Ironmaking & Steelmaking

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Reoxidation of direct reduced iron in ambient air

S. S. AbdElmomen

To cite this article: S. S. AbdElmomen (2014) Reoxidation of direct reduced iron in ambient air,
Ironmaking & Steelmaking, 41:2, 107-111, DOI: 10.1179/1743281213Y.0000000105

To link to this article: http://dx.doi.org/10.1179/1743281213Y.0000000105

Published online: 06 Dec 2013.

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Reoxidation of direct reduced iron in ambient
air
S. S. AbdElmomen*
Fresh reduced direct reduced iron pellets produced in a commercial furnace were reoxidised in
ambient air for 150 days at an average temperature of 27uC. The degree of reoxidation was
determined by weight gain. The reoxidation process is controlled by an irreversible first order
reaction with respect to oxygen. A model based on reaction between gas and porous solid was
used to calculate the degree of reoxidation with time. The calculation results agree satisfactorily
with the experimental data. The apparent rate constant of reaction varies between 1?6561023
and 4?5561023 g/cm2/day, and is inversely proportional to the initial radius of the pellet. The
effect of reoxidation on degree of metallisation and relative metallisation loss was also
investigated. In all cases, two distinct groups of data resulted, reflecting the behaviour of the
two types of oxide pellets charged in the furnace.
Keywords: DRI pellets, Reoxidation, Ambient air, Metallisation loss

List of symbols
b stoichiometric factor
Femet metallic iron content of the DRI
k apparent rate constant of the chemical
reaction
r correlation coefficient
ro initial radius of DRI pellet, cm
x1 equivalent amount of metallic iron converted
to Fe2O3
a degree of reoxidation
m degree of metallisation
mi, mt initial degree of metallisation and metallisa-
tion at time t
Dm, Dmr metallisation loss and relative loss in metalli-
sation
r density of metallic iron in the DRI pellet/
g cm23
SFe total iron content in the DRI
Introduction
Steel production based on the route of direct reduced
iron (DRI) and electric arc furnaces (EAFs) is expand-
ing in countries which have large reserves of natural gas.
Direct reduction normally depends on utilising high
quality iron oxide pellets and reformed natural gas. In
the reforming process, the gas is converted into a
mixture of CO and H2, which reduce the oxide to DRI.
The total world installed capacity of direct reduction
and DRI production at the end of 2011 were 86?7 and
73?32 Mt respectively.1 As a result of the growing
Department of Metallurgy, Tabbin Institute for Metallurgical Studies,
Tabbin, Egypt
*Corresponding author, email sanaa.said@hotmail.com
demand for high quality steel and the increasing price
of steel scrap, the production of DRI grew from 7?14 Mt
in 1980 to 73?32 Mt in 2011 and is expected to further
increase in the coming years. In the Middle East and
North Africa, a region having abundant reserves of
natural gas, the production of DRI increased from
12?06 Mt in 2000 to 25?04 Mt in 2011.1
Because of the high porosity of DRI, it is also called
sponge iron. The extremely high surface/volume ratio
makes DRI very reactive, increasing its susceptibility to
reoxidation and giving it its pyrophoric nature. The
reoxidation reaction in dry air is exothermic.2 The
reaction heat leads to a rapid rise in the temperature
when DRI is stockpiled in large heaps in air and during
its transportation. Because of its poor thermal con-
ductivity, the heat dissipation into the surroundings is
limited and the heat accumulation in a pile may lead to
spontaneous ignition and cause catastrophic fire
hazards. The severe climatic conditions in the Middle
East enhance the tendency of DRI to reoxidation and
hence to catching fire.
The sensitivity of DRI to reoxidation is affected by
the reduction temperature at which it is produced from
iron oxide pellets.3 The lower the temperature, the larger
the pore surface area and consequently the greater is the
tendency for reoxidation.4 A high carbon content leads
to an increase in its stability against reoxidation,
especially when the carbon is combined with iron as
cementite.5,6 Reoxidation behaviour is also affected by
the parent ore.7,8
Many studies and patents have been published, which
deal with the problem of DRI reoxidation and give
proposals for its resolution.914 A practical solution for
its passivation against reoxidation is achieved by its
cooling in a controlled, slightly oxidising atmosphere.3
Reoxidation greatly influences the economics of steel
making from DRI. The electric power consumption

2014 Institute of Materials, Minerals and Mining

Published by Maney on behalf of the Institute
Received 24 September 2012; accepted 25 January 2013
DOI 10.1179/1743281213Y.0000000105 Ironmaking and Steelmaking 2014 VOL 41 NO 2 107
AbdElmomen Reoxidation of direct reduced iron in ambient air

2 Photomicrograph showing topochemical structure of

partially reoxidised DRI pellet (degree of reoxidation
1 Schematic representation of experimental arrangement a50?0587)

increases by about 12 kW h t21 of liquid steel, and the
yield decreases by 0?4% for each decrease in 1% in the
degree of metallisation, when the metallic charge of a
70 t EAF contains about 88%DRI.15
The aim of the present work is to fill the gap caused by
the scarcity in the investigations on outdoor reoxidation
of commercially produced DRI pellets under the atmo-
spheric conditions in Egypt, which are similar to the
climatic conditions in other Middle East countries.
The main parameters to be studied include the
following:
(i) kinetics of reoxidation of DRI pellets under the
climatic conditions in Egypt
(ii) effect of pellet size on the apparent rate of the
reoxidation reaction
(iii) effect of the degree of reoxidation of DRI on
the degree of metallisation and relative metalli-
sation loss
(iv) influence of pellet type on the degree of
reoxidation of DRI.
Experimental
Fresh reduced DRI single pellets were carefully weighed
and put in 19 separate baskets made from NiCr wire
having enough openings to permit free access of ambient
air to the pellet. The radii of the pellets were in the range
from 0?57 to 0?85 cm. The baskets were attached to a
stand and kept in an outdoor unprotected industrial area.
The experimental arrangement is shown in Fig. 1. The
pellets were produced in a commercial Midrex direct
reduction plant and kept in airtight desiccators immedi-
ately after being cold discharged from the reduction
furnace. The furnace was charged with a mixture of two
types of iron oxide pellets imported from two different
sources and having the analysis given in Table 1. The
Table 1 Chemical analysis of iron oxide pellets/wt-%
Fe2O3 Gangue P S
97.01 2.985 0.004 0.001
97.05 2.907 0.003 0.04
average analysis of the two types of DRI pellets and their
physical properties are given in Table 2. The relatively
low apparent density of the pellets (2?93 g cm23) is due to
their high porosity (48?54%).The pellets were subjected to
reoxidation for a total period of 50 days. The degree of
reoxidation was found by weighing the pellets using a
sensitive analytical balance, before treatment and after
the elapse of different time intervals ranging from 1 to
50 days. The average temperature and relative humidity
of air during the investigation period were 27uC and 36%
respectively.
Results and discussion
The reoxidation reaction is assumed to take place in a
topochemical pattern in which an unreacted core is
enveloped by an oxidised layer, which moves parallel to
the surface of the pellet towards the centre. This
assumption is confirmed by the photomicrograph of a
partially reoxidised DRI pellet as shown in Fig. 2. A
schematic illustration of the pellet is given in Fig. 3. The
heterogeneous reaction between O2 in the air and
metallic iron in the DRI pellet is assumed to be
irreversible and of first order with respect to O2, and
can be represented by the general reaction
A(g) zbB(s) ?E(s) (1)
where b is a stoichiometric factor.
At relatively low temperatures, the rate controlling
step of the reoxidation process is expected to be the
chemical reaction.16,17 In this case, reaction rate is
proportional to the interfacial area of the unreacted
core. The rate equation for a spherical pellet of an initial
radius ro (cm) can be written as follows1621
k
1{1{a1=3 ~ t (2)
r ro
where r is density of metallic iron in the DRI pellet
(g cm23), ro is initial radius of the pellet (cm), k is the
apparent rate constant of the chemical reaction (g/cm2/
day), t is the time (day) and a is the degree of
reoxidation.

Table 2 Average chemical analysis (wt-%) and physical properties of two types of DRI pellets

SFe Metallic Fe FeO Gangue Metallisation C True density/g cm23 Apparent density/g cm23 Porosity/%

92.34 88.51 4.93 4.71 95.85 1.85 5.6944 2.9303 48.54

108 Ironmaking and Steelmaking 2014 VOL 41 NO 2


3 Schematic representation of partially reoxidised DRI
pellet
The degree of reoxidation a is defined as
a~
3
weight of oxygen gained by the DRI during reoxidation
weight of oxygen required for conversion of metallic iron and residual FeO to Fe2 O3
In this definition, the residual oxygen in the DRI (as
FeO) may be taken into consideration or it may be
neglected.21 In the present investigation, it is taken into
account. Therefore
weight gain initial weight of the DRI pellet
a~ P P (4)
Fe|48=111:7{ Fe{Femet |16=55:85
where SFe and Femet are the total iron and metallic iron
contents of the DRI.
Using the analysis of the DRI as given in Table 2 and
substituting for SFe and Femet in the above equation,
then
weight gain=initial weight of the pellet
a~
0:3858
Estimation of apparent rate constant
By plotting the left hand side of equation (2) against the
time, t, and assuming unchanging initial radius and
density of the pellets during reoxidation, a straight line
should be obtained, if the above mentioned assumptions
are valid and the reoxidation process is controlled by the
chemical reaction rate. Figure 4 presents the variation of
4 Variation of 12(12a)1/3 with reoxidation time, regres-
sion lines and experimental data
AbdElmomen Reoxidation of direct reduced iron in ambient air
(3)
5 Variation of degree of reoxidation with time: theoretical
curves calculated by using slopes of lines in Fig. 4 and
experimental data
12(12a)1/3 with the time for six pellets having close size
with an average initial radius of 0?69 cm according to
equation (2). It can be seen that the lines are more or less
straight. Furthermore, they are grouped into two groups
reflecting the two types of iron oxide pellets imported
from two different sources and fed to the reduction
(5) furnace. The origin of pelletised iron ore and the
temperature of green pellet induration influence the
reoxidation behaviour of DRI produced from these
pellets.7,8 The following regression equations describe
lines 16 respectively
1{1{a1=3 ~2:493|10{3 t, r~0:9896 (6)
1{1{a1=3 ~1:984|10{3 t, r~0:9823 (7)
1{1{a1=3 ~9:27|10{3 t, r~0:9836 (8)
1{1{a1=3 ~2:251|10{3 t, r~0:982 (9)
1{1{a1=3 ~1:066|10{3 t, r~0:9791 (10)
1{1{a1=3 ~8:83|10{4 t, r~9791 (11)
The high values of the correlation coefficient r in
equations (6)(11) indicate satisfactory linearisation of
the relationship between 12(12a)1/3 and the time. This
shows the applicability of the chemical model and
the validity of the above mentioned assumptions to the
problem at hand. The corresponding values of the
apparent chemical rate constant are 1?9461023,
1?7761023, 1?6561023, 3?0961023, 3?2161023 and
4?5661023 g/cm22/day respectively.
The remaining samples followed the same trend of the
six representative pellets they were grouped into the
above mentioned two groups, and their deviation was
only due to their size.
The slopes of the straight lines in Fig. 4 have been
used to calculate the variation of the degree of
Ironmaking and Steelmaking 2014 VOL 41 NO 2 109
AbdElmomen Reoxidation of direct reduced iron in ambient air

6 Variation of rate constant of chemical reaction with

reciprocal of pellet radius

7 Effect of reoxidation time on degree of metallisation

reoxidation a with the time for the same samples
according to equation (2). Figure 5 shows the calculated
lines together with the experimental points. It can be
seen that the experimental data are in reasonable
agreement with the calculated values, which again
supports the validity of the selected model.
Another equation of the type21,22
{ln1{a~kt (12)
was used to estimate the apparent reaction rate constant
and to check the result obtained by using equation (2).
In both cases, the results were in good agreement.
Furthermore, a trial to describe the experimental
data by using an exponential relationship was carried
out. This, however, did not improve the correlation
coefficient.
Effect of pellet radius on apparent rate constant
In order to ensure that the process is controlled by phase
boundary reaction at the interface between reoxidised
zone and unreacted core, the values of k were calculated
for four DRI pellets of different sizes. The radii of these
pellets were 0?58, 0?61, 0?73 and 0?80 cm. The correspond-
ing values of the apparent rate constant are 3?0861023,
3?2161023, 1?9461023 and 1?7761023 g/cm2/day. The
pellets were subjected to reoxidation for 50 days. The
values of k were plotted against reciprocal of the pellet
radius as illustrated in Fig. 6, where it can be seen that
k is inversely proportional to the radius of the pellet,
which also emphasises that the reaction is chemically
controlled.14 According to Fig. 6, the relationship
between k and 1/ro can be described by the formula
k~3:0|10{3 |1=ro {2:0|10{3
this time to find the equivalent amount of metallic iron
converted to Fe2O3, xt, as follows
weight gain
xt ~ |111:7=48 (16)
initial weight of the pellet
The degree of metallisation is then
mt ~0:8851{x1 =0:9234 (17)
The results of these calculations are summarised for the
above mentioned six pellets in Fig. 7, which shows the
decrease in metallisation with time. Here, also, the two
groups of curves reflect the behaviour of the two types of
iron oxide pellets imported from two different suppliers
and used as the furnace feed.
Effect of reoxidation on relative metallisation loss
The metallisation loss Dm is
Dm~mi {mt (18)
The relative metallisation loss Dmr was calculated as
follows
Dmt ~Dm=Dmi |100% (19)
where mi and mt are the initial and the degree of
metallisation at time t respectively.
The result for the six samples is presented in Fig. 8. It
is clear that the relative metallisation loss increases with
time as a result of reoxidation. The two groups of curves
(13)

Effect of reoxidation on degree of metallisation

The degree of metallisation m is defined as
Femet
m~ P (14)
Fe
The initial degree of metallisation mi was calculated
using the DRI analysis given in Table 2 as follows
mi ~0:8851=0:9234~0:9585 (15)
At a given reoxidation time, the value of the degree of
metallisation can be calculated using the weight gain at 8 Effect of reoxidation time on relative loss in metallisation

110 Ironmaking and Steelmaking 2014 VOL 41 NO 2


show that the relative metallisation loss is dependent on
the type of oxide pellet from which DRI was produced.
A trial to fit the experimental data in Figs. 7 and 8 to
an exponential relationship did not improve the result.
Conclusions
Fresh reduced single DRI pellets were reoxidised in
ambient air at an average temperature of 27uC, and the
reaction duration was varied from 1 to 50 days. The
degree of reoxidation was determined by weight gain.
Based on the results obtained, some important conclu-
sions can be made, which show the reoxidation
behaviour of DRI when stockpiled in air:
1. The reoxidation process proceeds topochemically
and is controlled by the apparent rate of chemical
reaction at the interface between the oxide layer and
unreacted core of metallic iron. The experimental data
could be fitted to a kinetic equation of the type
k EUR, Luxembourg, 2003, No. 20632, 1132.
1{1{a1=3 ~ t 12. Process for treating sponge iron for protection against reoxidation and
ro ro
This shows the variation of the degree of reoxidation with
time.
2. The apparent reaction rate constant is inversely
proportional to the pellet radius and varies between
1?9461023 and 4?5561023 g/cm22/day.
3. The increase in degree of reoxidation and accom-
panying decrease in metallisation are dependent on the
source of oxide pellets used for DRI production.
Acknowledgement
The author wishes to thank Alexandria National Steel
Co. for providing the DRI pellets.
AbdElmomen Reoxidation of direct reduced iron in ambient air
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