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

 Transactions ISIJ, Vol. 21, 1981 (881)

melt at 1570°C and the phase of iron oxide. Ex- hematite pellets is nearly the same as that of pure
periments with iron melts of carbon content below iron pellets. The temperature dependence of the
2% at 1 520°C could not be performed, because the melting rate of magnetite and wustite pellets above
inside diameter of crucible decreased due to the stick- 1 470°C differs from that below 1 470°C. The ap-
ing of a mixture of splashed metallic iron and iron parent activation energy of melting of pellets obtained
oxide. The sticking was not formed at 1 570°C. from these relations is 35 for hematite; 18 and 41 for
The time required for melting markedly increases magnetite above and below 1470°C, respectively; 44
at the carbon content below 1%. The minimum and 79 kcal/mol for wustite above and below 1470°C,
time required for melting is not recognized for iron respectively. The change of the apparent activation
oxide pellets. For partially reduced pellets, it was energy at 1470°C is considered to be due to the lique-
recognized 2.5'-.'3.5%C.2'4 ) faction of iron oxide.13) Because the melting point
Figure 4 shows the dependence of the time required of FeO is reported to be 1 378°N 1 420°C,'2'14'15)iron
for melting of pellets into the carbon saturated iron oxide liquefies above 1470°C. This is confirmed
melt at 1 520°C on the content of oxide additives in from the observation that the solid iron oxide liquefied
hematite pellets. The time required for melting in- at the last stage of melting above 1 470°C.
creases with increasing contents of CaO, Si02 and Figure 6 shows relations between the melting rate
CaO-Si02. The time for pellets containing 16% is and the carbon content (wt%) in iron melt at 1 570°C.
about 1.5N3 times longer than that of a pellet without Below 4%C, the melting rate of hematite, magnetite
additive. The time required for melting of pellets and wustite pellets is proportional to (wt%C)o.57,
containing up to 8%A1203 increases similarly to the (wt%C)° 45, and (wt%C)° 42, respectively. At
above pellets, but that of a pellet containing 16%A1203 1520°C, experiments with iron melts below 2%C
is extremely long. The time required for melting of could not be performed, and the dependence of the
pellet containing 2%MgO is shorter than that of melting rate on the carbon content was slightly
pellet without additive, but only 1.7 g of a pellet stronger than that at 1 570°C.
containing l6%MgO melted into iron for 10 min. Figure 7 shows the dependence of the ratio of
This pellet was quenched into water and dried at the actual amount of CO gas evolved to the
105°C for 6 h. The structure of this pellet was theoretical amount on the carbon content in iron
examined like the wustite pellet at 1 320°C. melt in alumina crucibles at 1 570°C. The ratios of
hematite, magnetite and wustite pellet in a graphite
I V. Discussion crucible are 1. 1, 0.96 and 1.3, respectively. The
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. 5. Arrhenius-type plot of the melting rate into carbon
saturated iron melts.

Fig. 4. Dependence of the time for melting of pellets into

carbon saturated iron melts at 1 520°C on the Fig. 6. Relations between the melting rate and the wt%C
content of oxide additives in hematite pellets. in iron melt at 1570°C.

Research Article
(882) Transactions ISIJ, Vol. 21, 1981

Fig. 8. Relations between K and 1/T. Values of K (reduc-

tion per cent/s) were obtained from the data in
Fig. 7. Dependence of the ratio of the measured volume
Fig. 1.
of CO gas evolved to the theoretical volume on
the carbon content in iron melt in alumina crucibles
at 1570°C. of a pellet. A constant reducing rate of solid iron
oxide is an indication that the reaction of zeroth order
reason why these values exceed unity would be due is controlled by the chemical reaction.8) However,
to the errors of the CO measurements ( ±5 % ) and as described later, the estimated thickness of the
the pellet weight measurements. Moreover, the diffusion layer at reaction interface was not thin
marked high value of Fe0 pellets is because the enough to deny the carbon transport in iron melt as
the controlling step.
purity was 93.8 %Fe0 and the rest was Fe203. The
ratio for a high cation iron melt in an alumina crucible In order to compare the present results with those
was nearly the same as the ratio for a graphite crucible. obtained by Dancy,5) the data in Fig. 1 were ana-
The amount of CO gas evolved shows a minimum lyzed with the equation of the first and the second
near. 2%C. For the experimental results at 1 520°C, order of reaction. But, both order of reaction did not
the amount of CO gas evolved decreased with de- fit the results. Moreover, the equation used by Kon-
crease of the carbon content in iron melt above dahov et a1.10)and Kato et a1.,11)did not fit the present
2%C. The minimum amount of CO gas evolved data either.
from 2%C melt would be due to the evolution of Figure 8 shows the relations between K and 1/ T.
C02 gas.2,7,9,10) Most of gas evolved from a high Values of K (reduction per cents) were obtained
carbon iron melt would be CO gas, while the amount from the data in Fig, 1. The data points for Fe203
of C02 gas would increase with decreasing carbon and Fe304 represented by a straight line, but the
content down to about 2 %. But the amount of CO point of Fe0 at 1 320°C is much below a best fit line
of Fe0 above 1 370°C. The apparent activation
gas produced as a result of reaction of C02 gas with
the graphite cylinder mounted on crucible would in- energy of the reduction of solid Fe203, Fe304 and Fe0
crease, because the gas evolving rate decreases with by carbon in iron melt was 23, 23 and 42 kcal/mol,
decreasing the carbon content below 2%. Therefore, respectively.
the ratio would again increase with decreasing the Table 2 shows the results of the present work and
carbon content below 2 %. other studies. The apparent activation energy ob-
tained in this work is nearly the same as the values
2. Reductionof Solid Iron Oxides by the Carbon in Iron reported in other work.
Melt The thickness of the carbon diffusion layer at
Solid pellets were observed to react with carbon in reaction interface in iron melt was estimated in the
iron melt except for the last stage of melting. Con- following equation assuming that the diffusion of
sequently, the reduction of solid iron oxides by carbon oxygen in solid iron oxide could be neglected.
in iron melt is considered to play the most significant N/A = K1• C~b, K1= D/o
role in the process of melting of iron oxide pellets
into iron melt. where, N: the CO gas evolution rate (mol/s)
Figure 1 shows the effects of the temperature of A : the area of reaction interface (cm2)
a carbon saturated iron melt and the phase of iron K1: the constant of carbon transfer in iron
oxide on the total reduction. The reaction rate at melt (cm/s)
a range of reduction from 20% to 70% is nearly Cab: the carbon content in bulk iron melt
constant5~9) and is controlled by the reduction of (mol/cm3)
solid iron oxide by carbon in iron melt. The in- D : the diffusion coefficient of carbon in iron
creasing reaction rate at a range of reduction below melt (cm2/s)
20% would be due to the heating of pellets. The o: the thickness of the diffusion layer at
decreasing reaction rate at a range of reduction above reaction interface (cm).
70% would be due to the liquefaction of iron oxide The area of reaction interface was calculated as the
and the decrease of the reaction area during melting 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.
 Transactions ISIJ, Vol. 21, 1981 (885)

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 35 for Fe2O3; 18 and 41 for Fe3O4 above and below

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

Research Article
(886) Transactions ISIJ, Vol. 21, 1981

REFERENCES 12) Handbook of Chemistry and Physics, 53rd ed., ed, by R. C.

1) A. Sato, R. Nakagawa, S. Yoshimatsu, A. Fukuzawa, T. Weast, CRC press, Cleveland, (1972-1973).
Ozaki, K. Kasahara, Y. Fukuzawa and T. Mitsui : Tetsu- 13) T. Sakuraya and K. Mori: Tetsu-to-Hagane, 63 (1977),
to-Hagane, 64 (1978), 385. 5115.
2) A. Sato, K. Kasahara, R. Nakagawa, S. Yoshimatsu, A. 14) JAMAF Thermochemical Tables, ed, by Amer. Chem.
Fukuzawa, T. Ozaki, Y. Iwai, Y. Fukuzawa and T. Mitsui : Soc. and Others, Nat. Stand. Ref. Data Ser . Nat. Bur.
Tetsu-to-Hagane, 65 (1979), 195. Stand. (U.S.A.), Washington, (1971).
3) A. Sato, R. Nakagawa, S. Yoshimatsu, A. Fukuzawa and 15) 0. Kubachewski and E. L. Evans: Metallurgical Thermo-
T. Ozaki : Tetsu-to-Hagane, 65 (1979), 1683. chemistry, Pergamon Press, London, (1958).
4) A. Sato, R. Nakagawa, S. Yoshimatsu, A. Fukuzawa and 16) A Handbook on Properties of Liquid Iron and Slag, ed.
T. Ozaki : Tetsu-to-Hagane, 66 (1980) 545. by Molten Iron and Molten Slag Div., Joint Soc, on Iron
5) T. E. Dancy: JISI, 169 (1951), 17. and Steel Basic Research, ISIJ, Tokyo, (1972).
6) D. R. MacRae: J. Metals, 17 (1965), 1391. 17) Iron- and Steelmaking, ed, by Editing Committee of Newly-
7) G. W. Lloyd, D. R. Young and L. A. Baker: Ironmaking printed Refining Book for a New-style Metal Course, JIM,
and Steelmaking,2 (1975), 49. Sendai, (1965).
8) Y. Sasaki and T. Souma: Tetsu-to-Hagane, 64 (1978), 376 . 18) K. Mori and H. Nomura: Tetsu-to-Hagane,55 (1969), 347.
9) K. Takahashi, M. Amatatsu and T. Souma: Tetsu-to- 19) A. Muan and E. F. Osbon: Phase Diagrams of Oxides in
Hagane, 61 (1975), 2525. Steelmaking, trans. by N. Somiya, Gihodo, Tokyo, (1971).
10) V. V. Kondahov, D. I. Rydjonkov and D. M. Golenko: 20) E. M. Levin, C. R. Robbins and H.P. McMurdie: Phase
Izo. VUZoV. Cher. Met., (1960), 23. Diagrams for Ceramists, Amer. Ceram. Soc. Inc., Columbus,
11) E. Kato, K. Sakuraya and S. Yamagata : Report of the (1964).
Casting Research Laboratory, Waseda Uni., (1973), No. 28, 67.