Coal Based Direct Reduction of Preoxidized Chromite Ore at High Temperature

Ferrochromium Pretreatment for Smelting
COAL BASED DIRECT REDUCTION OF PREOXIDIZED

CHROMITE ORE AT HIGH TEMPERATURE
G. Kapure1, V. Tathavadkar1, C.B. Rao1, S.M. Rao1, K.S. Raju2
1
Research & Development, Tata Steel Limited, Jamshedpur, India, gajanan.kapure@tatasteel.com

2
Ferro Alloys and Minerals Division, Tata Steel Limited, Bamnipal, India, ksraju@tatasteel.com
ABSTRACT
Reduction of preoxidized chromite ore composite pellets using coal reductant is investigated at high
temperature (1500 0C). Chromite ore oxidized in air at 900 0C for 2h duration is used as base material
for carrying out the reduction studies. During preoxidation of chromite ore, the FeO present in
chromite spinel oxidizes to Fe2O3 (sequioxide) in the form of exholved precipitate on the surface of
chromite grains and generates cation vacancies. The preoxidized ore is reduced using coal reductant
and fluxes (lime, quartz). The effect reductant coal, fluxes and degree of preoxidation of initial
chromite on Fe and Cr metallization is studied. About 80% of iron and 77% of chromium metallization
is observed in the reduced product. Clear slag and metal separation is achieved during reduction. It is
also observed that preoxidation of chromite ore improves the degree of Fe and Cr metallization during
reduction process. The aim of this research is to develop a pre-reduction process using oxidized
chromite ore which will help to minimize the energy and coke consumption in ferrochrome production
process.
INTRODUCTION
The mineral chromite is the only significant ore mineral of chromium. Chromite (with suitably high
chromium to iron ratio) is smelted to produce ferrochromium, an alloy of iron and chromium that is a
critical raw material in the production of stainless steel. Historically, ferrochromium is produced
worldwide mostly in submerged arc furnace (SAF) process. However, the SAF process is highly
energy intensive and requires Low Ash Minerals (LAM) coke as a reductant. In past, Outokumpu,
Kawasaki, and Krupp investigated various possibilities to improve the SAF process 1). Their
developments mainly included pre-reduction and preheating methods in order to improve chromium
recoveries and minimize smelting costs. However, most of these pre-reduction techniques can not be
used directly for processing MgO rich Indian Chromite ores especially Sukinda chromite ores due to
their highly refractory nature 2). Therefore a new process is developed with objective of effective prereduction of Sukinda Chromite ores, wherein chromite ore is subjected to oxidation before its
reduction 3,4,5). Preoxidation enhanced the reactivity of chromite spinel and thereby increased the
degree of reduction. In this paper, the effect of coal reductant, fluxes (lime, quartz) and also the effect
of degree of preoxidation on Cr and Fe metallization during reduction is examined with aim to gain a
better understanding of the reduction mechanism of preoxidized chromite ores.
1.1
Mineralogy of Chromite Ore
Natural chromite is a mixture of chromium and iron oxide, with varying amounts of magnesium and
aluminum with general formula (Fe2+, Mg)O.[Cr, Al, Fe3+]2 O3. Chromite being the spinel group of
mineral can be represented by chemical formula of chrome spinels as AB2O4, where A represents
divalent cations (i.e. Fe, Mg) in the tetrahedral sites, and B represents trivalent cations (i.e. Cr, Al, Fe)
in the octahedral sites. Each unit cell is made up of eight AB2O4 units, where the cubic close-packing
of 32 oxygen atoms provides 64 tetrahedral and 32 octahedral sites6). The relative proportions of the
various cations, oxidation state of iron and mineralogical properties of the ore vary from source to
source.
Page numbers removed!

The Twelfth International Ferroalloys Congress
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EXPERIMENTAL
2.1
Materials Preparation
The chromite ore from Sukinda chromite mines, Orissa, India is studied. The cumulative size analysis
and weights retained in different size fractions for chromite ore is given in Figure 1. It can be seen
from Figure 1 that the d80 (80% passing) of the particles in the ore is about 206 m. The chemical
analysis of the ore, reductant coal (anthracite), quartz, flux (lime) and bentonite (as binder) is given
Table 1. Anthracite coal and the fluxes are used in powdered form having average particle size of
about 55m. The raw materials are mixed at different ratios and agglomerated by using disc pelletizer
to form green pellets feed for reduction process.
100
Weight Percentage, [%]
90
80
d80 = 206 Micron
70
Retained
Cumulative Wt %
60
50
40
30
20
10
0
100
200
300
400
500
600
Size [Micron]
700
800
900
1000
Figure 1:
Cumulative size analysis and weights retained in different size fractions for chromite ore
Table 1:
Chemical analysis of raw materials for reduction process
Item
Chromite Ore
Lime
Quartz
Bentonite
Anthracite
Coal
2.2
Chemical analysis (wt%)

Fe(t)
Cr2O3
CaO
MgO
11.5
41.8
0.02
8.8
2.9
64.6
0.9
0.28
7.7
1.05
1.7
Proximate analysis of coal, wt % (wet basis)
FC
VM
73.5
12.5
SiO2
6.3
1.9
99.4
58.0
Ash
10.0
Al2O3
12.6
0.05
0.4
5.5
Moisture
4.0
Experimental Procedure
A chamber furnace is used to carry out the pre-oxidation of chromite ore. The oxidized chromite ore is
prepared by heating the initial chromite ore for 2h isothermally at 900 0C in a chamber furnace. A
constant flow rate of 40 lpm air is purged inside the furnace to maintain oxidized atmosphere during
the preoxidation stage. The preoxidized chromite ore is then used in reduction studies.
A horizontal tubular furnace is used to conduct the reduction experiments at 1500 0C. Throughout the
reduction experiments nitrogen gas having 99.0 % purity (rest impurities like oxygen and moisture)
purged at rate of 5.0 lpm through the furnace in order to maintain the inert atmosphere within furnace
during reduction. A schematic diagram of the horizontal tube furnace used in the reduction studies is
shown in Figure 2. The green pellets are produced by agglomeration of pre-oxidized chromite ore,
quartz, lime, binder (bentonite) and reducing agent (coal) for carrying out the reduction process. The
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weighed pellets were placed in the alumina crucible and inserted in the tube furnace at room
temperature (250C). The heating is done such that a constant heat cycle is followed in all the
experiments. A typical heating and cooling cycle used in the reduction experiments is shown in Figure
3. A constant holding time of 2.5h at 1500 0C is maintained in all the reduction experiments. After
each experiment, the crucible was taken out of the furnace and the weight of the reduced products is
noted and subsequently subjected to chemical analysis.
2
4
5
7
Gas Out
Gas in
Water
out
Water
in
1. Cooling Flanges, 2. Furnace, 3. Alumina Tube, 4. Heaters, 5. Cylindrical Alumina Crucible,

6. Composite Pellets Sample, 7. Gas Regulator
Figure 2:
Schematic diagram of horizontal tube furnace operation
1600
1400
Heating rate
= 1 0C/ min
Holding at 1500 0C
= 2.5 h
Temperature, [ C]
1200
Heating rate =
3 0C/ min
1000
Cooling rate
= 6 0C/ min
800
600
Heating rate
= 5 0C/ min
400
200
0
200
400
600
800
1000
1200
1400
Time, [min]
Figure 3:
2.3
Typical heating and cooling cycle used during reduction experiments
Estimation of chromium metallization
The method for estimation of total chromium analysis in a reduced sample is instituted process.
However, for estimation of metallic chromium in a reduced sample is developed in the present study.
For this, 0.25g of the finely ground (<100mesh) of the partially reduced chromite sample is taken in a
round bottomed flask fitted with a reflux condenser. An acid mixture is prepared by adding 100ml of
ortho-phosphoric acid and 400 ml of sulfuric acid to 500 ml of water. 100ml of the acid mixture is
added to the sample and the contents are refluxed for 90 minutes. The contents are cooled and
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filtered through Whatman No. 41 filter paper and the residue washed five times with hot water. The
filtrate and the washings are made up to 250ml in a volumetric flask and the chromium concentration
is measured by ICP emission spectrometric method.
The method is validated by analyzing a certified reference material of Ferro chrome having a known
concentration of metallic chromium. The recovery of metallic chromium is found to be complete. When
a pre-oxidized chromite ore sample containing only Cr2O3 and no metallic chromium is treated in a
similar manner, the chromium content of the solution is found to be less than 0.5%, indicating that
only a negligible amount of Cr2O3 passes into solution in the treatment process given above and the
method given is highly selective for the determination of metallic chromium. The chromium
metallization in a reduced chromite sample is obtained as a ratio of metallic chromium to total
chromium.
3
3.1
RESULTS AND DISCUSSION

Preoxidation of Chromite Ore
The raw chromite ore is oxidized in air for 2h duration at 900 0C using the chamber furnace. This preoxidized chromite ore is used as base material for the reduction studies. As the iron is present in the
form of FeO in Indian chrome spinel, during oxidation reaction, the FeO present in spinel gets
oxidized to Fe2O3 as exsoluted sequioxide (Fe2O3) phase on chromite mineral grain and additional
cation vacancies are generated. A representative comparison of the SEM micrograph for raw
chromite and pre-oxidized chromite at 900 0C for 2h duration is shown in Figure 4. It can be seen from
Figure 4b that after preoxidation of chromite the sequioxide phase has precipitated on the surface of
chromite grain in a typical Widmanstatten pattern. The bright lines are iron rich phases and the matrix
is magnesium rich phase. It is observed from these results that iron is precipitating from the matrix on
{111} crystallographic planes.
Exholved
Fe2O3
Iron oxide
Mg-Al
Silicates
Chromite
Iron rich
Chromite
Chromite
Point
Mg
Al
Si
Cr
Fe
Point
Mg
Cr
Fe
22.7
11.7
8.4
0.5
46.9
7.7
7.3
45.9
15.5
23.3
10.3
7.9
0.6
46.4
10.9
4.2
47.1
28.8
21.2
0.0
1.7
2.7
2.4
71.3
3.3
47.2
20.2
31.9
10.6
3.5
32.0
0.3
11.3
2.0
47.8
22.5
32.2
11.1
1.7
34.1
0.4
12.1
0.0
46.6
26.1
26.4
0.5
7.3
3.1
30.9
30.0
12.5
46.8
9.3
24.5
0.0
7.7
2.9
37.2
25.8
12.6
46.7
8.8
22.7
10.2
7.0
0.7
47.8
10.2
10
13.3
47.4
8.6
(a)
Figure 4:
(b)
SEM Micrograph of raw (un-oxidized) chromite-(a) and preoxidized chromite particle-(b)
The pre-oxidation of chromite resulting in a typical Widmansttten pattern on the surface of chromite
grain is in accordance with the established theory of oxidation and precipitation of sesquioxide phase.
According to this theory, the preferential crystallographic orientation of Widmansttten lamellae was
along the {111} plane of spinel matrix phase. The {111} planes of spinel and the {0001} planes of
sesquioxide have a similar close packing arrangement of oxygen ions, which account for the common
orientation of sesquioxide lamellae along the {111} plane of the spinel matrix. Tapered terminals
develop at the intersection of two or more lamellae, which are indicative of a diffusion-controlled
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process. Also, in an oxidizing atmosphere, in addition to the intrinsic driving force for phase
transformation, the imposed oxygen chemical potential promotes the diffusion of Fe2+ ion from the
core of chromite grain towards the solid-gas interface on the surface of the grain. This outward
diffusion of Fe2+ cations and oxidation to Fe3+ cations takes place via following reactions:
1
T
O2
Oo2 + Vcatn + 2.h

2
T
2 Fe 2 +
2 Fe3+ + 2 . e'
[1]
[2]
Oo2 represents oxygen anions on the cubic closed packed lattice, Vcatn is cation vacancy,
h is hole, and e' is electron. Oxidation of chromite ore results in opening up of the spinel structure.
Where
Thus newly formed Fe2O3 phase alonwith the additional vacancies generated during oxidation
improves the reactivity of chromite ore and helps in the slag formation at lower temperatures during
reduction.
3.2
Reduction of Pre-Oxidized Chromite Ore
The preoxidized chromite ore at 900 0C for 2h duration is used as base material for carrying out the
reduction studies. The effect of various reduction process parameters such as reductant coal and
fluxes (lime, quartz) on reduction of preoxidized chromite ore is investigated and discussed in the
following sections.
3.2.1
Effect of coal addition
Anthracite coal is used as carbon source for reduction process of pre-oxidized chromite ore. The
charge composition used consists of 100g preoxidized chromite ore, 15.6g quartz, 5g lime and 1.5g
bentonite as binder. The amount of quartz to be used in the reduction experiments is estimated based
on the theoretical requirement of silica in order to form the alumino-silicate and magnesio-silicate slag
during the reduction. The coal content in the charge was then varied from stiochiometric requirement
(18.6g) to 70% excess (31.6g) in order to understand the effect of coal addition on the Cr and Fe
metallization in the reduced product. The Cr-metallization is defined as the ratio of Cr recovered in
metal to the initial Cr present in the charge. Similarly the Fe-metallization is defined as the ratio of Fe
recoverd in metal to initial Fe present in the charge. The effect of variation in coal on the Cr and Fe
metallization at 1500 0C is shown in Figure 5. It can be seen from Figure 5 that the Cr-metallization
have improved up to 77% with increase in coal from 18.6g to 27.9g (50% excess of stiochiometry)
and then decreased with further increase in coal addition. In case of Fe-metallization similar
behaviour is observed and maximum Fe-metallization of about 82% is obtained at 27.9g of coal
addition. With increase in the carbon (from coal) content beyond certain limit (27.9g) the residual
excess carbon increases in the reduced product and results in decreased Cr and Fe metallization.
Therefore, the suitable coal mix established from reduction experiments is 27.9 coal for reduction of
100 g preoxidized chromite ore at given flux conditions.
3.2.2 Effect of Lime
In order to understand the effect of lime addition on the reduction of pre-oxidized chromite ore, the
charge composition is maintained constant (100g pre-oxidized ore, 27.9g coal, 15.6 quartz, 1.5g
bentonite) and the lime addition to charge is varied from 3.0g to 10g. The effect of variation in lime
content in the charge on the Cr and Fe metallization is shown in Figure 6. It can be seen from Figure
6 that increase in lime from 3.0g to 5.0g have improved the Cr metallization marginally upto 77% and
decreased with further addition of lime. Similarly it is observed that the Fe-metallization have
increased upto about 80% at 5.0g lime and dropped further to as low as about 60% with increase in
lime upto 10g. Increase in CaO content due to lime addition in the charge helps in forming fluid slag at
0
high temperature (1500 C) during the reduction and results in proper slag metal separation. However
excessive amount of lime (greater than 5.0g) also results in increase in slag volume and high fluidity
which may cause loss of metal values to slag. The maximum Cr-metallization of about 77% and Femetallization of 82% is achieved at 5.0g lime addition. Therefore, the optimum amount of lime quantity
is established at 5.0g per 100 g of pre-oxidized chromite ore.

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85
Metallization, [%]
80
75
70
Cr
Fe
65
60
15
20
25
30
35
Coal, [g]
Figure 5:
Effect of coal addition on Cr and Fe metallization in reduced product at 1500 0C
90
Metallization, [%]
80
70
60
50
40
Cr
Fe
10
12
Lime, [g]
Figure 6:
Effect of variation in lime on Cr and Fe metallization in reduced product at 1500 0C
3.2.3 Effect of Quartz

The effect of quartz (silica) addition on the Cr and Fe metallization is studied by varying the quartz
content in close range of 15.6g to 17.2g per 100 g of chromite ore. The minimum required silica is
15.6g for dissolving the alumina and MgO in the chromite spinel to slag and forming the alumino and
magnesio silicate slag. Therefore, the silica content is varied upto 10% excess (17.2g) than the
minimum theoretical required. The effect of variation in quartz on Cr and Fe metallization in reduction
product at 1500 0C is shown in Figure 7. It can be seen that the maximum Cr and Fe metallization is
obtained at 15.6g quartz addition, which was minimum required theoretically. However, with further
increase in quartz the metallization have decreased for both Cr and Fe due to increase in slag
volume. Based on the experimental results, the optimum amount of charge mix for achieving the
maximum Cr and Fe metallization in reduced product at 1500 0C is established at 100g pre-oxidized
chromite, 27.9g anthracite coal, 5.0g lime, 15.6g quartz and 1.5g bentonite as binder. It is also
observed that clear slag and metal separation is achieved at optimized flux conditions.

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90
Metallization, [%]
80
Cr
Fe
70
60
50
15.5
16
16.5
17
17.5
Quartz, [g]
Figure 7:
3.3
Effect of variation in quartz on Cr and Fe metallization in reduced product at 1500 0C
Effect of Degree of Pre-oxidation on Reduction Behaviour
The effect of degree of preoxidation on the reduction behaviour of chromite is investigated by

subjecting the raw chromite ore to oxidation at 900 0C for different duration. For this the raw chromite
ore is heated in air atmosphere upto 180 min duration in step of 30 min. These pre-oxidized chromite
ore samples heated for different duration were then reduced at 1500 0C at optimized coal and flux
conditions. The variation of Cr and Fe metallization in the reduced product with increase in degree
chromite ore oxidation is shown in Figure 8.
85
Metallization, [%]
80
75
70
Cr
Fe
65
60
30
60
90
120
150
180
210
Pre-oxidation Time, [min]
Figure 8:
Effect of pre-oxidation time on Cr and Fe metallization in reduced product at 1500 0C
It can be observed from Figure 8 that, with increase in degree of preoxidation of raw chromite the Cr
and Fe metallization in the reduced product have increased upto preoxidation time of 120min and
further increase in the preoxidation time did not have significant effect on the respective metallization.
It was also observed during reduction experiments that the slag and metal separation was better with
increase in the degree of pre-oxidation in raw chromite ore. With increase in the preoxidation degree,
the improvement in Cr and Fe metallization is expected since during reduction the sequioxide (Fe2O3)
phase formed in pre-oxidation stage reduces first to FeO and then this newly formed FeO acts like
flux even at low temperatures (1200 0C) for slag formation. The cation vacancies generated during the
preoxidation stage of chromite also results in increasing the reactivity of raw chromite thus resulting in

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high metallization of Cr and Fe during the reduction. About 77% of Cr and more than 80% of Femetallization is observed during reduction of chromite ore oxidized for 120 min duration.
3.4
Quality of reduction products
The slag and metal products obtained during reduction of preoxidized chromite at 1500 0C and 2.5h
reduction time are shown in Figure 9. The chemical composition of the metal and slag is given in
Table 2. It can be seen from Table 2 that, the metal nuggets contain high chromium of about 61%,
and iron upto 30%. It was also observed that the metal nugget is easily separable from the associated
slag by physical separation techniques.
Metal
Slag
Al-Crucible
15 mm
Figure 9:
Ferrochrome metal and slag obtained at 1500 0C and 2.5 h duration reduction time
Table 2:
Typical chemical compositions of the metal and slag at 1500 0C and 2.5 h reduction time
Item
Metal
Slag
Fe (t)
28
Cr2O3
26.5
Chemical analysis, wt%

Cr
Si
C
S
61
1.0
4.5
0.03
wt%
SiO2 Al2O3 CaO Fe(t)
19.9 19.4
5.2
6.1
P
0.15
MgO
14.1
CONCLUSIONS
The reduction behaviour of preoxidized chromite ore is studied at high temperature (1500 0C) with
objective of development of process for minimizing the coke and energy consumption in the
ferrochrome production process. It is observed that the preoxidation of chromite ore results in
oxidation of FeO present in chromite spinel to Fe2O3 (sequioxide) as exholved precipitate on the
surface of chromite grains and generates cation vacancies. The effect of various reduction process
parameters such as coal addition and fluxes on the reduction behaviour of pre-oxidized chromite is
examined. The optimum amount of charge mix for achieving maximum Cr and Fe metallization is
established as 100g pre-oxidized chromite, 27.9g coal, 5.0g lime, 15.6g quartz and 1.5g bentonite as
binder. It was seen during reduction experiments that more than 80% of iron and 77% of chromium
metallization is obtained by reduction of pre-oxidized chromite ore at 1500 0C. Clear slag and metal
separation is achieved during reduction. It is also found that increase in the degree of preoxidation in
chromite ore improves the Cr and Fe metallization during reduction process due to improvement in
the reactivity of chromite by preoxidation. The reduced metal obtained in lab reduction experiments is
found to contain high chromium of about 61%, and iron upto 30% and the reduction products (slag
and metal) were easily separable from each other by physical separation.

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REFERENCES
[1] J. M. Daavittila, M. Honkaniemi and P. Jokinen, The transformation of ferrochromium smelting

technologies during the last decades, The Journal of the South African Institute of Mining and
Metallurgy, 2004, 541-549.
[2] V. D. Tathavadkar, M. P. Antony and A. Jha, An investigation of the mineralogical properties of
chemical grade chromite minerals, Scandinavian Journal of Metallurgy, 2004, 33, pp 65-75.
[3] V. D. Tathavadkar, S. M. Rao, K. S. Raju and P. Roy, Indian Patent Application No.
368/KOL/2005.
[4] G. U. Kapure, V. D. Tathavadkar, S. M. Rao, Indian patent Application No. 802/KOL/07
[5] V. D. Tathavadkar, M. P. Anthony and A. Jha, The physical chemistry of thermal decomposition of
South African chromite minerals, Metallurgical and Materials Transactions B, 2005, 36B, pp
75-84.
[6] F. GU and B. A. Wills, Chromite-Mineralogy and properties, Minerals Engineering, 1988, 1, pp
235-240.

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