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ASSESSMENT OF REDUCTION
BEHAVIOR OF HEMATITE IRON
ORE PELLETS IN COAL FINES
FOR APPLICATION IN SPONGE
IRONMAKING
a a
M. Kumar & S. K. Patel
a
Department of Metallurgical and Materials
Engineering , National Institute of Technology ,
Rourkela, Orissa, India
Published online: 18 May 2009.

To cite this article: M. Kumar & S. K. Patel (2009) ASSESSMENT OF REDUCTION


BEHAVIOR OF HEMATITE IRON ORE PELLETS IN COAL FINES FOR APPLICATION IN
SPONGE IRONMAKING, Mineral Processing and Extractive Metallurgy Review: An
International Journal, 30:3, 240-259, DOI: 10.1080/08827500802498215

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Mineral Processing & Extractive Metall. Rev., 30: 240259, 2009
Copyright Taylor & Francis Group, LLC
ISSN: 0882-7508 print/1547-7401 online
DOI: 10.1080/08827500802498215

ASSESSMENT OF REDUCTION BEHAVIOR OF


HEMATITE IRON ORE PELLETS IN COAL FINES
FOR APPLICATION IN SPONGE IRONMAKING
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M. KUMAR AND S. K. PATEL


Department of Metallurgical and Materials Engineering,
National Institute of Technology, Rourkela, Orissa, India

Studies on isothermal reduction kinetics (with F grade coal) in fired


pellets of hematite iron ores, procured from four different mines of
Orissa, were carried out in the temperature range of 8501000 C
to provide information for the Indian sponge iron plants. The rate
of reduction in all the fired iron ore pellets increased markedly with
a rise of temperature up to 950 C, and thereafter it decreased at
1000 C. The rate was more intense in the first 30 minutes. All iron
ores exhibited almost complete reduction in their pellets at temper-
atures of 900 and 950 C in <2 hours heating time duration, and
the final product morphologies consisted of prominent cracks. The
kinetic model equation 1 (1 )1/3 = kt was found to fit best to
the experimental data, and the values of apparent activation energy
were evaluated. Reductions of D. R. Pattnaik and M. G. Mohanty
iron ore pellets were characterized by higher activation energies
(183 and 150 kJ mol1 ), indicating carbon gasification reaction to
be the rate-controlling step. The results established lower values of
activation energy (83 and 84 kJ mol1 ) for the reduction of G. M.
OMC Ltd. and Sakaruddin iron ore pellets, proposing their overall
rates to be controlled by indirect reduction reactions.

Keywords: activation energy, coal, iron ores, reduction

Address correspondence to S. K. Patel, Department of Mechanical Engineering,


National Institute of Technology, Rourkela 769 008, Orissa, India. E-mail: skpatel@
nitrkl.ac.in
REDUCTION BEHAVIOR OF HEMATITE IRON ORE PELLETS 241

1. INTRODUCTION
Many attractive features of direct reduced iron (DRI) have led to an
increase in its production worldwide over the past century, and direct
reduction processes are presently considered to be the most developed
alternative ironmaking route. The basic properties and features of
DRI, produced from different direct reduction processes, have been
well summarized in the literature by Anameric and Kawatra (2007a,b).
Besides emerging as the fifth largest crude steel-producing country
in the world, India has achieved the number one position in DRI
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production in the global market due to the mushrooming growth of coal-


based sponge iron units in the mineral-rich states (Orissa, Jharkhand,
Chhatisgarh, and West Bengal) of the country. Bountiful iron ore and
noncoking coal deposits in the state of Orissa have attracted many steel
magnates in the recent past to invest in the sponge iron sector of the
state. Tables 1 and 2 show the state-wise recoverable reserves of iron
ore (hematite and magnetite) (Ministry of Steel-Government of India
2008) and coal (Economy Watch 2008) in India, indicating Orissa and
Jharkhand to be the largest iron ore (hematite)- and coal-bearing zone
in the country, with reserves of 5951 and 100,959 million tons (MT).
Most of the coal reserves of Orissa are of low-grade (D, E, F and G),
noncoking variety, which has forced the sponge iron industry to utilize
these coals. At present, there are approximately 130 coal-based sponge
iron plants in Orissa with an installed capacity of about 8.22 MT per
annum. This has led to the development of new iron ore mines around
the potential iron zones of the Keonjhar, Sundargarh, and Mayurbhanj
districts of the state. For judicious selection of these ores in sponge
ironmaking, their detailed characterization is essential. The chemical
and physical properties of hematite iron ores, obtained from 10 such
proposed mines, have been reported in our previous article (Kumar
et al. 2008), recommending the majority suitable for use in sponge
ironmaking. However, thorough studies to understand the reduction
kinetics of these iron ore lumps and pellets by easily and abundantly
available low-grade coals with an objective to produce highly metallized
sponge iron have not been attempted so far.
In light of favorable chemical compositions and physical properties
of these iron ores to be exploited in sponge ironmaking, the present
work aims to investigate and compare the kinetic aspects of reduction
of M. G. Mohanty, D. R. Pattnaik, Sakaruddin, and G. M. OMC Ltd.
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Table 1. State-wise recoverable reserves of hematite and magnetite iron ores in India (million tons, MT)

Hematite

High grade Medium grade Low grade


Zone/State (Fe: +65%) (Fe: 6265%) (Fe: <62%) Unclassified Blue dust Magnetite Total

Zone A
Jharkhand 2400 159400 84400 14400 5100 517 26622
Orissa 28000 191600 73700 35000 1100 32940
Zone B
Madhya Pradesh 59690 48070 51700 41150 1890 19980
Maharashtra 730 12870 4680 4420 020 2272

242
Zone C
Karnataka 29990 60080 7310 9770 050 278390 38559
Zone D
Goa 270 21950 46920 4220 1140 16320 4082
Zone E
Andhra Pradesh 1430 190 3170 310 41790 4689
Rajasthan 028 768 104 030 93
Kerala +
Tamilnadu 3710
Grand total 119810 494188 272648 109374 9280 340777 134608
REDUCTION BEHAVIOR OF HEMATITE IRON ORE PELLETS 243

Table 2. Coal reserves in Indian states (million tons)

Madhya Jhar- West Chhattis- Andhra Maha-


State Pradesh Orissa khand Bengal garh Pradesh rashtra Others

Reserves 72204 60984 39975 27813 19232 16926 8582 2131

hematite iron ore pellets by F grade noncoking coal fines in the temper-
ature range of 8501000 C. The gradation of Indian noncoking coals
has been outlined in our previous article (Kumar and Patel 2008). This
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study has been undertaken from the viewpoint of utilization of iron ore
and coal fines generated during mining and handling operations, and
may help in designing a rotary kiln and process parameters. The data
were subsequently used to determine the values of activation energy for
the reduction.

2. SOLID WASTES FROM SPONGE IRON PLANTS


AND THEIR POSSIBLE UTILIZATION
Sponge iron plants and their related mines generate huge amounts of
iron ore, coal, char, and limestone fines as wastes, and their major
portions are sold to other countries at reduced price, resulting in a
substantial financial loss. These fines not only attribute to a huge
loss of valuable resources but also cause environmental problems.
About 60% of the total production of iron ore comes in the form of
fines (5 mm) during the course of mining operations (Tripathy 2007).
Further, 1012% of fines are generated while converting lumps into
calibrated lump ore (CLO) for sponge/pig iron plants. On average,
one has to process 2.5 tons of iron ore lumps to get one ton of
CLO (Tripathy 2007). These data indicate that nearly 7075% of the
total countrys iron ore production is fine. An overview of iron ore
production, consumption, exports, and available surplus in India is
provided in Table 3 (FIMI 2008; Sengupta 2006). It is evident from this
table that after meeting the entire domestic and export demands, there
was still a surplus of 15.30, 19.65, 12.63 and 15.72 MT of iron ore fines
in the last four financial years up to 200607. Further, the share of fines
in total iron ore export is increasing year after year. It was about 74%
in 200203 and increased to about 84% in 200506 (Table 3). Approx-
imately 20% of the coal procured by sponge iron plants becomes fines
(3 mm) and these fines are either sold at a highly reduced price or
244 M. KUMAR AND S. K. PATEL

Table 3. Production, consumption, export and surplus availability of iron ore in India
(million tons)

Production Export
Domestic Surplus
Year Lumps Fines Total consumption Lumps Fines Total (Fines)

200001 33.56 47.20 8076 36.02 3727 747


(41.56) (58.44)
200102 34.57 51.65 8622 37.71 4164 687
(40.09) (59.91)
200203 39.58 59.49 9907 40.94 12.48 35.54 4802 1011
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(39.95) (60.05) (25.99) (74.01)


200304 48.96 73.88 12284 44.97 13.45 49.12 6257 1530
(39.85) (60.15) (21.50) (78.50)
200405 58.15 87.79 14594 48.15 13.54 64.60 7814 1965
(39.85) (60.15) (17.33) (82.67)
200506 62.64 91.79 15443 52.52 11.61 77.67 8928 1263
(40.56) (59.44) (13.00) (87.00)
200607 17200 56.28 10.00 90.00 10000 1572
(10.00) (90.00)

Note: Figures in parenthesis indicate the percentage in the total.

stockpiled (Tripathy 2007). The generation of char fine is about 15% of


the sponge iron produced (Jena 2007).
The availability of fines in large amounts, loss of revenue in their
export, and problems associated with their management have changed
manufacturers thinking in favor of conversion of these wastes into
value-added products that can contribute to lowering the production
cost and effective energy and environmental management. On the
basis of the available literature (Misra and Gupta MG94; Gupta 1999;
Chakravorty 2005; Pani et al. 2007), the following are the suggestions
for exploiting these iron ore, coal, and char fines inside the sponge iron
plants:

i) +35 mm iron ore fines could be processed in rotary kiln directly by


adjusting the coal size and process parameters.
ii) The iron ore fines could be pelletized/sintered and used in direct
reduction or blast furnace ironmaking processes.
iii) CPR (composite prereduced) pellets could be prepared from these
fines for use in iron blast furnaces.
REDUCTION BEHAVIOR OF HEMATITE IRON ORE PELLETS 245

iv) DRI blocks, rods, granules, and cakes could be manufactured from
iron ore and coal/char fines packed in alternate layers in ceramic
saggers.
v) Coal and char fines could be utilized in captive power generation
through fluidized bed combustion boiler. A sponge iron plant with a
capacity of 300 tons/day can produce around 7 MW of electricity.
vi) Coal and char fines could be used in heat hardening of iron ore pellets.

Recycling of iron ore and coal fines in the form of agglomerates in the
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manufacture of sponge iron is the theme of the present study.

3. EXPERIMENTAL
3.1. Materials Selection
In the present study, hematite iron ore samples were collected from
four different mines (D. R. Pattnaik, M. G. Mohanty, Sakaruddin, and
G. M. OMC Ltd.) of Orissa, India. Their chemical compositions have
been outlined in Table 4 (Kumar et al. 2008). Low-grade (F) noncoking
coal, used in the reduction studies, was procured from Brajrajnagar mine
of Orissa and examined for its chemical composition (Indian Standard
IS: 1350 1969), reactivity towards CO2 gas (Indian Standard IS: 12381
1994), caking index (Indian Standard IS: 1353 1993) and ash fusion
temperatures (DIN: 51730 1984). A brief description of the procedures
adopted has been outlined in our previous article (Kumar and Patel
2008), and the results obtained have been listed in Table 5.

3.2. Preparation of Iron Ore Pellets


The pellets were made by rolling moistened (water 15%) iron ore
fines of 100 mesh size for 30 minutes in a drum pelletizer without the

Table 4. Chemical compositions of selected hematite iron ores (wt%, air-dried basis)

Loss on
Iron ore mine Fe (total) Fe2 O3 Al2 O3 SiO2 TiO2 MnO ignition

D. R. Pattnaik 65.22 93.26 1.62 0.92 0.07 0.06 4.07


M. G. Mohanty 64.52 92.27 2.11 1.81 0.08 0.02 3.71
Sakaruddin 64.51 91.74 3.06 1.43 0.14 0.02 3.61
G. M. OMC Ltd. 64.06 91.60 2.52 2.61 0.10 0.01 3.16
246 M. KUMAR AND S. K. PATEL

Table 5. Chemical composition, reactivity, caking index, and ash fusion temperatures of
studied Brajrajnagar non-coking coal

Proximate analysis Ash fusion temperatures



(wt%, dry basis) Sulphur Reactivity ( C)
Volatile Fixed content (cc of CO/g Caking
matter Ash carbon (wt%) of C sec) index IDT ST HT FT

39.25 40.25 20.50 0.55 5.17 Nil 1138 1421 1585 1638

IDT, initial deformation temperature; ST, softening temperature; HT, hemispherical


temperature; FT, flow temperature.
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addition of any other binder. A few pellets of 15 mm diameter were


chosen and dried at 110 C for 2 hours. Induration of these dried iron
ore pellets (contained in fireclay crucibles) was carried out by heating
them in an oxidizing atmosphere from room temperature to 1200 C at a
rate of about 7 C min1 and kept there for 1 hour, followed by furnace
cooling. The indurated pellets were then processed for reduction studies.

3.3. Procedure for Reduction Studies


In the present work, single-pellet type reduction experiments have been
carried out under isothermal heating condition at four different temper-
atures ranging from 8501000 C for varying time periods (range: 15120
minutes). One weighed fired iron ore pellet was placed centrally inside
the packed bed of coal particles (size: 2 + 1 mm) in each of the six
stainless steel reactors (size: 75 mm height 40 mm diameter) tightly
closed with an airtight cover with an outlet for the exit of gas. The
reactors along with their contents were then inserted inside the muffle
furnace maintained at the predetermined reduction temperature. In
doing so, the furnace first cools down by about 30 C, then takes nearly
3 minuts to reach the required temperature reduction. The temper-
ature was controlled within 5 C. After reduction, the reactors were
taken out one after the other at an interval of 15 minutes and cooled
to room temperature. The same procedure was followed for all the
selected varieties of hematite iron ore pellets. The reduced pellets were
weighed and the degree of reduction was expressed as the wt% of
oxygen removed from each of them.
REDUCTION BEHAVIOR OF HEMATITE IRON ORE PELLETS 247

4. RESULTS AND DISCUSSION


4.1. Characteristics of Studied Hematite Iron Ores
and Noncoking Coal
Qualities of raw materials greatly affect the efficiency and economy of
direct reduction processes. Under Indian conditions, the recommended
chemical and physical properties of iron ore and coal to be used in
sponge ironmaking have been summarized in Table 6A (Parts A and B)
(Tripathy 2007; Kumar et al. 2008).
Data for the chemical compositions of selected iron ores (Table 4)
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and their comparison with the requirements in sponge ironmaking


(Table 6AA) indicate the complete suitability of these ores for use in
direct reduction processes. Further, the results for the CO2 reactivity,
sulfur content, caking index, and ash fusion temperatures of the coal
taken under present investigation are extremely encouraging for its
utilization in rotary kilns. However, the fixed carbon content in this
coal is lower, which may increase coal consumption during industrial
operation. Undoubtedly, this is a problem, but the solution is not
difficult, as discussed in our previous article (Kumar and Patel 2008).

4.2. Reduction Behavior of Fired Hematite Iron Ore Pellets


The degree of reduction values of selected hematite iron ore pellets
(fired), reduced under isothermal heating conditions at temperatures
of 850, 900, 950, and 1000 C for different time periods in the range
15120 minutes have been presented graphically in Figures 1 through
4, while Figures 5 and 6 outline the kinetic analysis of the results of
M. G. Mohanty iron ore pellets.

4.2.1. Effects of Temperature and Time on Degree of Reduction.


The results (Figures 1 through 4) established that in all the studied fired
iron ore pellets, the extent of reduction improved greatly with increase of
temperature up to 950 C followed by a decrease at 1000 C. As suggested
by Bodsworth and Taheri (1987), this increase is most probably because
of increased degree of cracking of hydrocarbons of coal volatile matter
and more availability of reducing gases (H2 and CO) at higher temper-
atures. The lower reduction rate at 850 C is more likely to be due to
the combined effects of insufficient cracking of hydrocarbons, higher
tendency of CO gas decomposition and poor availability of reducing
gases, whereas the slowing effect at 1000 C most probably resulted
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Table 6A. Specifications of iron ores for different direct reduction processes

Characteristics of iron ore

Physical

Chemical (wt%) Tumbler Abrasion Shatter


Particle index index index
Fe Al2 O3 + size (wt% of (wt% of (wt% of

248
Process (total) SiO2 S P Alkali (mm) +63 mm) 05 mm) +10 mm)

Midrex 67.0 3.2 0.016 0.015 0.15 635 90.0 7.0 95.0
(min) (max) (max) (max) (max) (min) (max) (min)
HyL 65.5 2.2 0.020 0.10 625 85.0 10.0 90.0
(min) (max) (max) (max) (min) (max) (min)
Rotary 64.0 4.0 0.010 0.040 518 90.0 7.0 95.0
kiln (min) (max) (max) (max) (min) (max) (min)
REDUCTION BEHAVIOR OF HEMATITE IRON ORE PELLETS 249

Table 6B. Characteristics of noncoking coal for use in rotary kilns

Ash
Volatile Fixed Reactivity softening Bulk
matter Ash carbon Sulphur (cc of CO/g temperature Caking Swelling density
(wt%) (wt%) (wt%) (wt%) of C per sec) ( C) index index (kg/m3 )

2732 2125 3042 <10 >20 1300 <30 <10 800

because of covering of unreduced oxides by dense iron layers developed


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through sintering and recrystallization, and formation of viscous slag.


The formation of pasty slag and dense metallic layer reduces or even can
cut off the access of reducing gases inside the pellets and slows down
the reduction. It is also expected that rapid heating at a temperature of
1000 C causes a higher rate of volatile escape from the coal, providing
less time for hydrocarbons to undergo the process of cracking. Almost
complete reduction (>95%) in these fired hematite iron ore pellets was
obtained at temperatures of 900 and 950 C in about 90120 minutes,
indicating higher reducibilities of these ores.
As can be seen in Figures 1 through 4, the heating time has an
approximately identical effect on the reduction behavior of almost all the

Figure 1. Effects of temperature and time on degree of reduction of M. G.


Mohantyfired hematite iron ore pellet.
250 M. KUMAR AND S. K. PATEL
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Figure 2. Effects of temperature and time on degree of reduction of D. R. Pattnaikfired


hematite iron ore pellet.

Figure 3. Effects of temperature and time on degree of reduction of G. M. OMC


Ltd.fired hematite iron ore pellet.
REDUCTION BEHAVIOR OF HEMATITE IRON ORE PELLETS 251
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Figure 4. Effects of temperature and time on degree of reduction of Sakaruddinfired


hematite iron ore pellet.

hematite iron ore pellets studied. With increase in heating time, the
degree of reduction increased at all the studied temperatures, with
the rate being faster up to about 5060% reduction, followed by a
decrease thereafter. The higher reduction rate in the first 30 minutes

Figure 5. Plots of 1 (1 )1/3 vs. time at different temperatures for reduction of M. G.


Mohantyfired hematite iron ore pellet.
252 M. KUMAR AND S. K. PATEL
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Figure 6. Arrhenius-type plot for an isothermal reduction of M. G. Mohantyfired


hematite iron ore pellet.

may be attributed to the combined effects of rapid release of volatile


matter from the coal and less resistance offered in the flow of reducing
gases inside the pellet, as suggested by Bodsworth and Taheri (1987).
It is believed that the released volatile matter gets almost completely
re-formed into H2 and CO, which contributes significantly in giving a
boost to the reduction rate. On the other hand, the formation of dense
iron morphology around the unreduced oxides, decreased availability
of iron oxides, sintering of pores, and diminished evolution of volatile
matter from coal may be held responsible for the slowing of reduction
rate in the latter stage (i.e., after 5060% reduction).

4.2.2. Cracking of Reduced Iron Layer. Visual examination revealed


that the surface characteristics of pellets underwent changes during
reduction, and cracks were formed in the final products. These cracks
were more prominent in the products resulting from the reduction exper-
iments at 900 and 950 C. As suggested by John et al. (1984), this
appears to be due to sufficient generation and expansion of CO and
CO2 gas bubbles at the iron-wustite interface, which eventually leads
to fracture of the covering iron layers. Only fine cracks were observed
in the pellets reduced at 850 C, most probably because of their lower
reduction rates and insufficient nucleation and growth of gas bubbles.

4.2.3. Kinetic Aspects of the Reduction Results. For design of the


rotary kiln, its production rate, and process parameters, a clear-cut
REDUCTION BEHAVIOR OF HEMATITE IRON ORE PELLETS 253

understanding of the kinetics of iron ore reduction by coal is essential.


It has already been established that the overall reaction is a combination
of the gasification of carbon and reduction of iron oxides. Isothermal
reduction kinetic studies were carried out for each type of fired hematite
iron ore pellets at four different temperatures in the range 8501000 C.
A large number of solid-gas reaction models have been formu-
lated, some of which have been applied to the solid-state reduction
of iron ores, as indicated in Table 7 (Ray et al. 1991; Duong and
Johnston 2000). Of these, the kinetic model equation 1 (1 )1/3 =
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kt best fit the present experimental data, as shown in Figure 5 for


M. G. Mohanty-fired hematite iron ore pellet, and the values of rate
constant k at temperatures of 850, 900, 950 and 1000 C were deter-
mined from the slope of respective lines. These rate constants were
then plotted according to an Arrhenius equation to obtain the values
of activation energy, as shown in Figure 6 for M. G. Mohanty iron
ore pellet. Similar plots were obtained for other studied iron ores. The
apparent activation energy values for the reduction of fired pellets in
coal were calculated to be 183, 150, 83, and 84 kJ mol1 (Table 8) for
D. R. Pattnaik, M. G. Mohanty, G. M. OMC Ltd., and Sakaruddin
hematite iron ores. Table 9 lists the activation energies for iron
oxide/ore reduction in various carbon reductants, as reported in the
literature. The presently determined values are small compared to the
values reported for iron ore/oxide-graphite/char systems by Otsuka and
Kunii (1969, 314 kJ mol1 ), Rao (1971, 300 kJ mol1 ), Fruehan (1977,
292336 kJ mol1 ), Srinivasan and Lahiri (1977, 252400 kJ mol1 ),

Table 7. Kinetic model equations usually used in reduction of iron oxide with carbon

Equation Type of reaction kinetics

ln(1 ) = kt Chemical: first order phase boundary reaction


control model equation
1 (1 )1/3 = kt Chemical: contracting spherical reaction control
model equation
[1 (1 )1/3 ]2 = kt Diffusion: Janders equation
1 23  (1 )2/3 = kt Diffusion: Ginstling-Brounshtein (GB) diffusion
control model equation
[(1 )1/3 1]2 = kt Diffusion: Zhuravlev-Lesokhin-Tempelman (ZLT)
diffusion control model equation

, fraction reacted; k, reaction rate constant; t, time.


254 M. KUMAR AND S. K. PATEL

Table 8. Calculated values of activation energy for an isothermal reduction of different


hematite iron ore pellets in coal (temperature range: 8501000 C)

Iron ore pellet D. R. Pattnaik M. G. Mohanty G. M. OMC Ltd. Sakaruddin

Activation 183 150 83 84


energy
(kJ/mol1 )

Abraham and Ghosh (1979, 230305 kJ mol1 ), and Wright et al. (1981,
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290335 kJ mol1 ). This suggests that the kinetics of iron ore reduction
is highly sensitive to the characteristics of carbon used, and the relatively
lower activation energies obtained in the present study with coal may
be attributed to its higher reactivity. Despite somewhat different experi-
mental conditions in the present study, the apparent activation energies
obtained for the reduction of D. R. Pattnaik and M. G. Mohanty
hematite iron ore pellets are fairly comparable to the values reported
for iron ore-coal/char systems by Seaton et al. (1983, 125 kJ mol1 ),
Ray et al. (1991, 186 kJ mol1 ), Haque et al. (1993, 153160 kJ mol1 ),
and Nasr et al. (1994, 121230 kJ mol1 ). An important feature to be
noted is that these values of activation energy for D. R. Pattnaik and
M. G. Mohanty iron ore pellets are very close to that of C + CO2 =
2CO reaction (176218 kJ mol1 ) (Filippov 1975), indicating that the
reductions of these iron ore pellets are most probably controlled by
gasification of carbon. Another interesting finding is that the reduc-
tions of G. M. OMC Ltd. and Sakaruddin iron ore pellets were accom-
panied by lower apparent activation energies (83 and 84 kJ mol1 ) than
D. R. Pattnaik and M. G. Mohanty iron ore pellets, and these results
are in good agreement with the values reported by Ghosh and Tiwari
(1970, 78 kJ mol1 ), Chakravorty et al. (1991, 4270 kJ mol1 ), Dey et al.
(1993, 3544 kJ mol1 ), and Wang et al. (1998, 6983 kJ mol1 ). As
suggested by Otsuka and Kunii (1969), the catalytic enhancement of
carbon gasification reaction by metallic iron could be assumed to be
responsible for lower activation energies in this case and these values
(8384 kJ mol1 ) are comparable to the data for indirect reduction
reactions (6380 kJ mol1 ) (Filippov 1975), indicating reduction of iron
oxide by CO gas to be the rate-controlling step.

4.2.4. Effect of Ore Type on the Reduction Behavior. The hematite


iron ores studied in the present investigation did not show a clear-cut
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Table 9. Activation energies (E) for reduction of iron ores/oxides by solid carbons, as found in the literature

Temperature E
Investigators Charge materials range ( C) (kJ/mol1 )

Otsuka and Kunii (1969) Ferric oxide + graphite 314


Ghosh and Tiwari (1970) Hematite iron ore + lignite char 9001100 78
Rao (1971) Hematite iron ore + graphite 8501087 300
Fruehan (1977) Ferric oxide + coconut charcoal, 9001200 292336
coal char and coke
Srinivasan and Lahiri (1977) Hematite iron ore + graphite 9251060 252400
Abraham and Ghosh (1979) Ferric oxide + graphite 8801042 230305
Wright et al. (1981) Hematite iron ore + coal char 9001200 290335

255
Seaton et al. (1983) Hematite iron ore + coal char 8001200 125238
Magnetite iron ore + coal char 8001200 158
Ray et al. (1991) Hematite iron ore + coal char 9001000 186
Chakravorty et al. (1991) Hematite iron ore + coals 9001100 4270
Haque et al. (1993) Hematite iron ore + coals 9001050 153160
Dey et al. (1993) Chemical grade hematite + coal 9001050 3544
Nasr et al. (1994) Hematite iron ores + petroleum coke 9501100 121230
Wang et al. (1998) Iron ore + coal 10501300 6983
Santos and Mourao (2004) Iron oxides + graphite, 12001350 46120
coke fines and charcoal
Shalini et al. (2005) Hematite iron ore + coal 9001050 59
256 M. KUMAR AND S. K. PATEL

difference in the rate of reduction of their fired pellets, most probably


because of their similar chemical characteristics (Table 4). However,
they showeda difference in their rate-controlling mechanisms, as
discussed in Section 4.2.3 of this article.

4.3. Predictions for the Rotary Kiln Process


of Sponge Ironmaking
In sponge ironmaking by the rotary kiln process, iron ore lumps or
pellets are fed with small pieces of coal, and the production rate is
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very much sensitive to the characteristics of these materials. The present


reduction results of currently studied fired hematite iron ore pellets
are extremely encouraging for their use in rotary kilns. It is worthy to
note here that the higher CO2 reactivities of F grade coals (412 cc
of CO/g of C per sec) (Kumar and Patel 2008) and greater reducibil-
ities of these iron ore pellets could be exploited to reduce the kiln
operation temperature and time, thus the energy consumption. Based
on the data generated in the present investigation (Figures 1 through 4),
the authors suggest that with these iron ore pellets and F grade coals,
the kiln operation should be carried out at a temperature somewhat

below 1000 C to avoid the chance of ring formation and to get a higher
degree of reduction (>95%). Otherwise, sintering of partially reduced
pellets, softening of the slag-forming constituents, and consequent ring
formation inside the kiln may occur, which can completely block the
movement of the bed.

5. CONCLUSIONS
Based on the findings of the present investigation, the following conclu-
sions may be drawn:

1. As expected, the results showed a pronounced effect of temperature


on the extent of reduction in all the studied hematite iron ore pellets.
The reduction rate was enhanced substantially by an increase in

temperature up to 950 C and then decreased at 1000 C.
2. At all studied temperatures, the degree of reduction increased with
heating time, the rate being faster in the first 30 minutes because of
greater influence of volatile matter.
3. The kinetic data for the reduction of studied iron ore pellets by coal
fit best in the chemical control model equation 1 (1 )1/3 = kt.
REDUCTION BEHAVIOR OF HEMATITE IRON ORE PELLETS 257

4. For their reduction in coal, M. G. Mohanty and D. R. Pattnaik


hematite iron ore pellets exhibited apparent activation energy values
(150 and 183 kJ mol1 ) very close to that of carbon gasification
reaction, indicating Boudouard reaction to be the rate limiting over
a considerable range of reduction.
5. The calculated seeming activation energies (83 and 84 kJ mol1 ) for
the reduction of G. M. OMC Ltd. and Sakaruddin hematite iron
ore pellets were found to be comparable to the values for indirect
reduction reactions, suggesting the overall rate to be controlled by
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the reduction of iron oxide by CO gas.


6. The results established almost complete reduction in all studied
iron ore pellets at temperatures of 900 and 950 C in <2-hour time
intervals, indicating their higher reducibilities.
7. The majority of hematite iron ore pellets, reduced at 900 and 950 C,
contained a substantial number of broad cracks, most probably
because of build-up of high gas pressure at the iron-wustite interface.
8. Reduction results indicate that all studied hematite iron ores are quite
suitable for utilization in sponge ironmaking.

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