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Developed Model For Reduction Mechanism of Iron Ore Pellets Under Load
Developed Model For Reduction Mechanism of Iron Ore Pellets Under Load
Developed Model For Reduction Mechanism of Iron Ore Pellets Under Load
of freshly formed metallic iron that increased with Results and discussion
temperature and reduction extent.
The present study is designed to investigate the X-ray phase analysis and microscopic examination
influence of the reduction parameters of temperature, indicated that hematite (a-Fe2O3) is the predominant
load applied and chemical composition on the structural phase in both fluxed pellets. In acidic pellets, iron-
changes accompanying sticking of high grade iron ore aluminium silicate phases were identified while calcium
pellets. A developed model was demonstrated to study and magnesium ferrites were identified in basic pellets.
the effect of reduction conditions on the kinetics and These phases were formed during firing of pellets at high
mechanism of reduction of iron oxide pellets under load. temperature (.1200uC) by a solid state reaction between
Fe2O3 and the corresponding constituents of associated
gangue minerals and fluxing materials added in the
Experimental pelletising process. The photomicrographs showing the
The physical and chemical characteristics of two types of internal structure of both acidic and basic pellets are
fluxed iron ore pellets are given in Table 1. The basicity given elsewhere.20 In acidic pellets, silicates of iron and
of pellets in terms of (CaOzMgO) and (SiO2zAl2O3) is aluminium were observed whereas in basic pellets,
0?37 and 1?62 indicating that the former is acidic while calcium and magnesium ferrites were formed at the
the later is basic. These pellets were isothermally reduced grain boundaries.
at 750–1000uC in synthetic gas mixture composed of
55%H2, 36%CO, 5%H2O, 3%CO2 and 1%N2. This gas Sticking phenomena
mixture represents the actual composition of reformed The sticking tendency of the pellets was determined
natural gas used in Midrex processes at ANSDK using average drop number method. Table 2 shows the
(Alexandria, Egypt). The reduction experiments were results of the average drop number test for two acidic
carried out under different loads ranging from 0 to samples. Sample 1 represents, the pellets reduced at
0?57 kg cm22. The course of reduction was followed by 950uC without load while sample 2 represents, the pellets
measuring the weight loss as a function of time under reduced at the same temperature under 0?4 kg cm22. It
controlled operational conditions. The schematic dia- can be noticed that sample 1 showed some disintegration
gram for the system used for carrying out the reduction as it was subjected to drop test up to 7 times, whereas for
experiments is given elsewhere.20 In order to have more drops up to 100 times no further weight change
detailed information about the microstructure of the was recorded. The same observation happened in sample
pellets reduced under load, an optical microscope was 2 but after 55 drops which means that the pellets are
used to examine some of the partially reduced pellets stuck together more strongly compared to sample 1. The
under different temperatures and loads. A pore size final sticking percentage for the two samples indicates
analyser (Pore sizer 9320, Micromeritics, USA) also that they acquired a more or less the same value.
used to characterise the pore size distribution of the Accordingly, the final sticking value has to be related in
original and reduced pellets. one way or another to the number of drops after which
The sticking tendency of the iron ore pellets under no weight change occurred. Consequently, a more
load was determined by an average drop number test. A reliable parameter was designated and called sticking
sample weight of about 33–37 g consisting of some eight index in order to represent sticking phenomenon more
pellets was dropped from 50 cm height for 100 times. accurately. It is calculated by multiplying final per cent
After each drop, the weight of the pellets that remain of sticking and number of drops. The sticking index
stuck together was determined. The sticking per cent is values obtained at different temperatures and different
represented by the weight of sticking pellets after each loads give a meticulous measurement for the degree of
drop divided by the original weight of the pellets. The sticking. The clustering tendency and per cent of sticking
final sticking per cent that corresponds to the last drop were found to be dependent on chemical composition,
was taken as the degree of sticking. temperature and applied load.
Table 2 Results of average drop number test of two acidic samples reduced at 950uC under different loads
Load, kg cm22 Total no. of drops No. of drops after which no change occurred Final per cent sticking, %
Sample 1 0 100 7 19
Sample 2 0.4 100 55 21
Chemical composition Fig. 1a and b respectively. The basic pellets showed the
Unlike in the basic pellets, the reduced acidic pellets at formation of a highly porous structure in which a large
temperatures >950uC were stuck together forming number of macropores between iron grains were
cluster on applying load >0?4 kg cm22 and below which developed together with micropores inside grains. The
the sticking of pellets was not considered. The tendency structure given in Fig. 1a for the acidic pellets shows
of iron ore pellets to form clusters during reduction that much more dense and relatively large sintered iron
under load at higher temperatures is affected by the grains are connected forming a coherent matrix with
original chemical composition and physical properties of only large macropores separating dense iron aggregates.
pellets. It was found that iron ore sinter having 1?8 Moreover, fayalite phase was also detected by applying
basicity behaves fairly well while that of 1?6 basicity a suitable etching solution on the polished section of
shrunk rapidly.10 This showed a good indication that the reduced samples and was also confirmed by X-ray phase
chemical composition of pellets has a pronounced effect identification. This phase was formed from the solid
on the physical changes occur during thermal treatment state reaction between the wüstite (FexO) resulted from
of pellets. Consequently, acidic iron ore pellets (0?37 the reduction of iron oxides and SiO2 associated with
basicity) show a greater tendency for clustering than gangue minerals. This phase is barely reduced under the
basic pellets (1?62 basicity). The variation in clustering FexO present reduction conditions. The presence of
tendency is most probably related to the difference in silicate phase has a pronounced effect on the enhance-
their chemical and mineralogical composition. The ment of cluster formation of acidic than in basic reduced
photomicrographs showing the internal structure of pellets and consequently increasing the sticking
acidic and basic pellets reduced at 1000uC are given in tendency.
Reduction temperature
The influence of temperature on the sticking index
calculated at different loads for acidic iron ore pellets is
represented in Fig. 2. It shows that the temperature has
no measurable influence on the sticking index of samples
reduced under small load ((0?2 kg cm22). At higher
loads, the sticking index increases to large extent with
temperature giving an anomalous value at 850uC and a
minimum value at 900uC. This could be attributed to a
relatively long time taken to reduce pellets at 850uC as
shown in Table 3, since time has a significant effect on
Table 4 Relation between shrinkage core modulus s2 and Table 5 Experimental parameters of iron ore pellets
mechanism of reduction
Surface area, m2 g21 0.517
2
s Controlling mechanism Porosity, % 32%
Average weight, g 32–35
s2,1 Chemical reaction Gas mixture, % 55%H2, 36%CO, 5%H2O,
1,s2,10 Mixed chemical reaction and gaseous diffusion 3%CO2 and 1%N2
s2.10 Gaseous diffusion Reduction temperature, uC 750–1000
obtained for either chemical reaction, gaseous diffusion concentration of gaseous reactant ‘A’ on surface, CCS
or mixed control for both pellets reduced under different is the concentration of gaseous product ‘C’ on surface,
loads. Accordingly, a developed kinetic model was KE is the equilibrium constant, and t is time.
derived here in after from reaction parameters to The shrinking core reaction modulus is defined by the
elucidate the reduction mechanism under load as given following formula
in the following section. " #1=2
1
2 Vp kFp Ag (1{e)(1{ KE )
Derivation of reduction mechanism from reaction model s ~ (6)
Ap 2De Fg Vg
parameters
In order to have good comprehension about the effect of where Vp is the particle volume, Ap is the particle area,
both reduction temperature and applying loads besides Fp is the particle shape factor, e is the porosity, and De is
finding out which mechanism controls the reduction the effective diffusivity.
process, a mathematical modelling for kinetics and According to equation (4), the shrinking core reaction
mechanism was used. According to the grain model modulus (s2) can be used as the factor which determines
developed by Szekely et al.,23–25 the different controlling the relative contribution of both gaseous diffusion
mechanisms were represented by equations (2)–(4). The mechanism and chemical reaction in the mixed control
dimensionless time (t*) can be defined according to the formula. Hence, the mechanism of reduction can be
following equation estimated according to the value of s2 as shown in
Table 4. To calculate the value of s2, some experimental
bk Ag CCS
t ~ CAS { t (5) parameters (given in Table 5) should be incorporated.
rs Fg Vg KE
The values of s2 were calculated for different extents of
where, b is the mole fraction, k is Boltzmann constant, reduction (5, 25, 70 and 90%) in the temperature range
Ag is the grain area, Fg is the grain shape factor, rs is the of 750–1000uC and under different loads (Fig. 7). It was
solid density, Vg is the grain volume, CAS is the found that s2 has different values between 1 and 10;
consequently the reduction process is controlled by
mixed mechanisms. This is in agreement with the relationship between total porosity and loads at
controlling mechanism derived from the values of the different extents of reduction for both acidic and basic
activation energy.26 As temperature increased, the value pellets. It was observed that at the early intermediate
of the shrinking core modulus increased. At the early stages (40% extent) of reduction, the per cent of porosity
stages of reduction, the values of s2 were highest increased by increasing the load and temperature. Also,
especially at lower loads whereas at intermediate and the pellets become more porous with the progress of
final stages of reduction, the temperature has a less reduction process but near the final stages of reduction
pronounced effect on the value of s2. The relation (85% reduction extent) the effect of load on the per cent
between s2 and temperature at different loads for both of porosity was less significant.
iron ore pellets at 5% extent of reduction is given in In order to investigate the effect of load and
Fig. 8. It can generally be seen that the value of s2 temperature on the mechanism of reduction, particularly
depends on both the reduction temperature and applied in the mixed control mechanism region, the ratio of the
load. The values of s2 increase steadily by either contribution of chemical reaction mechanism to gas
increasing the temperature or decreasing the load. This diffusion mechanism, called hereinafter the mixed
means that the contribution of gaseous diffusion is more control ratio Q, was calculated according to the
pronounced by increasing the temperature and following formula
decreased with increasing applied load. The increase in
the value of s2 by increasing temperature can be Gfg (X )
Q~ (7)
attributed to the enhancement of the chemical reaction s2 Pfg (X )
caused by increasing temperature. Accordingly, the
This ratio determines to some extent the contribution of
diffusion of the gas is the slowest step and the
each of the mechanisms in the mixed control. Figure 10
contribution of gaseous diffusion in the controlling
shows the relation between Q and reduction extent (X) at
mechanism decreases with temperature. The variation of
s2 with load can be attributed to the change in the different temperatures for both pellets. It is observed
structure of pellets during reduction. Figure 9 shows the that at the early stages of reduction this ratio shows a
higher value which in turn indicates that the contribu- above mentioned conventional methods. The model
tion of a chemical reaction mechanism is more effective enables good analysis about the actual effect of
than that of a gaseous diffusion mechanism. As the reduction temperature and applied load upon the
reduction increases to 15–20% a sharp drop in the value controlling mechanism. It also indicates the relative
of Q is shown and kept more or less constant for most of effects of the different mechanisms for case which are
the reduction course at about 1–2. This is an indication controlled by mixed mechanisms.
that the contribution of gaseous diffusion control
increases on the expense of the chemical reaction control
share in the mixed control reaction. At the final stages of References
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