approach is to classify the deposits
in terms of their geological complexity and the reserves in terms of their reliability so that the
quantum of exploration could be decided for a given deposit to arrive at proved, probable, and
possible reserves required for setting up a cement plant.
After proving a limestone resource, it is essential to undertake its thorough compositional assessment. A limestone with a minimum of 44% to 45% CaO and maximum 3.0% to 3.5% MgO, 0.6%
R2O, 0.6% to 0.8% SO3 , and 0.015% to 0.05% Cl is regarded as a cement grade limestone,
provided its SiO2 , Al2O3 , and Fe2O3 contents satisfy the ultimate modulii values of raw mixes. The
compositional ranges of aluminosilicate materials cannot be defined as rigidly as they have to
match the principal carbonate component. In general, an argillaceous component with more than
3% R2O and/or 1% SO3 may be considered, prima facie, unsuitable. For most of the minor
constituents, 0.5% is regarded as a safe limit. A special examination is called for if some of the
constituents exceed this limit.
The comminution and thermal behaviors of raw materials primarily depend on their mineral
phases and microstructural features. The crystal size of calcite and the associated mineral assemblage define the dissociation characteristics of limestone in a very effective manner. The mineralogy of argillaceous materials is quite complex due to their layered structure, frequent ionic
substitutions in the layers, unbalanced charges, and inclusion of interlayer materials. Because of
these complications, the choice of clay can be guided more by Si: (A,F) ratio, volatile contents,
fusibility, granulometry, cation exchange capacity (CEC), etc. In the ultimate evaluation it is
important to note that the concurrence of carbonate dissociation and thermal decomposition of
aluminosilicate components is considered a basic necessity for high reactivity and proper burning.
The above concepts are equally applicable for all other siliceous, ferruginous, or aluminous corrective materials, when their use becomes unavoidable due to stoichiometric needs. Different forms of
silica, aluminum hydrates, ferri/ferous minerals, etc., present in the above corrective materials
influence the burning process quite significantly and hence demand careful evaluation in terms of
overall impact on the raw mix burnability.
In cement production, size reduction is an important material preparation step. The amenability
of limestones to size reduction processes is apparently controlled, inter alia, by the free and fixed
silica content and the crystal size variations of calcite and quartz phases. The hardware selection
for comminution is also dependent on the above mineralogical and microstructural features.
Since the ultimate burning process is involved with the prior size-reduction steps, there has been a
progressive evolution of the limiting particle size for different mineral forms, supported by experi-
61
62
mental findings. In raw materials selection the attainability of such particle size distribution
patterns requires specific attention.
All in all, it should be realized that the production of cement is to a large extent dependent on
natural raw materials, and more specifically on limestones.
Since the scale of cement operation is large, the location of a plant for its life is decided by the
occurrence of a limestone deposit. The technological suitability and consistent supply of raw materials are, therefore, of paramount significance. All efforts for proper selection of raw materials are
absolutely essential.
ACKNOWLEDGEMENTS
The author is thankful to his colleagues at the Companys Research and Consultancy Directorate
and more particularly to Mr. S. A. Khadilkar and Mr. P. G. Lele for providing test data on raw
materials from the Directorates database and also, to Dr. S. K. Jatty for helping with the scanning
electron micrographs of limestone samples.
REFERENCES
Bissell, H. J., and Chilingar, G. V., Developments in Sedimentology, 9A, Elvesier Publishing
Company, Amsterdam 1967, page 37.
Bond, F. C., Crushing and Grinding Calculations, Parts I & II, Bulletin 07R9235C, Allis-Chalmers,
Milwaukee, USA, pages 1-14.
Boynton, R. S., Chemistry and Technology of Lime and Limestone, John Wiley and Sons, New York,
1980, 578 pages.
Brindley, G. W., and Brown, G., Crystal Structures of Clay Minerals and Their X-ray Identification,
Mineralogical Society, London, 1980, 495 pages.
Chatterjee, A. K., Chemico-mineralogical Characteristics of Raw Materials, Advances in Cement
Technology, Ed. Ghosh, S. N., Pergamon Press, Oxford, 1983, pages 39-68.
Chilingar, G. V., Jour. Sedimentary Petrology, Vol., 27, 1957, page 187, as referred to in by S. P.,
Ghosh, 1983.
Chilingar, G. V.; Bissell, H. J.; and Fairbridge, R. W., (Editors), Carbonate Rocks: Physical and
Chemical Aspects (Developments in Sedimentology 9B), Elsevier Publishing Co., Amsterdam 1967,
413 pages.
F. L. Smidth & Co., Kiln Operation and Optimization Training Module, International Cement
Review, May 1997, pages 60-64.
Ghosh, S. P., Raw materials Geological Characteristics, Advances in Cement Technology, Ed.
Ghosh, S. N., Pergamon Press, Oxford, 1983, pages 1-38.
Ghosh, S. P., and Chatterjee, A. K., Norms for Exploration, Opening-up and Quarrying of
Cement-grade Limestone Deposits, Process Technology of Cement Manufacturing, VDZ Congress
77, Bauverlag GmbH, Wiesbaden and Berlin, 1979, pages 91-98.
Grim, R. E., Applied Clay Mineralogy, McGraw-Hill Book Co., New York, 1962, 422 pages.
Makashev, S. D., Effect of Raw Materials Physico-Chemical Properties on Reactivity of Raw Mix
and Clinker Minerogenesis Processes, 6th ICCC, Moscow, September 1976, Section I-4,
pages 1-17.
McCaffrey, L., Quarry Optimisation, Middle Eastern Cement and Construction Materials,
February 1999, pages 25-29.
McCarter, J., Crushing It Right, International Cement Review, February 1996, pages 51-57.
Oates, J. A. H., Lime and Limestone, Wiley-VCH Verlag GmbH, Weinheim, 1998, pages 1-25.
Pettijohn, F. J., Sedimentary Rocks, Harper & Row, New York, 1957, 660 pages.
Schnatz, R., Selecting Grinding Systems, World Cement, January 1999, pages 61-69.
Schwarzkopf, F., Lime Burning Technology A Manual for Lime Plant Operations, 3rd Ed., Svedala
Industries, Kennedy Van Saun, 1994.
Scoffin, T. P., An Introduction to Carbonate Sediments and Rocks, Blackie, 1987.
Sinha, S. K.; Handoo, S. K.; and Chatterjee, A. K., Communition and Dissociation Characteristics
of Indian Limestones, 7th ICCC, Paris, II, 1980, pages I-108 I-113.
Strakhov, N. M., and others, Formation of Sediments in Recent Basins, (in Russian), Izt-vo Akad.
Nauk, USSR, Moscow, 1954.
Tucker, M. E., and Wright, V., Carbonate Sedimentology, Blackwell Scientific Publications, London,
1990.
Tucker, M. E., Sedimentary Petrology, An Introduction to the Origin of Sedimentary Rocks, Blackwell
Scientific Publications, London, 1991.
Velde, B., Introduction to Clay Minerals Chemistry, Origins, Uses and Environmental Significance,
Chapman & Hall, London, 1992, 198 pages.
Volkonskii, V. V.; Makashev, S. D.; and Shteirt, N. P., Technological, Physico-mechanical and
Physico-chemical Studies of Cement Raw Materials (in Russian), Izd-vo Literatury Po Stroitelstvu,
Leningrad 1972.
Wiersma, D. J., The Geology of Carbonate Rocks, Proc. International Lime Congress, September
1990, pages 13-14.
Worral, W. E., Clays, Their Nature, Origin and General Properties, Maclaren and Sons, London,
1968, 124 pages.
63
64