Fuel 296 (2021) 120640

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Full Length Article

Effect of basicity on the activation energy during reduction of highly fluxed

iron ore pellets
Raj Kumar Dishwar *, Om Prakash Sinha
Indian Institute of Technology (BHU), Department of Metallurgical Engineering, Varanasi 221005, India

A R T I C L E I N F O A B S T R A C T

Keywords: The reduction behaviour of high flux hardened iron ore pellets of basicity 2, 4, 6 and 8 (Basicity = CaO/SiO2)
Iron ore pellet reduced at temperature (900–1050 ◦ C) were examined and reported here. The kinetic model [(1 − α)(− 1/3) − 1]2
Highly fluxed = kt was found to be the best fit model with the present experimental data. Activation energy was calculated
Porosity
based on the above model. It was found to be 31.92, 30.75, 25.97, 20.87 kJ/mol for the pellets of basicity 2, 4, 6
Reduction
and 8 respectively after reduction in the bed of coal. These reduced pellets could be used for steelmaking in the
Kinetics
Activation energy Electric arc furnace (EAF)/Linz- Donawitz (LD) Converter.
Steel making

1. Introduction
Currently Direct reduced iron (DRI) has become an important feed
material for steel industries. Steelmaking processes are slowly shifting
from blast furnace (BF)-basic oxygen furnace (BOF) to DR-EAF route due
to the involvement of huge investment, long gestation period, environ­
mental problems, cost and scarcity of coke used in the blast furnace. DRI
is the main feed material for the DR-EAF route. Lime is an essential
ingredient for steelmaking. Lime works as a fluxing agent during steel­
making and works as binder during pellets making [1]. Availability of
high amount of fines generated during the mining and beneficiation
process (iron ore fines 67%, lime fines 50%) [2] in India open up a way
to produce fluxed DRI. India is the top producer of DRI in world (99.8
million tonnes) with a production of 30.4 million tonnes [3]. So many
researchers have been working on the reduction of iron ore and its
pellets but only few studies are reported in literature for excess lime (2–8
basicity) pellets [4–6]. The reduction kinetics and activation energy for
DRI production depend upon the quality of iron ore, chemical compo­
sition of pellets and reductants being used. Thermodynamic and kinetic
factors such as residence time, temperature and coal consumption ratio
play a vital role in the production of sponge iron [7]. Activation energy
is the key factor which affect the reduction behaviour of pellets. Acti­
vation energy depends on the temperature, residence time and ar­
rangements of the bonds between different materials (iron ore and lime)
which formed earlier during hardening process. The present paper
mainly deals with excessive lime (2–8 basicity) iron ore pellets to derive
various benefits during its use. These excessive lime containing pellets
have been studied with the aim to increase calcium based compound in
the pellets rendering benefits like weather resistance, early slag forma­
tion and insitu lime availability for fixing acidic constituents in the slag.
The high basicity pellets could be used in the electric arc furnace, L.D
converter etc. [6,8]. By using high basicity (8) pellets external charging
of lime can be minimized. Lime can be provide in the calcium ferrite
form or insitu lime which provides better weather resistant properties
compare to free lime therefore lime storage problem can be overcome.
Hardening behaviour of these highly fluxed pellets was studied in my
previous research paper [9]. In this paper, the reduction behaviour of
highly fluxed iron ore pellets (basicity 2 to 8) at different temperature
and time interval have been studied to calculate the activation energy.
Effect of time and temperature on activation energy studied by so many
researchers but only few studies [10,11] seem to be available on the role
of basicity therefore the main aim of this study is to know the effect of
basicity (lime) on the activation energy during reduction of highly
fluxed pellets.
2. Experimental
2.1. Materials and methods
In the present study, the highly fluxed pellet hardened at 1180 ◦ C
temperature were selected for the study of their reduction behaviour.
These highly fluxed pellets were made by using iron ore and lime fines.

* Corresponding author.
E-mail addresses: rajkd.rs.met16@iitbhu.ac.in (R.K. Dishwar), Opsinha.met@iitbhu.ac.in (O.P. Sinha).

https://doi.org/10.1016/j.fuel.2021.120640
Received 3 December 2020; Received in revised form 5 March 2021; Accepted 6 March 2021
Available online 30 March 2021
0016-2361/© 2021 Elsevier Ltd. All rights reserved.
R.K. Dishwar and O.P. Sinha Fuel 296 (2021) 120640

Table 1 earlier report [9].Physical and Chemical properties of pellets and their
Physical and Chemical properties of pellets and their raw materials. raw materials shown in Table 1.
Chemical Composition (Wt. %) Chemical composition of hardened pellets shown in Table 2.
The whole experiment was carried out at four different reduction
Iron Ore (Dry) Lime (Dry)
temperatures (900, 950, 1000 and 1050 ◦ C) for 30, 45, 60, 90 and 120
Fe2O3 Al2O3 SiO2 MnO Others CaO LOI min. Each experiment was performed for a single pellet under
92.50 3.70 2.94 0.09 Rest 95 5
Proximate Analysis of Reductant (Wt. %)
isothermal conditions. Each highly fluxed hardened iron ore pellets were
Reductant Fixed Carbon Moisture Volatile Matter Ash Content weighed and placed separately inside the bed of coal in the steel crucible
Coal 62.50 8.10 14.70 14.70 (60 mm height and 25 mm inside diameter) which was covered using
Properties of Flux Pellets Hardened at 1180 ◦ C grog (crushed refractory powder). Schematic diagram of furnace and
Basicity 2 4 6 8
crucible is given in Fig. 1.
Porosity 36.08 38.02 40.84 43.65
CCS (kg/pellet) 81.62 69.53 99.33 103.10 The crucibles containing pellet were kept one by one inside the
resistance furnace at the predetermined reduction temperature. After
reduction, the crucibles were taken out from the furnace one by one after
a given interval of time. The same procedure was followed for all set of
Table 2
experiments. The degree of reduction and the activation energy was
Chemical composition of hardened pellets.
calculated based on the results obtained for the different set of experi­
Chemical composition of pellets (wt. %)
ments. Scanning Electron Microscope (SEM) and EDS (Model ZEISS
Basicity (CaO/SiO2) Fe2O3 Al2O3 MnO SiO2 CaO Rest EVO-18, OXFORD instrument with software INCA ENERGY 300, accel­
~2 86.95 3.48 0.09 2.76 6 0.72 eration voltage = 20 kV, beam current ~ 5nA) used to identify the
~4 82.33 3.30 0.08 2.61 11 0.68 microstructure and chemical composition of the samples. X-Ray
~6 78.63 3.15 0.08 2.50 15 0.65 Diffraction (XRD) (Model Rikagu Miniflex-600 model with Dtex ultra
~8 74.00 2.96 0.07 2.35 20 0.62
detector and Co-Kα radiation λ = 0.179 nm, acceleration voltage = 40
kV, current = 15 mA) was used to determine the phases present in the
reduced pellets. Samples were scanned at the rate of 2◦ / minute from
20◦ to 110◦ . Expert High Score and PCPDF Software used to determine the
phases of the material.

3. Results and discussion

Figs. 2 and 3 show the effect of temperature and basicity on the

Fig. 1. Schematic drawing of the crucible and resistance heating furnace used
in the experimental study a) Crucible arrangement b) Resistance heat­
ing furnace.
The iron ore and lime fines size were found to be − 72 + 100 mesh
(0.20–0.14 mm). Coal was used as a reductant. Physical and chemical
properties of hardened pellets and their raw materials given in Tables 1
and 2 respectively.
2.2. Experimental procedure
Initially, iron ore and lime fines were weighed separately according
to the required basicity (2, 4, 6 and 8). After weighing the raw materials,
water was mixed in the lime to make a cold slurry and then mixed with
iron ore fines thoroughly to prepare a green mix for making pellets. The
pellets were made by hand rolling. These hand rolled pellets were
spherical in shape having ~ 18 mm diameter. The green pellets were air
dried for one day followed by oven drying for 24 h at 100 ± 5 ◦ C. These
oven dried pellets were hardened by heating at 1100 ◦ C, 1150 ◦ C,
1180 ◦ C and 1200 ◦ C for one hour using resistance heating furnace. The
heat hardened pellets were cooled in the furnace before being taken out.
During heat hardening no sticking between the pellets was observed up
to 1180 ◦ C however these pellets got fused with each other when heat
hardened at 1200 ◦ C. 1180 ◦ C hardened pellets were chosen for studying
the reduction behaviour on the basis of hardened pellets properties i.e.
cold crushing strength (CCS) and porosity. ISO 4700:2015 is used to
measure the CCS and hot boiling water method was used to measure the
porosity of the pellets and explained in detail by the authors in their
reduction behaviour of hardened pellets of basicity 2, 4, 6 and 8
respectively. Values of percentage reduction used to draw the graphs are
average of five samples for each basicity, time and temperature.
It is evident from the Fig. 2 that the reduction of pellets increases
with increasing temperature for a fixed composition of lime (basicity)
[12–14]. In the case of lower temperature (900 and 950 ◦ C), the per­
centage of reduction increases up to 120 min while for the higher tem­
perature (1000 and 1050 ◦ C) reduction increases up to 90 min
afterwards it becomes constant. It may be due to increasing coal reaction
(carbon gasification) with an increasing holding time and temperature,
which enhanced the degree of reduction [15]. The result of this exper­
iment agree with the result of Kumar et al. who achieved more than 90
percent reduction in 2 h at 900 ◦ C [16] and Nargin et al. who achieved
more than 90 percent metallization in 90 min at 1000 ◦ C [7].
Fig. 3 shows that the reduction of pellets increases with increasing
amount of lime (basicity) at a constant temperature. As the percentage
of lime increases the formation of calcium ferrite phases in the pellets
increases which may be responsible for the higher reduction degree with
increasing amount of lime or flux [4,11,17–19]. At the lower tempera­
ture (900 and 950 ◦ C) reduction of pellets increases with basicity for
each interval of time from 30 to 120 min. At temperature 1000 ◦ C
reduction increases up to 90 min while for 1050 ◦ C temperature it in­
creases up to 60 min only afterwards it become constant. At lower
temperature lime have a significant effect on the reduction while at a
higher temperature, it does not play a significant role. It may be either
due to slow diffusion rate of reducing gases at low temperature compare
to higher temperature or lower gasification rate of carbon at lower
temperature compare to higher temperature. Fig. 4B shows that on
increasing basicity chances of free lime availability increases inside the
pellets. It may be due to the reduction of calcium ferrite phases which
formed earlier during hardening process. An increasing amount of free
lime creates more porosity in the pellets which may provide additional
free sites/surfaces for the reaction.
From the above data it was observed that 1-hour holding time at
1000 ◦ C temperature provide sufficient reduction value which is

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R.K. Dishwar and O.P. Sinha Fuel 296 (2021) 120640

Fig. 2. Effect of temperature on the reduction behaviour at a) 2 basicity b) 4 basicity c) 6 basicity d) 8 basicity.

Fig. 3. Effect of basicity on the reduction behaviour at temperature a) 900 ◦ C b) 950 ◦ C c) 1000 ◦ C d) 1050 ◦ C.

desirable for steelmaking. Further to know the behaviour of reduction of pellet before and after 1-hour reduction at 1000 ◦ C temperature. This
optimized samples, XRD (phase analysis) and SEM (morphology) was figure is used to explain the phase changes during reduction with
performed. Fig. 4 shows the presence of different phases in the iron ore different basicity at constant time and temperature. It is clear from the

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R.K. Dishwar and O.P. Sinha Fuel 296 (2021) 120640

Fig. 4. Comparative study of the phases a) phase analysis of hardened pellets (before reduction); b) phase analysis of reduced pellets (after reduction).

Fig. 5. Effect of Basicity on the Rate of Reduction at temperature a) 900 ◦ C b) 950 ◦ C c) 1000 ◦ C d) 1050 ◦ C.

figure that phases present before the reduction changes after reduction.
Calcium ferrite and calcium diferrite phases may dissociate in the iron
oxides and lime after that iron oxides get reduced in the iron. Phases
formed during hardening disappear after reduction. It can be seen from
the figure as the percentage of lime (basicity) increases the intensity of
iron peak increases sharply. In the case of lower basicity (2 and 4), no
peaks of free lime observed it may be due to the presence of free lime less
than 5% which cannot be detected with the help of XRD. For the 2 ba­
sicity FeO peaks are highest with small amount of iron peaks, which
indicates the major presence of iron oxide phase. For basicity 4 intensity
of iron phase increases with few small peaks of FeO. At higher basicity (6
and 8) some peaks of free lime were observed, which indicates the
presence of free lime at higher basicity. It may be due to the higher
reduction of calcium ferrite phases compare to the low basicity pellets.
The presence of free lime provides the more porous media for gas
diffusion which promotes the reduction of hematite into iron.
The effect of basicity and temperature on the rate of reduction are
shown in Fig. 5. Temperature and basicity both were increasing the rate
of reduction, and apparently as the time of reduction increases the rate
of reduction decreases. Coal, which is used as reductant, contains 14.7%
volatile matter. The rate of dissociation of hydrocarbons into the
hydrogen and carbon increases with increasing temperature and time
which may favor the high rate of reduction in the initial stage [20–23].
In initial stage, the amount of unreduced iron ore is high, as the time of
reduction increases the thickness of metallic layer also increases which
may offer resistance to the diffusion of reducing gases for further
reduction, which may reduce the rate of reduction with increase in time.
The reduction takes place in different steps as Fe2O3 to Fe3O4, Fe3O4 to
FeO and FeO to Fe. The reduction of Fe2O3 to FeO is faster than FeO to
Fe, so the rate of reduction in the initial stage is very high [24].

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R.K. Dishwar and O.P. Sinha Fuel 296 (2021) 120640

Fig. 6. SEM images of highly flux hardened iron ore pellets Reduced at 1000 ◦ C for 1 h at 2000× Magnification. a) 2B b) 4B c) 6B d) 8B.

Fig. 7. EDS images of highly flux hardened iron ore pellets Reduced at 1000 ◦ C for 1 h.

Fig. 6 shows change in the morphology of high flux hardened iron into long whiskers (Fig. 6b). The increase in growth could be noted up to
ore reduced pellets with basicity at constant time and temperature. 8 basicity. These growing whiskers push each other and result in shape
The cause of morphology change was found due to iron nucleation change. With further reduction, the fusion of whiskers resulted in
and growth in the form of whiskers. The iron whiskers nucleated shrinkage Fig. 6c and d) [17].
(Fig. 6a) due to reduction of iron oxide at a given site which then grows Fig. 7 shows the scanning electron microscopy (SEM)/energy
dispersive spectroscopy (EDS) analysis of the highly fluxed reduced iron
ore pellets. From the EDS analysis, it can be seen that with increasing the
Table 3 lime (basicity) the amount of free lime increases inside the pellets, which
Crushing Strength of Reduced 8 Basicity pellets. was confirmed by the X-ray diffraction (XRD) analysis. The value of
CCS of 8 basicity Pellets calcium is equivalent to the value added in the starting to make the
pellets, it means there were no loss of lime occurred during hardening
Reduction (%) 30 50 80
CCS (kg/pellet) 29.33 37.92 41.87
and reduction process.

5
R.K. Dishwar and O.P. Sinha
Fig. 8. Model fitting curve for activation energy calculation a) 2 basicity b) 4 basicity c) 6 basicity d) 8 basicity.
Fig. 9. Arrhenius Plot and Activation energy values for basicity 2, 4, 6 and 8 at temperature 900, 950, 1000 and 1050 ◦ C.
Crushing strength of 30, 50 and 80% reduced pellets was performed
and shown in Table 3. It was observed that the CCS after reduction de­
creases compare to hardened pellets but it does not affect the pellets
because after reduction it will be used in the melting unit. CCS value
increased with percentage reduction value. It may be due to the for­
mation of more metallic bonds. Here only high basicity chosen to
determine the CCS because these pellets will further use in melting
process to know the effect of different oxygen potential.
Fig. 8 shows the best fit model for the reduction of highly fluxed (2,
4, 6 and 8 basicity) hardened iron ore pellets. “[(1 − α)(− 1/3) − 1]2 = kt”
(α is the fraction of reduction and t is the time consumed in reduction)
was found best fit model for reduction of fluxed iron ore pellets in coal
bed. Fig. 8 is used to find out the value of constant k for calculating the
activation energy.
The activation energy of the reduction for pellets of different basicity
was calculated from the Arrhenius plots (Fig. 9). As the basicity of pellets
increases the amount of activation energy was found to decrease.
6
Fuel 296 (2021) 120640
Catalytic enhancement of carbon gasification by metallic iron [25] and
higher amount of reduction for high basicity could be responsible for
lower activation energy at higher basicity. The values of activation en­
ergy were 31.92, 30.75, 25.97, 20.87 kJ/mol for the pellets of basicity 2,
4, 6 and 8 respectively. Similar type of energy values were observed by
Mandal et al. 9.97–14.65 kJ/mol for iron oxide and carbon monoxide
combination [26] and Sah et al. 12.37–38.32 kJ/mol for iron ore coal
composite pellets[27].
4. Conclusions
This study resulted following conclusions:
• It is possible to prepare highly fluxed (8 Basicity) and reduced
(greater than80%) pellets by using iron ore and lime fines.
R.K. Dishwar and O.P. Sinha
• Reduction temperature and pellet basicity both affected the reduc­
tion process, giving higher reduction percent with increase in tem­
perature and basicity.
• The kinetic model “[(1 − α)(− 1/3) − 1]2 = kt” is the best fit model for
reduction of highly fluxed iron ore pellets in coal bed. The activation
energy of the reduction decreases with increase in basicity. The
values of activation energy are 31.92, 30.75, 25.97, 20.87 kJ/mol for
the pellets of basicity 2, 4, 6 and 8 respectively.
• The activation energy of the reduction decreases with increase in
basicity.
• The values of activation energy are 31.92, 30.75, 25.97, 20.87 kJ/
mol for the pellets of basicity 2, 4, 6 and 8 respectively.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
Finally, I would like to acknowledge with gratitude, the support and
motivation of Prof. R.C.Gupta Ex. Head of the Department, Department
of Metallurgical Engineering IIT (BHU) Varanasi. He kept me going, and
this paper would not have been possible without his valuable technical
as well as grammatical suggestions.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.fuel.2021.120640.
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