UDC 622.341.1-188:669.046.512:669.162.263.

24

Melting Rate of Iron Oxide Pellets into Iron Melt*

By Akira SATO,** Ryuichi NAKAGAWA,** Shiro YOSHIMATS U,**

Akira FUKUZAWA** and Tsuyoshi OZAKI**

Synopsis to first grade C.A.), and wustite of 98.3% purity

Themeltingrateof ironoxidepelletsintoironmeltandthereduction
rateof pelletsby carbonin ironmeltwereobtainedby measuring the
evolution rate of CO gas. The pelletsweremadefrom iron oxide
powderbypressingandsinteringand werenotcrushed intopieceswhen
addedontotheironmelt. Theeffects of theironoxidephase,theoxide
additivesin pellets,and the temperature
and thecarboncontentof iron
meltson the meltingand the reductionrateswereinvestigated.The
followingresultswereobtained:
(1) It hasbeen foundthattheheattransferwasnottherate-determin-
ingstepfor thetworates. It is considered that thecarbondiffusionin
a boundary layeron theironmeltsurfacecouldbe the rate-determining
step.
(2) The totalreduction ratewasconstant for reduction
degreesfrom
about20% to about70%, wheresolidiron oxideswerereducedby
carbondissolvedinironmelt.
(3) Theapparent activation
energyof themeltingof pelletsintothe
carbonsaturated iron meltwas 35for Fe203; 18 and 41for Fe304
aboveand below1470°C,respectively; 44 and 79 kcal/mol for FeO
aboveandbelow1470°C,respectively.
(4) The meltingrateof Fe203,Fe304 and FeO pelletsinto the
iron meltat 1570°C was proportional to C057,C045 and G042
respectively,
whereC denotestheweightpercentage of carbonin an iron
melt. Theminimum amountof CO gas evolved wasobtained at about
2%C.
I. Introduction
The melting behavior of reduced iron pellets into
iron melt in the continuous iron- and steel-making
process has been studied at National Research In-
stitute for Metals since 1974. It was shown that the
melting rate of reduced iron pellets into iron melt
depends greatly on the residual oxygen content, the
content and composition of gangue in pellets, the
carbon content of iron melt, the temperature and the
molten slag.1 3~ For a constant residual oxygen con-
tent the melting rate is same for wustite, magnetite,
and hematite at higher temperatures, but it is differ-
ent at lower temperatures.4~
In this report, the melting rate of iron oxide
pellets into iron melt and the reduction rate of iron
oxide pellets by carbon in iron melt were obtained
by measuring the evolution rate of CO gas. The
effects of the phase of iron oxide, the oxide additives
in pellets, and the temperature and the carbon con-
tent of an iron melt on the melting and the reducing
rates of iron oxide pellets have been investigated.
II. Experimental
Iron oxide powder used were pure hematite
[special grade chemical reagents (C.A.) and equiva-
lent to first grade C.A.], pure magnetite (equivalent
made by reducing pure hematite of first grade C.A.
l0-5O g of each kind of iron oxide powder before
and after sintering was formed into a pellet by press-
ing. The pressing under 4 to 6 t/cm2 was performed
using a die and a punch having 7 cm2 of sectional
area. Sintering of iron oxide powder and pellets
was performed in air or Ar gas at 1 000°~ 1 150°C
for 1-4h.
A hematite pellet of 10 g containing oxide powder
of CaO (95.2 % CaO ), A1203 (first grade C.A. ), MgO
(first grade C.A.), Si02 (99.8%Si02) or CaO-Si02
(CaO/ Si02=1) was sintered in air at 1 000°C for
1 h after pressing at 4 t/cm2.
The density of a pellet was calculated from the
weight measured by a direct-vision balance and the
height and the diameter measured by a micrometer.
A Tammann furnace for controlled atmosphere
melting was used.2~ The iron melt was kept at a
desired temperature within ±5°C, and the amount
of CO gas evolved was measured with an integrating
gas meter. Because the measurable range of this
meter was 5 3001/h, nitrogen gas was flowed at the
rate of 601/h in order to measure a small amount of
CO gas evolved.
Graphite crucibles and recrystallized alumina
crucibles of 55 mm ID and 190 mm L were used for
iron melts saturated and unsaturated with carbon,
respectively. Iron-carbon alloys were prepared in
graphite crucibles in an induction furnace.
The experimental procedure was as follows. An
iron melt weighing about 1.5 kg was melted in a
nitrogen atmosphere and held at an experimental
temperature for 30 min and its surface was cleaned
by scraping before and after adding a small amount
of Fe203. Samples for chemical analysis were taken
after stirring the iron melt. A pellet charged pre-
viously in the apparatus was dropped onto the iron
melt after the flow rate of nitrogen gas was recorded
every 30 s for 2 min. From that moment, the flow
rate was recorded every 5 s, and the recording was
continued for 2 min or longer after the end of reaction
was visually recognized. The reproducibility was
confirmed by comparing the results of repeated runs
in each experimental condition.
The time required for complete melting of pellets
was determined as the time from the moment of
dropping the pellet to the last evolution of CO gas.
The melting rate of pellets (g/s) was obtained by
dividing the weight of pellet by the above time. The

* Originally published in Tetsu-to-Hagane, 67 (1981), 303, in Japanese. English version received November 12, 1980.
** National Research Institute for Metals, Nakameguro, Meguro-ku, Tokyo 153.

Research Article (879)

0880) Transactions ISIJ, Vol. 21, 1981

reduction rate of solid iron oxides by carbon in iron saturated with carbon and the phase of iron oxide.
melt, which was considered to play a main role in The time required for melting of pellets increases with
the process of melting, was discussed by using various decreasing temperature and with decreasing oxygen
reduction rate equations reported in Refs. 5) to 11). content in iron oxide. Particularly, the weight of
Fe0 pellet melted into the carbon saturated iron
III. Results melt at 1 320°C for 10 min was only 2.2 g. This
Table 1 shows the apparent density and the porosity pellet was quenched into water and dried at 105°C
of pellets, the latter of which was calculated with the for 6 h. The structure of this pellet was examined by
true density in Ref, 12). The X-ray diffraction an optical microscope, an EPMA and an X-ray
patterns of iron oxides were not changed by sintering. diffractometer. The transformation of iron oxide
Pellets used mainly in this report were those marked from solid to liquid was observed at the last stage of
by in Table 1. The diameter and the height of melting above 1 470°C.
a hematite pellet (15 g), a magnetite pellet (30 g), Figure 3 shows the dependence of the time required
and a wustite pellet (20 g) are approximately 30~x 4, for melting of pellets on the carbon content in iron
30~x 11 and 30~x 7 mm, respectively.
Figure 1 shows the effects of the temperature of
iron melt saturated with carbon and the phase of iron
oxide on the relation between the total reduction and
the time. The relations from about 20% to about
70% of the total reduction are linear, showing that
the reduction of solid iron oxide by the carbon in
iron melt proceeds at a constant rate. The reducing
rate of solid iron oxide increases with increasing
temperature.
Figure 2 shows the dependence of the time for
melting of pellets on the temperature of iron melt

Fig. 2. Dependence of the time for melting of pellets on

the temperature of carbon saturated iron melts.

Fig. 1. Changes of the total reduction rate with time and Fig. 3. Dependence of the time for melting of pellets on
temperature for carbon saturated iron melts. the carbon content in iron melts at 1570°C.

Table 1. Density and porosity of pure iron oxide pellets.


melt at 1570°C and the phase of iron oxide. Ex-
periments with iron melts of carbon content below
2% at 1 520°C could not be performed, because the
inside diameter of crucible decreased due to the stick-
ing of a mixture of splashed metallic iron and iron
oxide. The sticking was not formed at 1 570°C.
The time required for melting markedly increases
at the carbon content below 1%. The minimum
time required for melting is not recognized for iron
oxide pellets. For partially reduced pellets, it was
recognized 2.5'-.'3.5%C.2'4 )
Figure 4 shows the dependence of the time required
for melting of pellets into the carbon saturated iron
melt at 1 520°C on the content of oxide additives in
hematite pellets. The time required for melting in-
creases with increasing contents of CaO, Si02 and
CaO-Si02. The time for pellets containing 16% is
about 1.5N3 times longer than that of a pellet without
additive. The time required for melting of pellets
containing up to 8%A1203 increases similarly to the
above pellets, but that of a pellet containing 16%A1203
is extremely long. The time required for melting of
pellet containing 2%MgO is shorter than that of
pellet without additive, but only 1.7 g of a pellet
containing l6%MgO melted into iron for 10 min.
This pellet was quenched into water and dried at
105°C for 6 h. The structure of this pellet was
examined like the wustite pellet at 1 320°C.
I V. Discussion
1. Time Requiredfor Melting
The time required for melting of pellets includes
the time required of heating pellets, the time required
for reducing solid iron oxide by carbon in iron melt,
and the time required for reducing partly or fully
liquefied iron oxide by carbon in iron melt. In the
development of a new iron- and steel-making process,
the time required for disappearing of pellets, which
is equal to the time required for melting, is consid-
ered to be most important and will be discussed at
first.
Figure 5 shows variations with temperature of the
melting rate (g/ s) into the carbon saturated iron melt.
The temperature dependence of the melting rate of
Fig. 4. Dependence of the time for melting of pellets
carbon saturated iron melts at 1 520°C on
content of oxide additives in hematite pellets.
Transactions ISIJ, Vol. 21, 1981 (881)
hematite pellets is nearly the same as that of pure
iron pellets. The temperature dependence of the
melting rate of magnetite and wustite pellets above
1 470°C differs from that below 1 470°C. The ap-
parent activation energy of melting of pellets obtained
from these relations is 35 for hematite; 18 and 41 for
magnetite above and below 1470°C, respectively; 44
and 79 kcal/mol for wustite above and below 1470°C,
respectively. The change of the apparent activation
energy at 1470°C is considered to be due to the lique-
faction of iron oxide.13) Because the melting point
of FeO is reported to be 1 378°N 1 420°C,'2'14'15)iron
oxide liquefies above 1470°C. This is confirmed
from the observation that the solid iron oxide liquefied
at the last stage of melting above 1 470°C.
Figure 6 shows relations between the melting rate
and the carbon content (wt%) in iron melt at 1 570°C.
Below 4%C, the melting rate of hematite, magnetite
and wustite pellets is proportional to (wt%C)o.57,
(wt%C)° 45, and (wt%C)° 42, respectively. At
1520°C, experiments with iron melts below 2%C
could not be performed, and the dependence of the
melting rate on the carbon content was slightly
stronger than that at 1 570°C.
Figure 7 shows the dependence of the ratio of
the actual amount of CO gas evolved to the
theoretical amount on the carbon content in iron
melt in alumina crucibles at 1 570°C. The ratios of
hematite, magnetite and wustite pellet in a graphite
crucible are 1. 1, 0.96 and 1.3, respectively. The
Fig. 5. Arrhenius-type plot of the melting rate into carbon
saturated iron melts.
into
the Fig. 6. Relations between the melting rate and the wt%C
in iron melt at 1570°C.
Research Article
(882) Transactions ISIJ, Vol. 21, 1981
Fig. 7. Dependence of the ratio of the
of CO gas evolved to the theoretical
the carbon content in iron melt in alumina crucibles
at 1570°C.
reason why these values exceed unity would be due
to the errors of the CO measurements ( ±5 % ) and
the pellet weight measurements. Moreover, the
marked high value of Fe0 pellets is because the
purity was 93.8 %Fe0 and the rest was Fe203. The
ratio for a high cation iron melt in an alumina crucible
was nearly the same as the ratio for a graphite crucible.
The amount of CO gas evolved shows a minimum
near. 2%C. For the experimental results at 1 520°C,
the amount of CO gas evolved decreased with de-
crease of the carbon content in iron melt above
2%C. The minimum amount of CO gas evolved
from 2%C melt would be due to the evolution of
C02 gas.2,7,9,10) Most of gas evolved from a high
carbon iron melt would be CO gas, while the amount
of C02 gas would increase with decreasing carbon
content down to about 2 %. But the amount of CO
gas produced as a result of reaction of C02 gas with
the graphite cylinder mounted on crucible would in-
crease, because the gas evolving rate decreases with
decreasing the carbon content below 2%. Therefore,
the ratio would again increase with decreasing the
carbon content below 2 %.
2. Reductionof Solid Iron Oxides by the Carbon in Iron
Melt
Solid pellets were observed to react with carbon in
iron melt except for the last stage of melting. Con-
sequently, the reduction of solid iron oxides by carbon
in iron melt is considered to play the most significant
role in the process of melting of iron oxide pellets
into iron melt.
Figure 1 shows the effects of the temperature of
a carbon saturated iron melt and the phase of iron
oxide on the total reduction. The reaction rate at
a range of reduction from 20% to 70% is nearly
constant5~9) and is controlled by the reduction of
solid iron oxide by carbon in iron melt. The in-
creasing reaction rate at a range of reduction below
20% would be due to the heating of pellets. The
decreasing reaction rate at a range of reduction above
70% would be due to the liquefaction of iron oxide
and the decrease of the reaction area during melting
Fig. 8. Relations between K and 1/T. Values of K (reduc-
tion per cent/s) were obtained from the data in
measured volume
Fig. 1.
volume on
of a pellet. A constant reducing rate of solid iron
oxide is an indication that the reaction of zeroth order
is controlled by the chemical reaction.8) However,
as described later, the estimated thickness of the
diffusion layer at reaction interface was not thin
enough to deny the carbon transport in iron melt as
the controlling step.
In order to compare the present results with those
obtained by Dancy,5) the data in Fig. 1 were ana-
lyzed with the equation of the first and the second
order of reaction. But, both order of reaction did not
fit the results. Moreover, the equation used by Kon-
dahov et a1.10)and Kato et a1.,11)did not fit the present
data either.
Figure 8 shows the relations between K and 1/ T.
Values of K (reduction per cents) were obtained
from the data in Fig, 1. The data points for Fe203
and Fe304 represented by a straight line, but the
point of Fe0 at 1 320°C is much below a best fit line
of Fe0 above 1 370°C. The apparent activation
energy of the reduction of solid Fe203, Fe304 and Fe0
by carbon in iron melt was 23, 23 and 42 kcal/mol,
respectively.
Table 2 shows the results of the present work and
other studies. The apparent activation energy ob-
tained in this work is nearly the same as the values
reported in other work.
The thickness of the carbon diffusion layer at
reaction interface in iron melt was estimated in the
following equation assuming that the diffusion of
oxygen in solid iron oxide could be neglected.
N/A = K1• C~b, K1= D/o
where, N: the CO gas evolution rate (mol/s)
A : the area of reaction interface (cm2)
K1: the constant of carbon transfer in iron
melt (cm/s)
Cab: the carbon content in bulk iron melt
(mol/cm3)
D : the diffusion coefficient of carbon in iron
melt (cm2/s)
o: the thickness of the diffusion layer at
reaction interface (cm).
The area of reaction interface was calculated as the
contact area between a solid iron oxide pellet and
 Transactions ISIJ, Vol. 21, 1981 (883)

Table 2. Experimental results in the present work and other work.

the iron melt on the condition of its floating. Using

the data in Refs. 16) and 17) the estimated thick-
ness was 24x
N10.3 cm for the carbon saturated iron
melt and 8 X 10_4cm for the iron melt of 1%C at
1 570°C. These values are smaller than those for
the melting of steel scrap into an iron-carbon melt
by Mori and Nomura.l8~ In the experiment by Mori
and Nomura, the melt was stirred by induction of
high frequency. The small values obtained in this
work would be due to the stirring of the reaction inter-
face by the bubbling of CO gas evolved. However,
the estimated values are not small enough to deny
the carbon transfer in iron melt as the rate controlling
step. Fig. 9. Dependence of K (reduction per cents from about
Figure 9 shows the dependence of K (reduction 20% to about 70% of total reduction) on the con-
per cents from about 20% to about 70% of total tent of oxide additives in pellets reduced with
reduction) on the content of oxide additives in pellets carbon saturated iron melts at 1 520°C.
reduced by the carbon saturated iron melt at 1 520°C.
Ca0-Si02 (simultaneous addition of 1; 1), A1203 and
Si02 decreased the reduction rate. The reduction
rate slightly increased with increasing addition of
Ca0 and Mg0 up to about 2%, and decreased greatly
above 8 % of their addition.

3. Heating of Iron Oxide Pellets

Figure 10 shows the effect of the heating of pellets
on the total reduction. The heating of pellets was
performed by suspending them with a Pt wire at
about 2 cm above the iron melt for 5 min at 1 320°C
and 1 370°C, and for 2.5 min at 1 420°C. Because
a liquid droplet from all iron oxide pellets dropped in Fig. 10. Effect of the heating of pellets on the time de-
3.5 min after heating at 1420°C, the above heating pendence of the total reduction. The heating of
conditions were considered to be adequate. The pellets was performed by suspending them with
effect of heating on the reduction rate differed in Pt wire at about 2 cm above the iron melt for
different phases of iron oxide. The heating increased 5 min (1320°C) and 2.5 min (1420°C).
the reduction rate of wustite pellets, but it decreased
the rate of hematite and magnetite pellets. In par- the controlling step.
ticular, the difference was remarkable at 1320°C. The heating of Fe203 and Fe304 in nitrogen gas
Since the time required for melting of wustite pellets containing 0.5 ppm of oxygen is known to transform
heated at 1370°C and 1420°C was about 90% of these phases to FeO.19~ This was also confirmed from
the time for a cold one, the heat transfer could not be an observation in this study that the amount of CO
( 884 ) Transactions ISIJ, Vol. 21, 1981

gas evolved from a heated Fe203, Fe304 or FeO pellet

was less than that from a cold one by 29%, 19% or
3%, respectively. Therefore, the decrease of the
reduction rate by heating is considered to be due to
the transformation of Fe203 and Fe304 to FeO.
However, the reason why the FeO formation decreases
the reduction rate is unknown yet.
Photograph 1 shows the microstructures of the
melting interface of iron oxide pellets floated for
10 min on the carbon saturated iron melt (not shown).
At the melting interface of an FeO pellet (a) at
1 320°C, a dense layer consisted of metallic iron and
iron oxide was observed, while MgO enriched and
condensed in the progress of melting was observed in
an Fe203 16%MgO pellet (b). The structure in the
middle of these pellets was very porous.
Photograph 2 shows the electron and the X-ray
images of the melting interface of a wustite pellet in
Photo. 1. The white phase is confirmed to be metal-
lic iron because the 0 !La intensity is nearly zero.
The existense of metallic iron and wustite were con-
firmed by the X-ray diffraction of this pellet.
Photograph 3 shows the electron and the X-ray
images of the melting interface of an Fe203 16%MgO
pellet in Photo. 1. MgO is known to be enriched
and condensed near the melting interface and also dis-
solved in solid FeO.20~ The transformation of Fe203
to FeO was confirmed by X-ray diffraction of this
pellet. Photo. 1. Microstructures of the melting interface of iron oxide
pellets floated for 10 min on the carbon saturated
iron melt (lower not shown).

Photo. 2. Electron and X-ray images at the melting

interface of wustite pellet floated for 10 min
on the carbon saturated iron melt (lower,
not shown) at 1 320°C.

Photo. 3. Electron and X-ray images at the melting
interface of an Fe203 16%Mg0 pellet float-
ed for 10 min on the carbon saturated iron
melt (lower, not shown) at 1 520°C.
V. Conclusion
Uncrushed iron oxide pellets were added onto
iron melt. The melting rate of pellets into iron melt
and the reduction rate of pellets by carbon in iron
melt were obtained by measuring the evolution rate
of CO gas. The effects of the phase of iron oxide,
the oxide additives in pellets, the temperature, and
the carbon content of iron melt on the melting and the
reduction rates were investigated. The following
results were obtained :
(1) The melting and the reduction rates of heated
hematite and magnetite pellets were smaller than
those of cold pellets, while those of heated wustite
pellets were slightly greater than those of cold pellets.
This indicates that the heat transfer was not the rate-
determining step.
(2) A constant reduction rate was observed at
the range of reduction from about 20% to 70%, and
hence the chemical reaction is considered to be the
rate-determining step.
(3) The estimated thickness of the diffusion layer
of carbon in iron melt was 2N4 x 10.3 cm for the
carbon saturated iron melt, and 8 x 10.4 cm for the
iron melt of 1%C at 1 570°C. These values are not
small enough to deny the carbon transfer in iron melt
as the rate-determining step.
(4) The apparent activation energy of melting
of pellets into the carbon saturated iron melt was
Transactions ISIJ, Vol. 21, 1981 (885)
35 for Fe2O3; 18 and 41 for Fe3O4 above and below
1470°C; 44 and 79 kcal/mol for FeO above and below
1470°C. The change of the apparent activation
energy at 1470°C is considered to be due to the lique-
faction of iron oxide.
(5) The melting rate of hematite, magnetite
and wustite pellets into the iron melt at 1570°C
was proportional to (wt%C)o.57, (wt%C)o.45, and
(wt%C)° 42, respectively. The minimum amount of
CO gas evolved was observed at about 2%C, and
this is considered to be due to the maximum CO2
gas evolution.
(6) Addition of CaO-SiO2 (simultaneous addi-
tion of 1: 1), A12O3 and SiO2 decreased the melting
and the reduction rates of hematite pellets. The
melting and the reduction rates of pellets containing
CaO or MgO were slightly larger than those of pellets
without CaO or MgO below 4% addition, but much
smaller above 8% of addition.
(7) The melting and the reduction rates of wustite
pellets in the carbon saturated iron melt at 1 320°C
were extremely small as a result of the formation of
a dense layer consisted of metallic iron and iron
oxide at the reaction interface. On the other hand,
the rates of hematite pellets containing 8 % and
16%MgO were extremely small as a result of the
enrichment and the condensation of MgO at the
reaction interface.
Research Article
(886) Transactions ISIJ, Vol. 21, 1981
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