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Ore
By
of Alkalis
on Reduction
Behavior
Iron
Pellets*
Taymour
ELKASABGY**
Synopsis
Under conditions relevant to the process of an iron blast furnace with
alkali cycling, acid iron ore pellets were tested. The alkalis were introducedin three different ways: as part of thepellets gangue phase, as fine
crystals of alkali carbonatesnear the pellets surface, and, as metal vapor
mixed with the reducinggas.
During reductionalkalis flux thesilicate binding bridges and react with
ferrous iron oxideforming low melting point slag which weakensthepellets
and causes them to degrade. A mechanism of degradation will be given
which relates the behavior of the pellets to theformation of this primary
slag. Also, certain measuresto control the reductionwill be discussed.
I.
Introduction
Alkalis are known to cycle and sometimes to accumulate in the iron blast furnace.)-4) This phenomenon is related to the counter current character of the
furnace and the existence of two gradients of temperature and oxygen potential between its top and the
tuyeres level.5'6~ By sampling and direct observation, during relining of the furnace refractories, it is
known the alkali contents in the burden materials increase as they move down towards the melting zone
in the blast furnace.3'5,6> The higher the alkalis in
the raw materials the easier it is for them to circulate
and accumulate and to build up to dangerously high
levels.
The adverse effects of alkalis are higher coke rate,
poor quality of hot metal and deterioration of the furnace lining. Also, they cause irregularities in the
operation process and decrease the production. However, the determinate effects of alkalis are more pronounced when the stability of the coke and/or the
iron ore is relatively low.
In the present work it is intended to simulate to a
certain extent reduction conditions relevant to the
process of an iron blast furnace with alkali cycling and
to investigate the behavior of a typical acid iron ore
pellets before the formation of a strong metallic shell.
II.
of Acid
Horas Investments (Kingston), Kingston, Ontario K7L 3C7, Canada. On leave from Department of Metallurgy & Materials Science,
The Catholic University of Rio de Janeiro, Rio de Janeiro, CEP 22453, Brazil.
612 ) Research
Article
Transactions
formation, the practical solution is to decrease the alkali content, and/or, the alkali to silica ratio in the
used ore.9'10~ On testing ordinarily acid pellets, which
contains about 5 wt% silicate gangue phases, it was
found that they swell and crack without evidence of
iron whiskers formation.12,13)
In designing the experiments alkalis were introduced in three different ways corresponding to an
iron blast furnace with alkalis cycling:
(1) As part of the gangue phases : representing
pellets originally of high alkali content.
(2) As alkali carbonate fine crystals near the pellets outer surface : representing pellets with precipitated alkali compounds, as a result of condensation
and chemical reactions involving alkali vapors in the
blast furnace stack. Alkali cyanides cannot be used
for safety reasons; however, they are assumed to behave much like alkali carbonates.5,s~
(3) As alkali metal vapors mixed with the reducing gas : representing the conditions of reduction by a
blast furnace gas contains alkali vapors.
III.
Experimental
Chemical
analysis
of iron
24,
1984
(613)
2.
ExperimentalApparatusand Procedures
The experimental apparatus consisted, mainly, of
a Marshall resistance heated tubular furnace, which
contained a movable quartz tube of 40 mm inside diameter. The components of the reducing gas mixture : CO, CO2 and N2 were supplied by separate
cylinders, with flow rates monitored by individual flow
meters, and, mixed before entering the reaction tube.
The specimens were placed in the middle zone of the
tube on top of ceramic or platinum boats, during the
reduction tests. They were moved together with
the quartz tube to the hot zone of the furnace, and
left under N0 flow for about 10 min until the isothermal temperature level was reached, which was checked using a separate thermocouple placed just above
the specimens. Then, the reducing gas mixture was
allowed into the tube and the reduction time was
counted using an automatic stopwatch. Once the reduction is over, the gas mixture was switched off, and
purified N2 was allowed to flow, while the partially
reduced pellets were taken together with the tube to
the cooler end of the Marshall furnace.
To simplify the comparison of the results, most of
the reduction test were carried out under the same
standard conditions for 1 hr using a gas mixture of
CO, CO2, and, N2 at a total flow rate of 500 cc (STP)/
min (the individual flow rates were : N2 300, CO
160, and CO2 40 cc (STP)/min, respectively), at a
temperature of 900 C, which corresponds to that of
Vol.
Work
Table
ISIJ,
ore
concentrate
and
commercial
pellets.
Research
Article
( 614)
Transactions
1984
the thermal
and chemical
reserves zone of some blast
furnaces.14)
Weighing
and volume measurement
by a mercury
displacement
were carried
out before and after the
reduction
experiments
to obtain the extents of reduction and swelling.
The degree of reduction
was calculated based on the initial oxygen content with the
iron oxides, from chemical
analysis, and, the amount
of oxygen taken during
reduction.
The swelling index is defined
as the percentage
increase
of the apparent volume of the specimen
after reduction.
some occasions, due to the effect of alkalis, cracks
fissures were developed
during
reduction.
The
On
and
ap-
Table
Research
Article
2.
Standard
reduction
Iv.
Experimental Results
As received commercial acid pellets, which had a
porosity of about 25 %, swelled normally (about
18 %) after the standard reduction test. SEM observation indicated no iron whiskers formation, also,
the pellets did not show a tendency to form macrocracks or fissures during reduction. Of course, care
was exercised not to choose pellets with defects orr irregularities, which may arise during their industrial
making, and, effect the results, for any of the tests in
this work.
To study the effect of gangue, the pellets made
from chemical reagent hematite were tested. Those
of a porosity of about 20 % disintegrated during reduction, but more compact specimens of porosity less
than 10 % swelled normally, after the standard reduction test.
1.
free
specimens.
Transactions
Effect
tory
Fig . 2.
of firing
and
alkalis
on the
swelling
Fig.
3.
alkalis
and
prior
reduction
to standard
of acid
reduction.
pellets
with
and
reduction
dipped
drying
24,
(615)
1984
in alkali
and
standard
Alkali impregnated
of commercial
carbonate
pellets
solution
which
followed
by
reduction.
commercial
pellets reduced
with
of 1abora-
doped
Swelling
were
pellets.
Swelling
Vol.
Fig. 4.
Fig . 1.
ISIJ,
Fig.
5.
Swelling
duced
and
with
reduction
gas
mixture
of commercial
containing
pellets,
re-
alkali vapors.
Research
Article
(616)
Transactions
ISIJ, Vol.
24,
1964
Photo.
Research
Article
1.
Some
SEM
photographs
of partially
reduced
s pecimens
after
standard
reduction.
Transactions
lets:
(1) A cylindrical specimen of about 1 g was made
by cutting and shaping a commercial pellet. It was
placed on top of about 0.1 g potassium carbonate, in
the upright position. The specimen was then reduced
using the standard reduction procedures.
(2) A commercial pellet was left, immersed in
molten potassium carbonate, under flowing N2 for
1 hr at 900 C.
The two specimens were examined using an electron probe microanalyzer (with electron beam of
about 30 pm in diameter), and the distributions of K,
Si, and Fe were plotted. The results given in Fig. 6
indicate that although the pellet was completely immersed in molten potassium carbonate under flowing
N2 for 1 hr there was relatively poor penetration.
Near the surface the silica was moved inward with the
potassium to a distance of about 200 dim (region AB
in Fig. 6). Beyond this region where silica was depreciated there was another region BC, of about 900
im where Si and K, appeared to be in phase. Further inward, the penetration of potassium nearly stopped, and larger peaks of Si, representing the silicate
gangue phases was observed in the pellets interior.
The reproducibility of these results was checked in
three different locations which showed almost the same
profiles for K, Si, and Fe. It was confirmed that the
potassium carbonate was in its molten state by its appearance in the platinum crucible after cooling the
specimen to room temperature.
In the experiment with the specimen which was
left to be reduced on top of potassium carbonate melt,
all the potassium carbonate was taken up by the speci-
Photo.
2.
SEM
shows
photographs
clearly
and
that
the
X-ray
slag
mapping
areas
are
of Fe,
high
ISIJ,
Vol. 24,
1984
(617)
Discussion
After firing
their strength
and induration
the iron ore pellets owe
to the formation
of hematite,
and,
Si, and
in both
Si and
after
reduction
of
alkali
impregnated
pellets.
It
K.
Research
Article
(618)
Transactions
Fig.
Is",
6.
Fig . 7.
gue
which
Distribution
pellets
Research
Article
was
contains
phases.15-17)
The experimental
oratory
24,
1984
Distribution of K, Si, and Fe near the pellet surface after heated under N2
no reduction) but was immersed totally in molten K,C03 during testing.
which
compacts,
Vol.
made
results
without
of K,
placed
Si, and
on
reasonable
given
alkali
the
Fe
across
top of K2C03
amount
in Fig.
addition,
the
center
melt
of gan-
1 with
lab-
showed
line
during
after
standard
reduction
(300 CC STP/min
flow
of
acid
pellet
and
specimen
reduction.
index decreased
with elevating
the
On the other hand, high purity
had structure
and overall porosity closer
pellets
tended
to disintegrate
as ex-
Transactions
Table
Photo.
3.
taking
Photographs
us, prior
duction
to standard
and
3.
Standard
reduction
of
modified
to the cooling
and heating
Vol.
24,
1984
(619)
pellets.
ISIJ,
procedures
pellet, impregnated
occur during early
under
N2.
The experiments
carried out to simulate
the influence of alkali on the reduction
behavior
of acid pellets
showed, clearly, that the formation
of iron whiskers is
not the cause of their degradation.
Visual observation, and, SEM examination
of the partially
reduced
specimens,
showed the pellets to swell, and to form
macrocracks
and fissures as result of alkalis attack.
The results given in Figs. 1 to 3, and 5 suggest that
the extent of swelling and reduction
to increase with
alkalis.
Also, Fig. 4 supports
the idea that the observed swelling
is independent
of the metallization
step.
The correlation
between
the existence of liquid
slag high in both alkalis and silica and the formation
of cracks is supported
by SEM and electron
probe
microanalyzer
examinations.
The first step of reduction
from hematite
to magnetite seems to be necessary
for the movement
and
progress of the alkali contained
slag inside the pellets.
This important
piece of information
can be seen if the
results in Figs. 6 and 7 are compared.
Reduction
and liquid formation
are necessary
conditions,
however, not sufficient.
Uneven
distribution
of alkali
liquid slag inside the pellets is needed.
The results
given in Table 3, with alkali impregnated
modified
pellets, indicated
no big change in swelling and cracking, when alkalis were relatively
more uniformly
dis-
Research
Article
(620)
Transactions
ISIJ,
Vol.
24,
1984
tributed.
During drying of green wares in ceramic industry
different shrinkage rates, due to uneven moisture content between the surface, and the interior parts can
cause cracking. The case under investigation may be
close but in the reverse direction. During reduction
liquid alkali silicate slag is formed near the surface,
and moves inward most probably due to capillary
forces. However, at any moment its distribution is
not uniform. The uneven distribution can be understood in the following way : the fine crystals of alkali
carbonates were concentrated near the surface when
reduction started (alkali impregnated pellets) ; when
they were added prior to pelletizing and firing, alkalis
were more or less distributed uniformly, however, reduction started near the surface; therefore, the distribution of liquid slag was also not uniform (alkali
doped pellets) ; with reduction using alkali contained
gas, both the reduction and the slagging processes occurred at the gas/solid contacts near the surface, in a
way very similar to the case with impregnated pellets.
The slagging process near the surface started the cracks
(Photo. 1(A)), while its movement, and, in later stage,
its aggregation with the iron oxide grains, facilitated
their propagation (Photo. 1(B)).
Testing commercial acid pellets in the laboratory
showed they swell and crack due to alkalis, the important question is whether it happens inside the blast
furnace. If alkali contents are high in the ore, which
is of ordinary composition, at the moment when ferrous oxide becomes available, cracking and swelling
are expected. Also, when the first stages of reduction
are taking place using blast furnace gas containing
alkalis : ferrous oxide and alkali oxides are formed
simultaneously at the gas/solid interface creating favorable conditions for cracking and swelling. However, these two cases are not quite normal. It is reasonable to assume the conversion of hematite to
magnetite, for the locations near the pellets surface, is
completed before they arrive to the higher alkali zones
in the blast furnace. Swelling and cracking are not
expected to cause serious problems if the alkalis are
introduced after prereduction as illustrated in Table
3. However, since the pellets contain relatively large
quantities of liquid phase due to the formation of alkali
iron silicate slag, and are subject to compression load,
they are expected to soften during reduction inside the
blast furnace.
In most of the experiments carried out, the alkalis
to silica ratio was varied; however, the initial gangue
was kept the same. Figure 8 is given to illustrate the
case when the silica content of the ore is modulated.
It was calculated based on equilibrium between wustite, silica, and potassium oxide at 900 C. Of course
the formation of liquid phase and its relative amount
depend on kinetic factors; however, the informations
given in Fig. 8 suggest the amount of liquid slag to be
sensitive to the absolute amount of the acid gangues.
Therefore acid pellets subject to the same level of
alkali cycling are expected to have better resistance
when the relative amount of gangues exceeds certain
limit. The silica rich gangues may have a dual effect.
Research
Article
Fig.
8.
Formation
based
Fe0
on
of
the
in presence
alkali
iron
equilibrium
silicate
between
slag
at
900
Si0 2, K20,
C,
and
of iron.
Conclusions
As a general mechanism
formation
of iron whiskers
cannot
adequately
be accepted
to explain
all the
causes of degradation
of iron ore pellets due to circulation
and accumulation
of alkalis in the blast furnace.
It seems the alkalis react with the silica rich
gangue and ferrous iron oxide to form primary
liquid
slag, at relatively
lower temperature
levels.
Its formation and movement
between
the iron oxide grains
cause the binding phase to disintegrate
during reduction.
When acid pellets were tested in the laboratory,
and the alkalis were introduced
in three ways relevant
to alkalis' cycling in the blast furnace,
they showed a
tendency
to swell and crack due to formation
of unevenly distributed
liquid slag coupled by hematite
to
Transactions
magnetite
phase transformation.
Formation
of liquid
alkali iron silicates lowers the pellets resistance
and
the phase transformation
is likely to create stresses
which
may act as a driving force for cracking
and
swelling.
Inside
the blast furnace
the reduction
process
is
accompanied
by compression
load.
Therefore,
the
formation
of liquid alkali iron silicate slgas is expected
to weaken the pellets.
However,
they are not likely
to swell, and crack because the first reduction
steps to
magnetite
usually takes place in the upper parts of the
furnace
stack, where the extent of alkalis is a minimum.
Softening
may be the real cause of degradation when relatively
large
quantity
of liquids
are
formed due to alkalis.
Of course, the pellets resistance is a function of both the alkalis and gangue quantities, under
similar reduction
conditions.
Minimization of alkalis, which are cycling in the blast furnace,
is always desirable.
Also, there is a minimum
amount
of gangue
contents
to ensure smooth
operation
and
optimum
behavior,
which in turns is a function
of
alkalis to silica ratio during reduction.
Acknowledgements
3)
4)
5)
6)
7)
8)
9)
10)
11)
12)
13)
14)
15)
Professor,
Science,
Canada,
REFERENCES
1) F. D. Richardson and J.H.E. Jeffes: JISI,163 (1949), 397.
2) "Alkalis in Blast Furnaces ", 1st McMaster Symposium on
16)
17)
18)
19)
20)
ISIJ,
Vol.
24,
1984
(621)
Research
Article