Limestone
is calcareous sedimentary rock composed of mineral
calcite (CaCO3) which upon
calcination yields lime (CaO) for commercial
use. Cement and Iron & Steel are the major consumers
of limestone. It is also consumed in chemical industries
like calcium carbide, bleaching powder, soda-ash,
precipitated calcium carbonate, etc. Besides,
it is used as fluxing material in ferro-alloys,
pelletization plants, foundries and in the production
of sponge from iron, as refining materials in the
production of sugar; as an additive in glass industry;
as a coating material in fertilizers industry; and
in the cooking of range and grass in the paper industry.
The
details of specifications on limestone required
by various industries are discussed below:
1.
Cement Industry: -
Limestone
containing about 45% CaO and above is usually
preferred for the manufacture of cement. Magnesia
content in the stone should ideally be less than
3%, although as high as 5% MgO is used by the
industry. The proportion of Al2O3
+ Fe2O3: SiO2
should be 1:2:5. Magnesia sulphur and phosphorus
are regarding as most undesirable impurities.
The presence of phosphorus and P2O5
more than 1% slows down the setting time of Portland
cement. The cement industry in India in general
prescribed the following specification of limestone.
CaO
42% (min.) Al2O3 2 to 4%
(min.), Fe2O3 1 – 2% SiO2
12 to 16% and MgO 4% (max.)
2.
Iron & Steel Industry:
-
Limestone
is used in this industry both in the blast furnace
to lower the temperature of melting and second
to from calcium silicate by combining with silica
of the iron ore, which comes out as slag.
i.
Blast furnace: - Specifications of limestone
in various steel plants in India for use in Blast
furnace are given below:
|
Plant
|
Size |
CaO |
MgO |
SiO2 |
Al2O3 |
T.
I. |
|
BSP |
+50mm
10%
(max.)
-25mm
5%
(max.) |
42%
1% |
8% |
- |
- |
6.58%
1% |
|
BSL |
25mm
5%
(max.)
+85mm
5%
(max.) |
45%
-- |
6%
max.
-- |
--
5%
max. |
-- |
-- |
|
RSP |
+50mm
10%
(max.) |
--
44% |
-- |
-- |
--
2%
max. |
9%
1% |
|
BSP |
-25mm
10%
(max.)
+75mm
10%
(max.) |
45%
-- |
--
-- |
--
7.5%
max. |
-- |
--
12%
max. |
|
IISCO |
75mm
10%
(max.)
-25mm
10%
(max.) |
46%
-- |
-----------10%--------- |
--
11%
max. |
|
TISCO |
-75mm
+25mm
o/s
10% up to 100m
u/s
up to 10% |
6%
-- |
-- |
-- |
-- |
12%
max. |
(ii)
Steel Melting Shop: - For this purpose good
fluxing limestone low in acid constituents such
as silica, alumina, sulphur and phosphorus is
required. The limestone should be dense, massive,
preferably fine grained, compact and non-fretting
on burning. The specifications of limestone required
by steel plants in India for SMS purpose are given
below:
|
Plant
Size |
CaO |
MgO |
SiO2 |
Al2O3 |
T.
I. |
|
BSP:
(a)
O. H. -50mm
5%
(max.)
(b)
L. D. 40-80mm
5%
(max.) |
49%
53% |
4%
max.
2%
max. |
1.8%
max. |
1.7%
max. |
5%
max. |
|
BSL:
L.
D. -30mm
5%
(max.)
+60mm
5%
(max.) |
50%
-- |
3.5%
max.
-- |
--
|
-- |
--
|
|
DSP:
75-125mm
+125mm
10%
(max.)
-75mm
10%
(max.) |
48%
-- |
3.5%
max.
-- |
-- |
-- |
5%
max.
-- |
|
RSP:
80mm
10%
(max.)
-40mm
10%
(max.) |
51%
|
-- |
-- |
-- |
5%
1.5% |
|
TISCO:
+125mm
5%
(max.)
-75mm
10%
(max.) |
50%
|
-- |
4.0%
max. |
-- |
-- |
|
TISCO:
(a)
O. H. -75+35mm
(b)
L. D. -75+35mm
-35mm
5%
(max.) |
53% |
2%
max.
2%
max. |
-- |
-- |
4%
max.
1%
max. |
From
the above it is seen that limestone is L. D. furnace
must be of high purity with low silica content
as far as possible. Some plants are insisting
on as low as 0.5% SiO2.
The
BIS (IS: 10345 – 1982) has prescribed the under
mentioned guidelines for flux limestone for use
in steel plants:
|
Characteristics |
Grade-I
(for
use in lime manufacturing)
|
Grade-II
(for
use in steel making)
|
Grade-III
(for
use in Iron making)
|
|
CaO
|
52%
min. |
50%
min. |
42%
min. |
|
MgO |
2%
max. |
3%
max. |
9%
max. |
|
Acid
insoluble |
2%
max. |
4%
max.
out which SiO2 should not exceed
1.8% |
10%
max.
out which Al2O3 should
not exceed 2.5% |
|
Preferred
size |
* |
*
25-60mm, 25mm not to exceed 5% and 60mm
not to exceed 10% |
*
25-60mm, 25mm not to exceed 5% & 60mm
not to exceed 10% |
The size range other than specified above shall
be subject to agreement between the supplier and
the purchaser.
COMPARATIVE TABLE OF CHEMICAL, PHYSICAL &
SOME ENGINEERING PROPERTIES OF SMS GRADE LIMESTONES FROM JAISALMER AND GOTAN, RAJASTHAN
|
S.
No. |
Item
/ Property |
Trials at Bhilai Steel Plant
Trial, Jaisalmer Base, Gotan Limestone
Limestone
M/s RSMDC Gotan |
| |
|
1. |
Period
considered |
19
to 30 May, 1988 |
15-31
Dec. 1987 |
|
2. |
Total
limestone calcined in trial period |
3500
tonnes |
-- |
|
3. |
Average
Limestone Analysis |
% |
% |
|
|
(a)
Chemical:
CaO
MgO
SiO2
LOI
(b)
Screen
-35mm
-40mm
+80mm |
54.88
0.73
0.90
43.07
21.66
26.06
0.04 |
53.10
2.04
1.64
42.58
24.00
--
-- |
|
4. |
Average
Lime Analysis
CaO
LOI
Reactivity
Undersize
(-15mm) |
87.7
6.88
325cc
10.9 |
80.8
7.40
367cc
33.5 |
|
5.
|
Operational
factors in Kiln
i)
Yield of LD grade lime from limestone charged
into the kiln |
49.89%
(overall
yield 60.8%) |
38.87%
|
|
6. |
Operational
factors in converters
i) Specific lime consumption |
80
Kg / T (corrected)
|
106
Kg / T
|
| LABORATORY EVALUATION |
|
7. |
i)
Disassociation started
ii)
Finished
iii) Range |
720°
C
977° C
257° C |
725°
C 945°
C 220°
C |
|
8. |
DTA
Peak Temperature |
930°
C |
900°
C |
|
9. |
Weight
Loss (total) |
42.0% |
43.02% |
|
10. |
Decrepitation
Index (-15mm%) |
1.42 |
16.0 |
|
11. |
Crushing
Strength (Kg / cm2) |
320 |
358 |
3.
Chemical Industry: -
Generally
quick lime is used in the manufacture of calcium
carbide. The calcium carbide manufactures generally
prefer lime containing 95% CaO (min.), not more
than 3% SiO2, not exceed 2%. Though
chemical composition is the guiding factor, the
physical characteristics of the limestone are
also very important.
For
the manufacture of bleaching powder also, fat
lime-containing CaO 95% and above is required.
Total Fe2O3 + Al2O3
+ MnO2 should be less than 2%; MgO
should be below 2% and SiO2 less than
1.5%. Bleaching powder is prepared by absorption
of chlorine by dry hydrated lime. The hydrated
lime should not contain more than 2% of excess
water. Iron and oxides tend to discolour the bleached
material. Magnesia renders the bleaching powder
hydroscopic. Silica and clay impede solution and
setting of bleaching powder.
Limestone
suitable for bleaching powder can be advantage
utilized by alkali industry for the manufacture
of soda ash and caustic soda.
4.
Sugar Industry: -
In
sugar industry lime is used for the clarification
of juice form can be beets. Milk of lime 1% in
volume of cane juice is added to pre-heated juice.
Limestone to be used in sugar industry must be
high in active lime (CaO S 80% min.) must be low
in iron, alumina and silica, etc. Magnesia should
be less than 1%. Excess of silica in un-desirable
because it separates as a gelatinous precipitate,
which covers the sugar crystals and retards their
growth and filtration. Magnesia is objectionable
because magnesia carbonate is soluble in sugar
juice. Presence of Iron tends to color the finished
product.
T The BIS (IS: 3204 – 1978)
stipulates the following specifications of limestone
for use in
the
preparation of bleaching powder, caustic soda
and calcium carbide and sugar.
|
Characteristics |
Requirement
in percent by mass for
Bleaching
Caustic
Calcium Sugar
Powder
Soda
Carbide
|
|
1.
L O I |
46.0 |
46.0 |
46.0 |
44.0 |
|
2.
SiO2 (max.) |
0.75 |
-- |
1.0 |
2.0 |
|
3.
Fe2O3 (max.) |
0.15 |
-- |
0.25 |
-- |
|
4.
CaO (min.) |
54.0 |
53.0 |
54.0 |
50.0 |
|
5.
MgO (max.) |
2.0 |
1.0 |
0.8 |
1.0 |
|
6.
Mn2O3 (min.) |
0.06 |
-- |
-- |
-- |
|
7.
CO2 (min.) |
42.0 |
42.0 |
42.0 |
41.0 |
|
8.
S (max.) |
-- |
-- |
0.1 |
-- |
|
9.
P (max.) |
-- |
-- |
0.1 |
-- |
|
10.
Al2O3 + Fe2O3
(max.) |
-- |
-- |
0.50 |
1.50 |
|
11.
SiO2 + Al2O3
+ Fe2O3 (max.) |
-- |
3.0 |
-- |
-- |
5.
Glass Industry: -
Glass
industry required high limestone (CaCO3:
94.5%) combine CaCO3 and MgCO3
should be 97.5%. Iron and other coloring matter
like carbon are regarded as objectionable. Fe2O3
should be up to 0.20% (max.). For colorless glass,
limestone should not be more than 0.04%; and for
bottle glass Fe2O3 up to
0.05% is used. The BIS specifications (IS: 977
– 1973) for limestone for use in glass industry
are as follows:
|
1. |
Silica
as SiO2
|
2.5% |
|
2. |
Total
iron (Fe2O3)
(a)
Calcite or marble
(b)
Limestone
(c)
Dolomite Limestone or Dolomite |
0.05%
0.10%
0.15% |
|
3. |
Lime
(as CaO) |
53.00% |
|
4. |
Total
lime and magnesia (as CaO + MgO) |
54.50% |
6.
Fertilizers Industry: -
The
latest use of limestone introduced in the country
is in the manufacture of calcium ammonium fertilizers,
limestone is used only as carrier. For this purpose
limestone should contain MgCO3 + CaCO3
85% (min.) SiO2 5% (max.) and acid
insolubles 14% (max.)
7.
The Chemical requirements of limestone for use
in foundries as per BIS specifications (IS: 4140
– 1978) are given below:
|
S.
No. |
Characteristics |
Requirement
in percent by mass for
Grade-I
Grade-II Grade-III |
|
1. |
Calcium
Oxide (CaO) min. |
52 |
50 |
45 |
|
2. |
Silica
(SiO2) max. |
1.5 |
3 |
5 |
|
3. |
Mixes
oxides R2O3 (Fe2O3
+ Al2O3) max. |
1 |
1 |
1 |
|
4. |
Magnesia
oxide (MgO) max. |
2 |
3 |
5 |
|
5. |
Insoluble
matter, max. |
0.5 |
1 |
2 |
|
6. |
Sulphur
and phosphorus |
Trace |
Trace |
Trace |
Future
Trends: - it is noticed specifications are
prescribed by the steel industry should be 52%
(min.) and SiO2 1% (max.). Besides,
the physical characteristics are important. It
should be non-decapitating and should have low
content of alkalis.
In
the mineral inventory as on 01.01.1985, the reserves
of limestone have been classified in to cement,
BF, SMS and chemical grade taking in to consideration
(a) reported contents CaO, MgO, and SiO2;
(b) Judgments of the exploration agencies without
any separate chemical analysis data and (c) actual
reported use.
Where
chemical analysis data has been taken as a criterion,
the parameters are as under:
|
Cement
|
CaO
MgO |
42
to 45%
5%
(max.) |
|
BF |
CaO
CaO
+ MgO
SiO2 |
42%
(min.)
48%
(min.)
9%
(max.) |
|
SMS |
CaO
MgO
SiO2 |
48%
(min.)
3%
(max.)
4%
(max.) |
|
Chemical
|
CaO
MgO
SiO2 |
50%
(min.)
2%
(max.)
2%
(max.) |
For
BF and SMS grade limestone physical form i.e.,
hard lumpy is important. Currently for LD converters
very low silica limestone not susceptible to decapitation
is required. Thi