INORGANIC CHEMICAL INDUSTRIES

218 these
for processingpH of
process can be used
at a
molybdenum and iron. Adifferential leachingH,SO, is used as solvent and solution is 2.0 and
nodules.
The nodules are crushed to 50 mesh size, solution. The copper sulfuric separated
put into with acid at a pH
temperature of 77°F, copper is preferentially
subjected to second leaching solution.
and the solid phase is washed and is then nickel goes into By similar
point After
of 2.0 and a temperature of 120°F, at which
also can be put
into the solution. can
oxides
nickel, cobalt
be charged into
of
manipulation temperature and pH, cobalt manganese and iron
and copper are removed, he remaining mixture of The individual solutions separated
a furnace for the manufacture of ferromanganese. nickel,
from the
electrochemically converted to copper and
solid phases can he puriffed, concentrated and
cobalt metals.

IIK. CEMENT ANDLIME

is
products discussed in this section are based on limestone which
Pocesses and 3-4
predomnantly calcium carbonate (CaCo.). This material is distributed rather uniformly in
formations. Consequently
nroughout the earth's erust, coming largelyfrom igneous rock
Bihar, Assam and
ts Well distributed throughout India, beingsparse onlyin W. Bengal, northern Limestone rock is
Certan areas of Punjab, Rajasthan, Andhra Pradesh. and Tamil Nadu States.
usually available at the surface and can be collected by open-pit quarrying methods. Certain
deposits are low-grade and must be treated by beneficiation methods, largely froth flotation, to
remove excess silica and alumina.
The limestone-based industries of cement and lime are characterized by high tonnage low cost
low margin operations which require efficient management to create a profitable venture.
Cement

K Definition
Cement is a generic name for powdered materials which initially have plastic flow when mixed
with water or other liquid, but form asolid structure in several hours with varying degree of
strength and bonding properties which continue to improve with age. The most common is
Portland cement which is the basis for a number of cement products. Specifically, Portland
cement is defined as finely ground calcium aluminates and silicates of varying
hydrate when mixed with water to form a rigid continuous compositions which
structure with good compressive
strength.
A. Properties of Cement
2.1. Constituents of Cement
Code Chemical Formula Type %
(a) Portland
C,S 2CaO"Sio, Silicate Major
C,S 3CaO" SiO, Silicate Major
CyA 3CaO" Al,0,
CAF 4CaO " Al,O,"Fe,O, Aluminate Major
MgO
Aluminate Minor
CaO Minor
Minor
 CEMENT AND LIME 219
alumina
CsA 3CaO"Al,0, Aluminate Major
C,S 2CaO" Sio,
C,AS 2CaO "Al,0,Sio, Silicate Minor
c)Hydraulichydrated Mixed Minor
lime
Ca(OH), Hydroxide Major
C,S 2Ca0" SiO, Silicate Minor
C,A 3CaO" AI,O, Aluminate Minor
Types of Portland Cement
Varying the peroentage of constituents changes the rate of setting, heat evolution, and
strengthcharacteristics.
Type I - Regular: 40-60% C,S, 10-30% Ca,S, 7-13% Ca,A:
hardens to full strength in 28 days
Higher C,S/C,S to resist sulfate attack
" Type Il - Modified:
" Type II - High Early Strength: Attains strength of Type I in only 3days: high
structures;
heat rates--useless on massive
finer
higher C,S and CA percentage with
grinding to increase hydration rate
work; low C,S
Designed for massive structure
Type IV - Low Heat: and C,A which are largest
coniributors to heat
of hydration C,A<4%)
Resistant: Good for sea water contact;
Type V - Sulfate rate ot
Other Types of Cement fusing limestone and bauxite; rapidsuperior
2.3. alumina--manufactured by rate liberation;
2.3.1. High development to high values but with high heat
strength sulfate waters. in 2-4 parts
with
resistance to sea and
volcanic ash, burnt clay or shale
extender.
Pozzolana-mixture of cement as a cheap strength.
2.3.2.
lime. Mixed with Portland
composition, low price and forms
hydrated for brick mortar
lime--used only with MgCI,
Mgo mixed bonding
2.3.3. Hydraulic oxychloride-lightly calcined wear-resistant flooring; high with
Magnesium spark-proof, construction material
2.3.4. high-strength, indoor
excellent so useful in forming
fibers
strength to wood to water. tor
resistance
Characteristics and gravel is used
only fair sand strength.
Compressive Strength other ingredients such ashas very poor tensile
Z.4.Relative when mixed with compressive loading since it strength properties:
Cement under comparative
purposes general idea of H,0)
Structural give a : 3sand +
comparative data Compressive Strength, kelcm
(1cement
oOme Mortar composition 28 days
days
Type lday 3 340
37 120 260
83
Type 28 440
Portland 240
Type II 103 177
Type IiI 20
49 214
Type IV 88
28
Type
 INORGANIC CHEMICAL INDUSTRIES
222 subjected
composition. If not, it is remove to flotationmica
final thickener, being of
satisfactory
material which
must be floated
to
silica,
separation as well as the coarse minerale
wet certain
and talc
of a collecting
agent to
Flotation is based on the ability which rises to the surface and
overflows
the causing
flotation
these to be entrained in an air froth
latter units the
flotation liquor is recycled and
cell into the thickener cascade. Inthese directlytocement kilns.
the beneficiated cement rock slurry is fed
4.2.4. Major engineering problems selective weting. Oldest
agents-necessary for type is
Choice of flotation
Newer types of detergents
have better selectivity
oleic acid @200 gm/ton.
and lower consumption. with power input (see next section
Grinding- optimizing particle size range
on cement rock grinding).
4.3. Portland Cement Process
4.3.1. Reference flow sheet: Figure IIK-2
4.3.2. Chemical reactions
CaCO; 00C, CaO + CO,; +44 Kcal
CaO + Al,0; + SiO, ’ Mixture of C;S, C,S, C,A
4.3.3. Quantitative requirements
(a) Basis: 1ton of Type I cement
Clay 0.1-0.3 ton
Limestone 1.2-1.3 tons
Gypsum 0.03-0.05 ton
Coal 0.25-0.40 ton
Water 3 tons
Electricity 80 KWH
(b) Plant capacities: 200-1,200 tons/day
4.3.4. Process description
Cement-grade limestone (and possibly oyster shells) plus clay or
containing materials (such as blast furnace slag), gypsum and coal shale, sand, iron
where it is more plentiful than oil or gas for heating) are (especially in India
Grinding may be a wet or dry process, but dry process ground together.
because of savings in heat (less water to evaporate) and plants now predominate
sequence may include rough crushing, followed by accurate control possible. The
drying and fine grinding in tube mills followed by air gyratory and hammer mills then
The dry powdered feed (or wet
slurry)
separation and pneumatic blending
is then fed to a
rotary kiln. The residence time is l-3
hours and the
direct-fired counter-current
fused to form the cement feed mixture is decarbonated and
is dropped to a rotary compounds (C,S, C,S, C,A). The hot clinker (3-10 mm size)
cooler which also preheats
product from tube milling the clinker is a
powder of
combustion air for the kiln. The
bagged or bulk stored and shipped. which 90% passes 200 mesh; it 1s
4.3.5. Major engineering problems
(a) Type of grinding
As noted above, wet or
in most new plants. The dry grinding may be used
importance
of good design with dry grinding being used
here is
emphasized
by the fact that
 Gases
-Flue CEMENT AND LIME 223

Shipping
and
Bagging

Mill
Two Cement
Tube
Compartment
with to

Cooler Circuit
Classifiers
Air
Stk
To
Kiln manufacture.
Closed
Four
in cement
Heat
Waste Tails Portland
Air
Boiler
[Tails\
Fies IIK-2.
Circuit
Cosed Fig.
Wet-grind Screen
Peripheral
Beneficiated.
Sluny
Rock
Rotary
Filter

Pulverizer Jstorage
YCinker
Tube
Limestone
Grade
Mill

Cjay
High

Start
 INORGANICCHEMICAL INDUSTRIES
224 cement is
manufacture of used in the
consumed in the
about 80% of the total power
operations.
crushing, grinding and blending
(b) Kiln design CaO and firing at1,400-1,500°c
decompOsition of CaCO, to required for water
Calcining involves
to promote compound formation. Heat duty is also
volatilization of sulfates,
chlorides, andevaporation,
alkalies. A
oxidizing organic material, partial
typical performance graph is given:

30} Heat absorpton

for reaction
20} Weight koss
10

100%
% Distance in Kin

2.56 m diameter; rotating at

Wet process feed requires 90-170 m length kilns of short as 50 m.
corresponding speeds of 2 rpm->½ rpm. Dry process kilns may be as
(c) Heat economy
Minimizing fuel consumption is an economic balance between fuel costs and
addition of waste-heat boiler and air preheater with the equipment usually specified
because of favorable incremental investment.
The theoretical heat requirement is 430 Kcal/kg of Portland cement clinker.
Actual heat requirements vary from 1,300-1,800 Kcal/kg for processes using wet grinding
down to 700-1,000 Kcal/kg for processes using dry grinding.
(d) Quality control
Product performance is quite sensitive to rock composition, particle size, and
degree of calcining. Instrumentation and automatic control of the calcining kiln has
proven a worthwhile investment in improving Indian cement quality so that it now stands
high in world market comparisons.
4.4. Economics of Cement Industry
4.4.1. Raw materials
High grade and beneficiated circuit rock will have to be
blending with burnt clays and blast furnace slag to conserve native supplemented by
example of substituted raw materials is at Fertilizer Corp. of India limestone. Another
calcium carbonate sludge is utilized in producing 600 Ltd., Sindri, where
adjacent plant of the Associated Cement Companies Ltd. tons/cement per day via an
reaction: The sludge comes from the
CaSO, + (NH),CO, ’ (NH),SO, +
8Ypsum CaCO,
fertilizer grade sludge
ammonium
sulfate
Still another example of
aco-product in the substituted raw materials involves cement production a5
production of sulfuric acid from
Sulfur and Sulfuric Acid gypsum. See Section IIA on
for further discussion. This
process produces cement clinker