20 Cement Produc tion Technology

Some typical microstructures of limestone are shown in Figures 1.10

through 1.14.

Specification of The National Council for Cement and Building Materials in India has
cement-grade drawn up the specification for limestone that is considered suitable for
limestone making Portland cement. The specification is given in Table 1.11 (8).
The reasons for specifying the limits of the constituents in Table 1.11
are as follows:
1. Sometimes there are opportunities of enriching the lime content in
limestone by employing viable processes or to make available to
a plant a sweetener-grade limestone at economic cost. Hence, the
cut-off grade for the limestone is kept at 40%, although the desir-
able range of lime content is defined as 44–52%. If a limestone is
near-calcitic in composition, it can still be used as a raw material

FIGURE 1.10 Coarse-grained compact limestone.

FIGURE 1.11 Fine-grained moderately compact limestone.

Basics of miner al resources for cement produc tion 21

FIGURE 1.12 Limestone with inter-granular pores.

FIGURE 1.13 “Foraminifera” fossil in limestone.

0.5 mm

FIGURE 1.14 Limestone with “oolitic” microstructure.

22 Cement Produc tion Technology

Table 1.11 Specification of cement-grade limestone

Limiting values with

Desirable values for scope of beneficiation,
Constituents Portland cement (%) blending, etc. (%)

CaO 44.0–52.0 Min. 40.0

MgO (max) 3.5 5
SiO2 + Al2O3 + Fe2O3 To satisfy LSF* and SM**
TiO2 0.5 1.0
Mn2O3 (Max) 0.5 1.0
R2O (Max) 0.6 1.0
Total S as SO3 (Max.) 0.6 0.8
P2O5 (Max) 0.6 1.0
Cl (Max) 0.015 0.05
Free SiO2 (Max.) 8.0 10.0

*Lime saturation factor; **silica modulus

but the need for diluting the quality with corrective materials then
increases substantially.
2. Since some of the standard global specifications for Portland
cement permit composition of up to 6 per cent magnesia, the lim-
iting value for this oxide in limestone is set at 3.5%. If, in some
cases, it becomes unavoidable to admit higher contents of magne-
sia, for example, up to 5%, this can only be done by lowering the
proportion of magnesia to 3.5% by beneficiating the limestone or
by blending it with a high-purity limestone.
3. The limiting values of R2O, SO3, and Cl¯ have been defined as
they are volatile in nature and create “volatile cycles” in the kiln
systems, leading to various operational and quality problems.
4. The limiting values of titanium dioxide, manganese oxide, and
phosphorus pentoxide are dictated by the likely adverse impacts of
these constituents on clinker quality.
5. The limit of free silica in the limestone is due to its adverse effects
of abrasion on the crusher plates and in grinding mills, on one hand,
and difficulties caused in the clinker burning process, on the other.

Typical physico- It is important to note that a comprehensive characterization and evalu-

chemical ation of limestone includes the following:
properties of
• Hand specimen studies
some limestone
occurrences • Chemical composition
• Mineral phase composition
• Microstructural characteristics
• Physical properties
• Thermal properties
• Mechanical characteristics
 Basics of miner al resources for cement produc tion 23

The overall assessment scheme for carbonate rocks is presented in

Figure 1.15 and the scope of evaluation of the samples is given below:
• Chemical analysis for individual samples: CaO + MgO + CO2 or
CaO + MgO + Insoluble residue.
• Chemical analysis for composite samples: SiO2 + Al2O3 + Fe2O3 +
CaO + MgO + SO3 + Loss on ignition; if the sum total is 98.5% or
less, P2O5 and R2O (alkali oxides) should be determined; if neces-
sary, FeO, Mn2O3, Cl- may be determined.
• Petrographic analysis of parent rock and inseparable intercala-
tions: quantification of MgO, R2O, SO3, and P2O5-bearing mineral
phases, grain size, cementing material, and special textural fea-
tures, if any.
• Granulometric fractions obtained by mechanical analysis: com-
plete characterization and estimation of free silica in all fractions
and also details of mineral contents of inclusions, particularly with
sizes greater than 0.09 mm.
• Physical properties: specific gravity, bulk weight, porosity, natural
moisture content, and water absorption.
• Mechanical properties: hardness, compressive strength, crushing
index, grinding index, and abrasion index.
In order to help understand the pattern of physical and chemical
properties of limestone rocks belonging to geological basins of different
ages, some relevant Indian data are furnished in Table 1.12.
From Table 1.12 it is quite apparent that the physical properties of
limestone rocks cannot be easily correlated with their chemical com-
position. Hence, in most of the situations, limestone samples need to
be characterized as comprehensively as possible. By and large, it is
observed that the Mohs hardness of sedimentary limestone rocks falls
in the range of 3–4, and the density in the range of 2.5–2.7 g/cm3. The
porosity of compact limestone rocks may range from 1–20% and it may
go up to 30% in porous limestone. Water absorption depends on the
pattern and level of porosity. While it is generally negligible for com-
pact limestone, water absorption may go up to 20% in porous limestone.

Carbonate rock

Petrographic Physico-
Chemical
characterization mechanical
analysis
tests

Individual Granulometric Physical Mechanical

Composite Rock fragments
samples fractions properties properties
samples

FIGURE 1.15 An assessment scheme for the carbonate rocks.

24 Cement Produc tion Technology

Table 1.12 Physical and chemical characteristics of some Indian

limestone rocks of different geological ages

Limestone rocks of different geological ages

Parameters 1 2 3 4 5

CaO (%) 43.0 44.5 46.6 47.7 48.7

SiO2 (%) 13.0 18.0 11.7 12.6 10.5
LOI (%) 35.5 34.4 38.1 37.5 37.5
Quartz (%) 10.3 14.5 8.2 8.7 7.9
Dolomite (%) 7.9 3.3 5.0 – –
Calcite (%) 72.5 77.7 80.5 85.2 87.0
Sp. Gravity 2.70 2.62 2.63 2.59 2.70
Bulk density (g/cm3) 1.46 1.45 1.41 1.53 1.65
Porosity (%) 2.65 1.31 3.73 2.24 4.45
Abrasion (%) 22.96 18.45 30.64 23.74 65.38
Compressive strength 110.2 113.6 140.0 94.9 48.0
(MPa)
Bond’s grindability 10.1 12.35 6.82 12.61 4.64
(kWh/short ton)

The compressive strength of cylindrical specimens prepared from the

lumps of limestone samples vary from 10 to 200 MPa, and the Bond’s
grindability index from 4 to 14 units.
In general, the desirable characteristics of limestone from a cement
manufacturing point of view can be summarized as follows:
a. Average calcite crystal size: less than 0.25 mm, which is consid-
ered characteristic of fine-grained rocks
b. Absence of coarse quartz and silica veins
c. Low moisture content: less than 5%
d. Low compressive strength: less than 100 MPa

1.6 Limestone mining

Limestone is predominantly mined from a quarry that is an open pit

exposed to the surface. However, underground limestone mines can
be found in the central and eastern USA, Brazil, and some other coun-
tries, especially in and near cities. Underground mining obviously has
some advantages over surface quarrying but, since it is more expensive
and capital-intensive, the cement industry depends mostly on opencast
mining. The suitability of opencast mining is also due to the fact that
the sedimentary limestone deposits are quite extensive, covering hun-
dreds of square kilometers, and are reasonably uniform in thickness and
quality.
 Basics of miner al resources for cement produc tion 25

The selection of mining method is dependent on several factors. The

more important criteria are:
• Shape and configuration of the deposit
• Aerial extent and dimension
• Dip (inclination) and thickness of the bed
• Thickness of the overburden
• Physiographic and topographic conditions
• Climatic conditions including rainfall, snowing, wind pattern, etc.
• Daily and yearly raisings required for feeding the plant
Some variations in the opencast mining methods under different con-
ditions are briefly described below.

Variations in open- For deposits in plain land the mine is opened at a point where the thick-
cast mining ness of overburden is minimal. Inclined trenches and ramps are driven
from one bench level to another in order to create and develop each bench.
In hilly deposits, mining has to start from the top downwards, by slicing
or decapping. The benches are developed at pre-determined locations.
For thick limestone deposits that are horizontally bedded with a thick
layer of overburden, the mining operation is mostly mechanized with
large-capacity mining equipment, while for deposits with thin mineral-
ization and thick overburden, or vice-versa, the operation is mechanized
but with medium-capacity equipment. For deposits with a thin bed of
mineralization and a thin layer of overburden, only a semi-mechanized
scheme is adopted. The same principles hold good for deposits with dip-
ping beds but a major consideration in this case is the economic depth of
mining. The “stripping ratio,” signifying the ratio of limestone to over-
burden or waste rock, is normally very important in mining but turns
out to be critical in steeply dipping deposits. The economic or cut-off
stripping ratio (COSR) is defined by:

COSR = value of a unit quantity of limestone − average cost of production/

average cost of overburden removal

and the formula brings out the break-even point at which the mining
operation is no longer profitable. An important alternative method of
working for dipping deposits is to mine along the strike direction or per-
pendicular to the dip direction of the bed, instead of advancing along the
dip. This method of mining is known as “terrace mining” and is often
preferred for both economic and environmental reasons.
Most opencast mining operations are discontinuous. Nowadays, a
continuous system is preferred in appropriate situations by using a spe-
cial piece of mining equipment called a “surface miner.” This equipment
cuts the rock continuously and feeds the conveying system. One great
advantage over conventional systems is that it does not require drilling
26 Cement Produc tion Technology

and blasting as well as primary crushing of rock. At the same time, one
must take into consideration its limitations. It can cut freely only softer
limestone rocks with compressive strength of up to 50 MPa, or up to
80 MPa if the rock has cracks, crevices, and fissures, or if the seismic
velocity of the rock is low.

Operational Normally, cement plants are located near the limestone deposits, while
issues in mining shale or clay is either substituted by the overburden, if it is chemically
suitable and economical to use, or mined locally elsewhere and trans-
ported to the plant. Other corrective materials are usually brought from
outside.
Mining plans of the limestone quarry are developed according to the
nature of the deposit. If the limestone is not homogeneous, it may be
necessary to blend rock from different benches and faces of the mine in
order to maximize the recovery from the mine. In some mines, it may
be necessary to undertake selective mining in order to avoid low-grade
material or problems of associated harmful constituents like sulfates and
alkalis.
The mining operation proceeds with initial close-spaced advance
drilling and analysis of drill hole samples in order to ascertain the spa-
tial distribution of quality. The areas to be blasted are decided based on
such advance drilling. The conventional explosive used for limestone
quarrying is ANFO (ammonium nitrate with 5% fuel oil). The specific
consumption of explosives varies depending on the blasting behavior of
limestone, but tentatively it is in the range of 200 g/t.
If, after primary blasting, the limestone boulder size is larger than
the crusher feed size, there could be a need for secondary blasting or
mechanical size reduction of the biggest boulders. The run-of-mine
material, after blasting, is transported to the crusher. Mining and haul-
age operations are generally monitored by
a. Blasting factor: grams of explosive per metric ton of rock.
b. Overburden ratio: tons of waste rock removed per ton of useful
rock.
c. Loading rate: tons of rock per hour of loading equipment
availability.
d. Hauling factor: tons of rock transported per truck and truck
availability.
It should also be borne in mind that all mine output and inventory
records are kept on the basis of dry rock data but the moisture levels of
mined, hauled, and crushed rocks are used for assessing the equipment
efficiency.
Typical public concerns about limestone mining include dust, noise,
blasting vibration, and vehicular traffic. Some limestone rocks are aqui-
fers and there can be concerns about the contaminants from quarry oper-
ations escaping into the groundwater. In humid climates, large amounts
of limestone dissolve and are carried away in the flowing water, creating
sinkholes.
Basics of miner al resources for cement produc tion 27

1.7 Quarry design and operational optimization

The design of a pit for opencast operation may look simple but it involves
not only proper utilization of exploration data through build-up of a 3D
model of the deposit, but also reasonable integration of various other
factors such as geotechnical, economic, operational, and environmental
considerations. The configuration of the quarry, along with its bound-
ary limits, has to be defined through the development of a 3D model
from the exploration data. Parameters like slope stability, the dimen-
sions of the working benches and their compliance with the prevail-
ing mining regulations, water seepage and drainage, layout of the road
network, determination of blasting behavior of rocks, etc. fall primarily
under the purview of geotechnical modeling. Environmental planning
includes, apart from the minimization of dust and noise pollution at the
operational stage, the design of a waste rock dump, the systematic clo-
sure of mines, and the rehabilitation of the quarry after closure. The
economic model involves assessment of the economic stripping ratio,
determination of the net present value of future mining operations, and
the overall viability of the project. Thereafter, operational issues such
as grade control, scheduling of mining sequence, opening-up of mine
faces, planning of blasting pattern, advance drilling program, etc. are
decided. Long-term integrated mine planning is, therefore, complex and
has many components, as shown in Figure 1.16.
Regarding actual operations, in a quarry the planning system must
pass information to drill operators. Drilling operations need to send
samples from advance drilling operations to the laboratory, and the

Deposit model

Environmental Geotechnical
planning model
Mine
planning
and design

Output and Economic

production model
constraints

FIGURE 1.16 Components of integrated long-term mine planning.

28 Cement Produc tion Technology

grade control geologist needs to match up the quality of blast holes

with their actual positions and depths. The blasting engineer needs to
know which drill holes are in limestone and which are in waste rocks.
The dispatch system needs to know which faces are to be mined, what
the tonnages are, and where the crusher is. It is obvious, therefore,
that the quality control of run-of-mine limestone and the optimiza-
tion of quarry operation are quite involved and complex. Present-day
mining software packages allow rapid and accurate iterative investiga-
tions of mining scenarios to determine the most appropriate course of
action. Among the numerous software packages, those commonly used
include GEOVIASurpac, Maptek Vulcan, Datamine, XPAC, iGantt,
Micromine, and Promine.
The basic feature of these software packages includes a relational geo-
logical database that allows storage and query of all geochemical quality
parameters, in addition to physical attributes such as minimum mining
thickness. Complex 3D geological and quality models are developed to
assist in deposit visualization and estimation of fairly accurate volumes.
Statistical and multiple-element compositing tools can be used to inves-
tigate the quality distribution and undertake element combinations using
established algorithms. Estimation using a polygonal, grid, or block model
approach is available in such software. The effect of lateral quality varia-
tion can be minimized using the proper scheduling approach. A sched-
uler allows an engineer to examine multiple mining scenarios graphically
and with ease. Such software can assist the plant manager in optimiz-
ing a blend of raw material from available quarry faces. These solutions
use linear programming to achieve the required blend and are useful in
ensuring that short-term goals are met. The long-range quarry schedul-
ing problems require a rigorous solution and make use of dynamic pro-
gramming methods. The plant quality targets for cement making can
include several parameters such as directly measured minor constituents
like MgO, SO3, R2O, etc. and other critical modulus values. While the 3D
geological model is built to contain quality values, interpolated from drill
cuttings and face samples, the schedule optimizer is able to utilize these
basic quality attributes in constructing the target ratio of blending lime-
stone mined from different blocks and faces. On the whole, therefore, the
quarry production plan is essentially based on geological exploration data,
3D deposit modeling, grade control, scheduling of mining sequence, and
ore blending (Figure 1.17), and planning functions include blast design and
layout. Also included is the evaluation of blast operations and schedules
are developed to plan production from the working benches. It should also
be borne in mind that conventional economic analysis tells us that the
value of an ore block mined today is worth more than an ore block mined
one year from now. Hence, certain software packages have developed pro-
grams to solve the problems of how to discount the value of mining blocks
and consequently locate the optimal limit of mining.
 Basics of miner al resources for cement produc tion 29

Exploration data

Quantity Quality

Deposit modeling

Geostatistical Three-dimensional

Mine planning

Simultaneous mining of multiple faces with blending

Run-of-mine quality control and feedback

FIGURE 1.17 Sequential steps in quarry planning.

1.8 Argillaceous materials

The expression “argillaceous materials” refers to all fine-grained natural

earthy substances that are alternatively known as “clay,” including shale
and argillite. It is well known that the clay minerals are part of a larger
family of phyllosilicates and are characterized by interlinked tetrahedral
and octahedral sheets. The chemical composition and structural con-
figuration of clay minerals have been discussed in detail in (4,12). The
structure and properties of the major clay mineral groups are presented
in Table 1.13.
From the table it is evident that, chemically, these materials are
hydrous aluminum silicates, with magnesium or iron substituting alumi-
num wholly or in part in certain minerals, and with alkalis or alkaline
earth also present as essential constituents in a few others.
Some argillaceous materials are composed of a single clay mineral but
in many there is a mixture; in addition to the clay minerals, many argil-
laceous materials contain non-clay minerals like quartz, calcite, feld-
spar, sulfides, and so on. Many others may contain organic substances as
well as water-soluble salts, and some clay materials may contain phases
that are x-ray amorphous. 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
 30

Table 1.13 Structure and properties of the major clay mineral groups

Cation exchange
Structural grouping Major mineral phase Broad composition Structural features capacity meq/100g

2-layer kaolin group Kaolinite (OH)8Si4Al4O10 1:1 layer type (001) = 7.21 A 3–15
SiO2 46.54% B = 8.99 A
Al2O3 39.50% Flaky habit
H2O 13.96%
3-layer smectite Montmorillonite (OH2)4Si8 Al4O20.nH2O 2:1 layer 80–150
group (expanding lattice) Composition without interlayer material: Equidimensional, extremely
SiO2 66.7% thin flakes
Al2O3 28.3%
H2O 5.0%
Some substitution of Si by Al in tetrahedral layer
and of Al in octahedral layer by Mg, Fe, Zn, Ni,
Cement Produc tion Technology

Li, etc. Lattice always unbalanced

Illite (non- expanding Muscovite-like dioctahedral (OH)4K2 Si6Al2) Structural characterization 10–40
lattice) Al4O20. Biotite type is trioctahedral with same as micas, 2: 1 layer type.
incorporation of Mg and Fe. Illites differ from Small, poorly defined flake
mica in having less replacement of Al for Si, commonly grouped in
less K and less randomness of silicate layers irregular aggregates
Chain- structure Palygorskite– Composition of the balanced ideal cell of 2:1 inverted ribbons. Generally 20–50
palygorskite group Attapulgite–Sepiolite Attapulgite(OH2)4(OH)2 Mg5Si8O.4H2O. seen as bundles of lath-shape
Sepiolite and palygorskite show variations in units
the composition of Al, Mg, and Si
 Basics of miner al resources for cement produc tion 31

speaking, the property-controlling factors in argillaceous materials are

the following:
i. Clay minerals
ii. Non-clay minerals
iii. Organic substances
iv. Exchangeable ions and soluble salts
v. Particle characteristics including shape, size, and orientation
vi. Structural assembly 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

Thermo-chemical Argillaceous rocks generally show the presence of multiple clay miner-
reactivity of als. Shale generally contains illite and chlorite. Montmorillonite is also
clay minerals a common constituent of many shale occurrences of Mesozoic age and
younger. Kaolinite is a common mineral of certain types of shale but
usually in minor proportions. Slates are also composed of illite and chlo-
rites but with a higher degree of crystalline structure. The carbonate
rocks show the association of a wide range of clay minerals, illite and
chlorite being more predominant than kaolinite and montmorillorite.
Experience has shown that an aluminum silicate phase, when pres-
ent in raw mixes from the argillaceous component, turns out to be sig-
nificantly more reactive than fine-ground silica. It has been generally
observed that the water vapor and hydroxyl ions released from the argil-
laceous materials show some catalytic effect on the dissociation of cal-
cium carbonate and the subsequent solid-state oxidation reactions. The
trend of decomposition of a few clay minerals is shown in Table 1.14. It is

Table 1.14 Decomposition behavior of some clays of varying mineral composition based
on thermogravimetric analyses

Temperature Weight loss

Mineral composition range (°C) (%) Remarks

Kaolinite (90%), Anatase Up to 350 1.20 Moisture loss

350–650 13.34 Dehydroxylation of kaolinite
Kaolinite (70%), Quartz, Up to 250 0.42 Moisture loss
Muscovite 250–750 10.05 Dehydroxylation of kaolinite
Kaolinite (40%), Quartz, Up to 200 8.65 Moisture loss
Anatase, Goethite, 200–350 1.03 Breakdown of goethite
Hematite, Anorthoclase 350–750 4.36 Dehydroxylation of kaolinite
Quartz, kaolinite (50%), Up to 400 1.30 Moisture loss from illite
illite (14%), anatase 400–550 5.70 Incomplete dehydroxylation of
550–1000 4.00 kaolinite
Prolonged breakdown of clay minerals
Montmorillonite (80%), Up to 100 12.00 Moisture loss
kaolinite (6%), hematite, 100–700 7.00 Dehydroxylation of kaolinite further
quartz, cristobalite, 700–1000 1.06 weight loss for reactions not
anatase deciphered
32 Cement Produc tion Technology

evident that the temperature ranges over which different clay minerals
release water and hydroxyl ions to become amorphous and reactive are
not the same. It is obvious, therefore, that their reactivity with lime and
other oxides would not be identical in different situations. However, there
is still no unanimity in the views of different investigators regarding the
order of reactivity of different clay minerals. According to certain inves-
tigations (13), montmorillonite as a clay mineral is more reactive than
kaolinite, which in turn shows higher reactivity than chlorite. Minerals
like muscovite, biotite, vermiculite, pyrophyllite, etc. in general have low
reactivity.
It may also be borne in mind that the argillaceous materials have high
probability of containing titania, alkalies, sulfides, sulfates, and phos-
phates. The reactivity may get strongly influenced by the presence of the
above constituents.

1.9 Corrective materials

When the primary components of a raw mix do not jointly permit the
desired range of modulus values to be achieved, a third or even a fourth
component is added, known as corrective materials. It has been a prac-
tice to recognize that a material with more than 70% silica, 40% iron
oxide, or 30% alumina can be termed as siliceous, ferruginous, or alu-
minous corrective material (14).
Sand, sandstone, or quartzite acts as the source of siliceous correc-
tive 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.
The reactivity of different types of silica, free or combined, increases in
the following order:

quartz < chalcedony < opal < α − cristobalite and α- 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 magnetite or hematite. A hematite with colloidal
texture or martitized magnetite is quite reactive with lime and alumina.
Limonite (FeO.OH.H2O) often associated with laterite is more reactive
than the ferric oxide hydrate phases like goethite and lepidocrocite. It
has been observed that the reactivity of raw material is often favorably
influenced by the presence of iron oxide in the ferrous state, the appear-
ance of which is obviously dependent on the parent mineral. For example,
chlorite and glauconite may release FeO below 500°C, while goethite
and lepidocrocite yields Fe2O3 at about 300°C. The iron-bearing miner-
als, thus, play some important role in shaping the reactivity of kiln feed.
 Basics of miner al resources for cement produc tion 33

The correction of alumina is done with the help of bauxite or alumi-

nous laterite. These rocks contain such aluminous minerals as gibbsite
(Al2O3.3H2O), bohemite (α Al2O3.H2O), and diaspore (βAl2O3.H2O).
Generally, these phases show low crystallinity and high energy in the
green state, dehydrate at 300–500°C, and give rise to different forms of
alumina that ultimately define their reactivity at higher temperatures.

1.10 Natural gypsum

Gypsum (CaSO4.2H2O) is a common rock-forming mineral with thick

extensive beds formed by the evaporation of extremely saline water. It
is often associated with other minerals like halite or sulfur. It is depos-
ited from lakes, seawater, hot springs, volcanic vapors, etc. and usually
forms a solid nonporous rock near the Earth’s surface, and consequently
the mining of gypsum ore is generally carried out in quarries or shallow
underground mines. It is a mineral belonging to the monoclinic system
and mostly occurs as flattened crystals that are often twinned. It is a
very soft mineral, having a Mohs hardness of 1.5–2.0 and density in
the range of 2.31–2.33 g/cm3. Gypsum is white, grey, or reddish in color,
depending on the presence of clay or iron oxide; the color may be black
or nearly black if bitumen is present. Depending on the appearance and
crystalline characteristics, gypsum is known by certain other names. A
fine-grained white or slightly tinted variety is known as “alabaster”; a
transparent colorless variety with pearly luster is called “selenite”; and
a silky fibrous variety is named “satin spar.” When the white variety
is used for agricultural purposes, it is known as “terra alba” or “land
plaster.” An unusual and interesting occurrence of white gypsum is in
New Mexico in the USA, where it covers an expanse of 710 km2 with a
dune-like structure. This deposit is not being exploited and is preserved
as an uncommon occurrence (15).

Major gypsum pro- World production of gypsum in 2012 was 150 million metric tons, with
ducing countries China being the largest producer, followed by Iran, Spain, Thailand, and
the USA. The production statistics of the first ten countries of the world
in the same year are given in Table 1.15 (16).
According to IBM statistics, in 2010 gypsum production in India
totaled only 2.5 million metric tons. Over the years, the resource position
of the mineral gypsum has declined and the emphasis has been shifting
towards the use of chemical gypsum primarily from the fertilizer indus-
try. The state of Rajasthan alone accounts for over 81% of resources, and
Jammu and Kashmir 14%. The remaining 5% of resources are distrib-
uted in Tamil Nadu and other states.
Gypsum is worked by opencast manual mining, except in a few semi-
mechanized mines in Rajasthan. The deposits are found at shallow
depths and scattered over large areas. Production is classified into four
grades based on the calcium sulfate (CaSO4.2H2O) content: (i) above
90%; (ii) 85–90%; (iii) 80–85%; and (iv) less than 80%. High-grade
gypsum is mined in the Bikaner and Jaisalmer districts of Rajasthan.
34 Cement Produc tion Technology

Table 1.15 Major gypsum producing countries

and their production in 2012

Serial no. Country Quantity (thousand tons)

1 China 48000
2 Iran 14000
3 Spain 11500
4 Thailand 10000
5 USA 9900
6 Japan 5700
7 Italy 4100
8 Mexico 3840
9 Australia 3000
10 Canada 2200

Some gypsum mines in the Bikaner district also produce the selenite
variety. Rajasthan gypsum is used in cement plants in northern and
eastern states in India, while gypsum produced in Tamil Nadu is mainly
of cement grade and is consumed in plants located in the southern parts
of the country.

Chemical The CaSO4 – H2O system is represented by three solid phases that co-
properties exist at room temperature in air containing water vapor, namely cal-
of gypsum cium sulfate dihydrate (CaSO 4.2H 2O), calcium sulfate hemihydrate
(CaSO4.1/2H2O), and insoluble anhydrite (CaSO4 – insol.). In addi-
tion to these phases, another phase is identified as soluble anhydrite
(CaSO4 – sol.), which has the same crystal structure as hemihydrate.
Two transformations are very important for these substances. They are
(1) dehydration from the dehydrated state and (2) rehydration to the
dehydrated state. Dehydration refers to the stepwise loss of water of
hydration that is accomplished by increasing the temperature of dehy-
dration for the purpose of obtaining one of its dehydration products, i.e.,
hemihydrate, soluble anhydrite, and insoluble anhydrite. The tempera-
ture ranges applicable for the individual dehydration steps depend on
whether the process is static or kinetic. In general, the static conditions
appear to proceed at a lower temperature but they require more time.
For example, the dihydrate phase begins to dehydrate at about 46°C but
conversion takes months or even years to complete. Rehydration is the
exposure of these dehydrated materials (hemihydrate, soluble anhydrite,
and insoluble anhydrite) to liquid water for the purpose of obtaining the
dihydrate state again at standard conditions. This process proceeds by
the crystallization of the dihydrate phase in water. If the starting mate-
rial is a hemihydrate, a supersaturated solution is formed prior to crystal-
lization. In the case of an insoluble anhydrite as the starting material, the
rate of conversion to gypsum is affected by the degree of its solubility
and the temperature. The solubility of the dihydrate, hemihydrate, and
insoluble anhydrite phases are an important consideration for a vari-
ety of reasons but primarily because they allow a distinct separation
Basics of miner al resources for cement produc tion 35

between the three phases on a theoretical basis. Their approximate solu-

bility curves are shown in Figure 1.18 (17).
The intersection between two curves gives the equilibrium tempera-
ture, below which the less-soluble phase is stable. For example, the curves
show that above 40°C (point A) insoluble anhydrite is the most stable
phase. However, above this point, the dihydrate phase, if in contact with
water, should not convert to insoluble anhydrite, but in practice It may do
so but at a very slow rate. Below 100°C (point B) the dihydrate phase is
more stable than the hemihydrate. When the saturated solutions of hemi-
hydrate are supersaturated with respect to dihydrate, the dihydrate phase
precipitates from the solution. This dehydration-rehydration process
appears to be relatively simple but a number of critical conditions are
to be met that finally ensure the transformation process. For example,
water vapor plays a significant role in the dehydration and rehydration of
soluble anhydrite. Also, the hemihydrate phase occurs in the α-form and
ß-form depending on the method of dehydration. When the hemihydrate
phase is formed under normal atmospheric conditions it is referred to as
β-hemihydrate, while the α-form is obtained from the dihydrate phase
by autoclaving. Although the normal solubility of the dihydrate phase is
reckoned as 2.1 g/L at 20°C, the solubility of the β-hemihydrate is much
higher at about 8.8 g/L at 20°C but it reduces to 6.5 g/L for the α-phase.
For all practical purposes, the conversion temperature of dihydrate to
hemihydrate lies in the range of 100–180°C, hemihydrate to soluble
anhydrite in the range of 180–350°C under favorable water vapor
pressure conditions and to insoluble anhydrite above 1180°C. Insoluble
­anhydrite also occurs in natural deposits.

0.8

0.7

0.6
CaSO4 in solution (%)

Hemihydrate

0.5

0.4

0.3
Dihydrate
0.2 A
B

0.1 Insoluble
anhydrite

0 25 50 75 100 125 150 175 200

Temperature (°C)

FIGURE 1.18 Solubility curves of calcium sulfate phases.

36 Cement Produc tion Technology

1.11 Influence of raw materials on unit operations

In the cement production process, since there are quite a few unit opera-
tions employing different equipment and machinery, it is important to
examine the influence that the raw materials yield in this perspective.
For example, all three principle unit operations such as crushing, grind-
ing, and burning are strongly influenced by the characteristics of lime-
stone and other raw materials. Some key requirements include:
• Crushing strength (kg/cm2) or crushability index
• Grinding index
• Hardness
• Abrasion index
• Impurities present such as clay, quartz, etc.
• Degree of coarseness in terms of crystal size of the constituent
minerals
• Particle size distribution of the crushed and ground materials
• Moisture content (minimum and maximum)
While the first three parameters are important for selection of the
type and materials of construction of the crushing and grinding installa-
tions, the other parameters may have a strong influence on the process.
It is observed that the handling of wet sticky materials may affect the
throughput and increase the maintenance cost of the crusher. Similarly,
most materials to be crushed contain inclusions or impurities, which
behave quite differently from one another when introduced into a crusher
or a screening system. The characteristics of these inclusions play an
important part in the selection of the right equipment.
Coming to the grinding process, the objective is to achieve the tar-
geted particle size distribution, average particle size, and specific surface
with least consumption of energy and other operating costs. 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 profitably be
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. So far as burning is concerned, it is important
to note that different raw mixes with more or less the same chemical
composition and similar fineness may have greatly differing burning
behavior. The reason for the difference lies in the variation of the min-
eral composition of the raw mix constituents, their crystal size, and their
particle size. Worldwide experience has shown that the poor burning is
primarily caused by the presence of coarse grains of quartz (+ 44 μm),
calcite (+ 125 μm), feldspar (+ 63 μm), and shale (+ 50 μm).
The volatile matters and, more particularly, alkalis and chlorides
present in the raw materials have a very strong bearing on the process
of clinker formation 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.
Basics of miner al resources for cement produc tion 37

The determination of alkali-, sulfur-, and chloride-bearing minerals

in the raw materials becomes essential in this context. Some of these
aspects will be discussed in more details in chapters dealing with size
reduction and burning operations.

1.12 Summary

Cement production is dependent on a wide range of sedimentary and

metamorphic rocks, limestone being the essential one. A limestone
resource required for setting up a cement plant needs to be first exam-
ined from the point of view of its quality and quantity. The geologi-
cal disposition defines the complexity of a deposit and an appropriate
exploration program is necessary for proving the deposit and arriving
at a reliable estimate of reserves. A general approach is to classify the
deposits in terms of their geological complexity so that the quantum
of exploration could be decided for a given deposit, which in turn will
ensure that proper reserve estimates are made in “proved,” “probable,”
and “possible” categories of reserves. The limestone reserves can be
more rationally categorized by applying the United Nations Framework
Classification system, using three parameters, viz., status of geological
proving, extent of mining feasibility established, and compliance of eco-
nomic and social viability of the project studied. This system provides
a more dependable approach to transform a resource into a viable mine
through various intermediate stages of investigation.
The assessment of limestone deposits involves sampling of different
types at different stages of investigation. Standard operational proce-
dures have been evolved in practice for such sampling exercises, which
need to be observed in the studies. The dependability of technological
assessment of limestone deposits is related to the representativeness of
the samples drawn and evaluated.
Limestone mining is done mostly by the opencast method. The details
of the mining method depend on the shape, size, and configuration of the
deposit, terrain of its occurrence, disposition and thickness of the bed,
overburden or waste rock to be removed and dumped, and several other
factors. Parameters like the blasting factor, overburden ratio, loading
rate, and so on are required to be monitored in the mining operation.
Quarry design and operational optimization are essential steps in min-
ing and several software packages are available to undertake these steps.
After proving a limestone resource, it is essential to undertake its
thorough technological assessment. Limestone with a minimum of
44–45% CaO and maximum 3.0–3.5% MgO, 0.6% R2O, 0.6–0.8% SO3,
and 0.015–0.05% Cl is regarded as a cement-grade limestone, provided
its SiO2, Al2O3, and Fe2O3 contents satisfy the desired modulus values of
raw mixes. The specification of clay and other corrective materials can-
not be very precisely defined as they have to have compatibility with the
principle carbonate component. In general, an argillaceous component
with more than 3% R2O and 1% SO3 may be considered, prima facie,
unsuitable. For most of the minor constituents, 0.5% is regarded to be a
38 Cement Produc tion Technology

safe limit. If some of the constituents exceed this limit, a special exami-
nation is called for.
The size reduction and thermal behavior of raw materials primarily
depend on their mineral phases and microstructural features. The crystal
size of calcite and the associated mineral assemblage define the dissocia-
tion 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, unbal-
anced charges, and the inclusion of interlayer materials. Because of these
complications the choice of clay can be guided more by Si/(A,F) ratio,
volatile contents, fusibility, particle size distribution, cation exchange
capacity, etc. In the ultimate evaluation, it is important to note that the
concurrence of carbonate dissociation and thermal decomposition of
clay and other corrective materials is considered a basic necessity for
high reactivity and proper burning.
The above concepts are equally applicable for all other siliceous, fer-
ruginous, or aluminous corrective materials, when their use becomes
unavoidable due to stoichiometric needs. Different forms of silica, alu-
minum hydrates, ferriferous minerals, etc. present in the above cor-
rective materials influence the burning process quite significantly and
hence demand careful evaluation in terms of overall impact on the burn-
ing behavior of the raw mix.
Mineral phases carrying volatile oxides like alkalis, sulfates, chlo-
rides, etc. assume criticality in determining the likely nature of the vola-
tility cycle in a rotary kiln system. Hence, the selection of raw materials
depends on the quantitative contribution of such volatile components
from the raw materials under consideration.
In cement production, size reduction is an important material prepa-
ration step. The amenability of limestone 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 selection of
hardware for grinding is also dependent on the above mineralogical and
microstructural features.
Since the ultimate burning process is dependent on the prior size
reduction steps, there has been a progressive evolution of the concept of
limiting particle size for different mineral forms, supported by experi-
mental findings. In the selection of raw materials, the feasibility of attain-
ing such particle size distribution patterns requires specific attention.
All in all, it should be realized that the production of cement is solely
dependent on natural raw materials and, more specifically, on the qual-
ity and quantity of limestone. The scale of operation is large and 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 mate-
rials are, therefore, of paramount significance. Proper selection of raw
materials is the first step towards setting up a cement plant.
Basics of miner al resources for cement produc tion 39

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