Interim Report

Raw Mix Design

for
M/s Shiva Cement Ltd, Odisha

NCB

CRI-SP4342

April 2022
ational Council for Cement and Building Materials
BALLABGARH
 1.0 INTRODUCTION

Council for Cement and

to National
M/s Shiva Cement Ltd, Odisha, approached
of Shiva Cement".
"Raw Mix Design
for taking up a study on
Building Materials (NCB)
of work:
the following scope
NCB agreed to take up the studies with

1.1 Scope of Work

and gypsum are to be arrange

fine coal
. Representative samples of limestone, additives, (different slags),
by Shiva cement and delivered at NCB Ballabgarh.
2. Physical, chemical and mineralogical characterization of above samples.
from fine
of fine coal sample. Preparation of ash
co:
3. Proximate and ultimate analysis and calorific value

and its chemical analysis for oxide constituents.

5. Designing of different cement raw mixes (3 Nos.) using maximum permissible dosage of different sla
along with a set of other raw materials and fine coal for the manufacture of desired quality of clinker (C3
45-55%).
6. Burnability studies on the above designed cement raw mixes.
7. Mineralogical and microstructural evaluation of clinkers prepared from above cement raw mixes by

ray diffraction and optical microscopy.

8. Optimization of dosage of slags in clinker making on the basis of 6-7 above.

9. Preparation of one bulk clinker (10 kg) in a laboratory furnace from optimized raw mix and its chemicc

mineralogy evaluation.
10. Preparation of PSC and Composite Cement (with fixed level of SO3 and fineness GGBFS and flyy as
content as per the sponsor suggestion) from above bulk elinker and its performance evaluation as p
relevant Indian standard specification (Normal Consistency, Setting Time, Compressive Strength at 1, 3,

and 28 days)
11. Submission of Report.
 The objective of the sponsor is to design the suitable raw Mix for the manufacture of clinker
utilizing different slags as an altermative raw materials/additives. The list of samples received
dated on 7.03.2022 from the sponsor are as follows
SI. Raw Materials Quantity (Kg) Box. No.
No.
Limestone 100
Coal 50
Gypsum 50 2
Clay 50
AODSla 50
6
Flyash 25
7 GGBS 50
Laterite 20
AFR Slag 20
10 Ladle Slag 7.0
Sent Pot Liner 25
12 EAF Slag 20 3

2
 2.0 CHARACTERISATION
AND EVALUATION OR

RAW MATERIALS AND FUEL SAMPLES

=
mincrostructure evaluation of all the raw materialc
Chemical, minerlogy and

have been carried and the details

are discussed of each sample in this chapter,

2.1 Chemical Analysis of Raw Materials

Chemical analysis ofall the materials are given in Table 1. It is observed that CaO, MgO and
SiO2 content of limestone was 43.33 and 10.83 % respectively. Clay sample shows the SiOo and
AlzO as 62.94 and 15.38 % respectively. EAF and AFR slags shows maximum chemical constituent

of CaO in the range of 34.67 to 45.87 %, AlLOs was in the range of 10.4 to 25.5 % and Fe:03 was in

the range of 27.23 to 8.41 %.

Table 1: Chemical analysis of Raw materials

LOI% SiO2%| Ca0,% | MgO,% | Fe,0,% | ALOs,% SOs,% | Na,0,% | K;0,%|

Limestone 38.28 10.83 43.33 3.54 0.81 1.84 0.12 0.22 0.57
Clay 6.64 62.94 1.58 .88 11.16 15.38 0.21 0.08 0.24
Lat 8.05 23.03 0.60 0.46 32.63 33.0 0.08 0.21 0.50
LD Slag -0.34 15.19 48.33 6.00 26.51 1.38 0.11 0.20 0.25
GGBF -0.87 35.178 34.68 8.68 1.038 17.63 1.00 0.28 0.28
EAF -2.86 16.995 34.67 5.8 27.23 10.4 0.05 0.03 0.04
AFR 0.83 8.23 45.87 7.8 8.41 25.5 1.95 0.26 0.1
LOI means gain in weight on ignition.
The chemical analysis of other materials is under way
2.3 Proximate, Ultimate and GCV
analysis of Coal sample
The proximate, ultimate and GCV
analysis of coal sample was carried out on air
dry basis as per relevant Indian standard methods and the results are given in Table 2
and 3.

Table 2: Proximate Analysis of fine coal sample

Parameters Fine Coal

%)
Moisture 7.20
Ash Content 29.50
Volatile Matter 27.01

Fixed Carbon 36.29

3
 Table 3: Ultimate and GCV analysis of fine coal sample
Parameters Fine Coal

Carbon, (%) 64.32

Hydrogen(%) 4.39

Nitrogen, (%) 1.27

GCV(cal/g) 4607

The analysis of the coal sample showed presence of 7.20% moisture, 29.50%% ash
content, 27.01% volatile matter. The gross calorific value of fine coal sample was 4706

kcal/kg.

4
 3.0 RAW MIX
DESIG

3.1 Target Parameters for Raw Mix Design

The target parameters for raw mix design was provided by the plant officials

and the same are given below:

CS content of clinker 45-55%

3.2 Computed Raw Mix Design

h e raw mixes were designed with potential C3S content in the range of 49-53 with

iquid content being maintained in the range of 25.87 to 28.35%. The ground raw materials
(limestone, clay and laterite) were provided by the sponsor with the maintain the residue on 90
microns of 15% and the same materials as received were used for the raw mix. The coal ash
absorption for designed raw mix was calculated based on the thermal energy consumption of
720 kcal/kg clinker. The ash absorption of fine coal was 4.61%.
Raw mixes
prepared as per the designed weight proportions by blending computed
were

quantities of various raw materials. Thermal energy consumption of 720 kcal/kg clinker, as
per
value indicated by Plant, has been considered for
calculating fuel ash absorption in clinker in
this study. With gross calorific value of 4607
kcal/kg, ash content of 29.50% in the fine coal
sample, the fuel ash absorption works out to 4.61% on clinker basis. To account for the
fuel
ash absorption,
4.61% ash (on clinker basis) was blended with the designed mixes
raw
along
with the raw materials in the ball mill.
The weight proportions of raw materials in designed raw mixes are given in Table 4. Six raw
mixes were designed using different
proportions of the limestone and other additives. The total
limestone content in the raw mixes, RM1 to RM 6 was 92.0 to 94.3 percent
by weight.
Table 4: Proportion of raw materials in the designed raw mixes for Si LHF Slag
RM-1 RM-2 RM-3 RM-4 RM-5 RM-6
LST 94.0 92.6 93.5 92.0 94.3 92.2
Clay 2.0 1.2 2.0 2.2 1.0
LAT 0
1.5 1.I
LDSlag 0 2.1 0
GGBF 0 1.8 0 1.4 2.7
EAF 3.0 3.5 4.0 1.2 1.8 3.0
AFR 1.0 0.9 0.5 2.5
1.0
 The computed oxide composition and moduli values of the designed raw mixes are given in
Table 5. The LSF of
designed raw mixes coded RM1, RM2, RM3, RM4, RM5 and RMo
as
were 110.86, 109.98, 109.70, 109.87, 109.83 and 111.18%, respectively. The
and Si02 contents were in
computed Cad
the range of
42.0 to 42.48 % and 11.78 to 12.11 % respectively. The
silica modulus and alumina
modulus of the designed mixes were in the range of 2.46 to 2.0b8
and 1.22 to 1.52
respectively. The corresponding clinker mineral phases along with clinker
liquid content is given in Table 6 & the chemical analysis of the resultant clinkers is
provided in
Table 7.
Table 5: Computed chemical composition of the designed raw mixes
LOI SiO2 CaO MgO Fe20s AlOs LSF SM AM
(%) (%) (%) (%) (%) %)
RM-1
36.04 12.03 42.26 60 1.89
RM-2
2.60 110.86 2.68 1.38

RM-3
35.42 12.09 42.40 3.72 1.93 2.80 109.98 2.55 1.45
35.81 12.1142.17 3.60 2.11 2.57 109.70 2.58 1.22
RM-4
35.34 12.08 42.48 3.67 2.08 2.82 109.87 2.46 1.35
RM-5
36.22 11.99 42.00 3.58 1.87 2.82 109.83 2.56 1.51
RM-6
| 35.28 11.78 42.40 3.76 2.03 3.10 111.18 2.29
Table 6: Computed Mineral phases in resulted clinker of Raw Mixes 1.52

CaS C2S C3A CaAF LIQ.CONT.

(%) (%) %) (%) (%)
CLK-1 52.19 20.51 8.17 9.83 25.87
CLK-2 49.43 22.33 8.77 9.96 26.70
CLK-3 50.31 22.06 7.46 10.83 26.41
CLK-4
49.31 22.31 8.47 10.63
CLK-5
27.2
49.25 22.67 9.08 9.79 26.85
CLK-6 49.41 20.94 9.68 10.40 28.35
Liquid contentformula is =(3*AI203%)+ (2.25*Fe203%)+2+Na20%+K20%
Table 7: Chemical analysis of clinker
samples

SiO CaO MgO Fe:0s Al203 LSF SM AM

(%) (%) (%) (%) (%)
CL-1 20.88 63.07 .36 3.23 2.49
5.15 94.28 .59
CL-2 ).79 62.66 5.49 3.27 5.40 93.55 2.40 1.65
CL-3 20.93 62.71 5.34 .56 5.08 93.37 2.42 1.43
CL-4 20.76 62.7 5.41 3.49 .43 48 2.33 1.55
CL-5 20.86 62.86 5.35 3.22 5.48 93.4 2.40 1.70
CL-6 20.30 62.53 5.53 3.42 5.83 94.39 2.19 1.71

6
 4.0 BURNABILITY EVALUATION OF DESIGNED
RAW MIXES

Kaw mixes were prepared by grinding of all the raw materials separately with 15% residue in 90

microns. As per the designed weight proportions of each raw mix, raw materials were weighed

separately. Then computed ash absorption on clinker basis of 4.61% was blended with all the above
prepared raw mixes. Nodules of~5-10 mm size were prepared of the raw mixes manually and dried.
The raw mixes were evaluated for their bunability by firing of prepared nodules for 20 minutes in a

laboratory furnace at three different temperatures of 1350, 1400 and 1450°C. Burnability evaluation
of resultant clinker
samples were studied for free lime and its mineralogy.
4.1 Burnability Evaluation of Designed Raw Mixes
Free lime content in the resultant clinkers of
designed
raw mixes were estimated as
per
standard method i.e., Indian Standard, IS 4032-1985. The
free lime content in the resultent
clinkers fired at 1350, 1400 and 1450°C are
given in Table 8. All the designed mixes
showed good burnability with free lime content well
below 1.5 % at 1450°C.
Table 8: Estimated free lime content in clinker
samples
Sample Coal
Code Ash Burnability (% free lime at--)
(%)
1350C 1400C 1450C
CL-1 4.61 2.01 I.65 |1.10
CL-2 4.61 1.65 .20 0.80
CL-3 4.61 1.89 1.32 0.95
CL-4 4.61 1.91 1.19 0.85
CL-5 4.61 1.79 1.05 0.69
CL-6 4.61 |1.90 1.15 0.75
4.2 Chemical and
Mineralogical analysis of Lab fired clinkers
The CaO, SiO2, Al203, Fe203 and Mg0 content in the designed clinkers was
in the range of
63.00 to 63.54, 20.45 to 21.09, 5.12 to 5.87, 3.24 to 3.59 and 5.38 to
5.57%, respectively.
Table 9 shows the chemical analysis of lab fired clinker
samples fired at 1450°C. The free
lime content of the clinkers after firing at 1400 and 1450°C was in the range of 1.05-1.65%
and 0.69 to 1.10%, respectively and was as per target of less than 1.5% free lime content of
clinker. The chemical analysis of the designed clinkers indicated that
all the three

7
clinkers met the
target parameters of burnability mineral phase composton
as well as
and hquid content. Quantification analysis of clinker minerals were carried out by ARD ana
found that C3S of resultant
clinkers were in the range of 51.0 to 55.0 % and C2S was in the
range of 20.50 to 25.0 %. Based on this results, it was observed that all the clinker samples
were
meeting the desired level of C3S.

Table 9: Chemical
analysis of designed raw mixes and laboratory fired clinkers prepared
from designed raw mixes

Si02, Ca0, | Mg0, Fe203, | A1203, | S03, | Na20, K20, LOI

% % % % % % %
CL-1 21.03 63.5 40 3.25 5.19 0.21 0.20
0.33 0.83
CL-2 20.97 63.21 | 5.54 3.30 5.45 0.23 0.32 0.83 0.15
CL-3 21.09 63.18 5.38 3.59 5.12 0.19 0.32 0.84 0.30
CL-4 20.89 63.09 5.44 3.51 5.46| 0.25
CL-5 21.00 63.27 0.33 0.82 0.20
5.39 3.24 5.52 0.20 0.33 0.86 0.19
CL-6 20.45 63.00 5.57 3.45 5.87 0.24 0.33 0.83 0.25

Table 10: Mineralogical analysis of Clinker samples by XRD

CS C.S C3A CaAF Others
(%) (%) (%) (%)
CLK-1 55.0 20.5 7.0 12.0 6.0
CLK-2
52.0 23.0 6.5 12.5 6.0
CLK-3
55.0 21.0 7.0 6.0
11.0
CLK-4 51.0 25.0 7.0 12.0 5.0
CLK-5 52.5 23.0 7.5 11.0 6.0
CLK-6 53.0 22.0 8.0 11.0 7.0

The proposed mix

designs and results are applicable for the above materials. The mix

designs proportions and its burnability can vary with the quality of limestone, other raw
materials and quality of fuel.