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Kinetics of pre-reduction of manganese ore by

CO
Y. B. Gao*, H. G. Kim and H. Y. Sohn
The degree of reduction of the higher oxides of manganese to the lowest oxide, MnO, achieved
during the pre-reduction of manganese ore has a direct impact on the energy consumption for the
subsequent smelting process. For ferruginous manganese ores, understanding the kinetics of
pre-reduction is also useful for controlling the process parameters to optimise specific power
consumption and maximise the metal recovery for upgrading by magnetic separation. The effects
of reduction temperature, gas composition and particle size on the rate of reduction were
investigated. Based on experimental results, the controlling step and activation energy for this
reduction process were determined, and the rate expression was also developed.
Keywords: Kinetics, Manganese ore, Pre-reduction, Carbon monoxide, Gaseous reduction

Introduction are essential in developing an effective technique for the


pre-reduction of manganese ores. This paper focuses on
For the industrial production of ferromanganese alloy, the kinetics of pre-reduction of manganese ore by CO.
which is of vital importance in the steelmaking process,
naturally occurring manganese ores generally need to be Experimental
first subjected to pre-reduction. Pre-reduction can be
considered as a thermal beneficiation step, which im- Materials
proves the grade of manganese ore, and engenders such The manganese ore used in this study was provided by
benefits as utilisation of lean grade ores, savings in POSCO, and its chemical composition is shown in
transportation costs as well as reduction of power con- Table 1.
sumption in the subsequent smelting process. It was
reported (Hofmanne et al., 1989) that energy consump- Procedure
tion drops from about 3000 kWh/ton FeMn to about The original manganese ore was first milled to less than
1600 kWh/ton FeMn when a pre-reduced ore was used 1 mm and sieved. The reduction extent is defined as
instead of a natural ore in the electric furnace. In percentage removal of the removable oxygen, i.e. the
addition, the pre-reduction is also crucial for the effec- oxygen present in the ore associated with manganese
tiveness of upgrading of ferruginous manganese ore by and iron. However, during the reduction, the weight loss
magnetic separation both in power consumption and may be affected by the thermal decomposition of the
metal recovery. impurities and the removal of volatile components.
Currently, almost all of the pre-reduction of manga- Therefore, the samples obtained after ball milling and
nese ores employ solid carbon as the reducing agent, sieving were calcined at 900uC in argon prior to reduc-
and different aspects of the carbothermic reduction of tion so that the weight loss in the experiments would be
manganese ores have been reported (Ostrovski and totally attributable to the reduction of manganese and
Webb, 1995; Eric and Burucu, 1992; Hansen et al., 1993; iron oxides.
Yastreboff et al., 1998; Dewar and See, 1978; Kononov The reduction of calcined samples was conducted
et al., 2008; Yastreboff et al., 2003). In comparison with using a Cahn-balance system (Cahn, RTL no. 7000 for
solid carbon, the reduction of manganese ore by CO 110 V at 60 Hz, Cahn Instruments, CA, USA), which is
may result in a faster rate even at a lower temperature schematically shown in Fig. 1. The reactor used for
(Anacleto et al., 2004). At the same time, understanding reduction was a vertical quartz tube (internal diameter:
the kinetics of pre-reduction is helpful in optimising the 45 mm; outside diameter: 48 mm; length: 850 mm). In
operational parameters. However, compared with car- order to ensure good access of the reducing gas to the
bothermic reduction, research work on the kinetics sample particles, a shallow crucible was used as sample
study of the gaseous reduction of manganese ores by CO holder. The total flowrate of reducing gas consisting of
has been conducted to a much lesser extent, and more CO and CO2, was maintained at 1?5 NL min21, which
studies on the pre-reduction of manganese ore by CO was determined to be sufficient to eliminate the effect of
gas flowrate for a gassolid reaction of a similar rate (De
Micco et al., 2011). The CO/CO2 ratio of the gas mixture
Department of Metallurgical Engineering, University of Utah, Salt Lake used in this study ranged from 10 : 90 to 40 : 60. A
City, UT 84112, USA temperature of 600uC was used for most of the exper-
*Corresponding author, email yubogao@hotmail.com imental work, although temperatures in the range of

2012 Institute of Materials, Minerals and Mining and The AusIMM


Published by Maney on behalf of the Institute and The AusIMM
Received 26 September 2011; accepted 9 February 2012 Mineral Processing and Extractive
DOI 10.1179/1743285512Y.0000000003 Metallurgy (Trans. Inst. Min. Metall. C) 2012 VOL 121 NO 2 109
Gao et al. Kinetics of pre-reduction of manganese ore by CO

2 Equilibrium diagram of MnCO and FeCO systems

Reproducibility of experiments
1 Schematic diagram of Cahn-balance apparatus The reproducibility of the experimental data was tested
by the reduction of calcined samples under an identical
400700uC were included to determine the effect of experimental condition (temperature: 550uC; particle
temperature. size: 105150 mm; CO/CO2: 30 : 70). The results of these
All of the experimental conditions of reduction tests reproducibility tests shown in Fig. 3 indicate that there
were controlled at the overlapped stable region of MnO is little difference between the test results, implying a
and Fe3O4 in the corresponding equilibrium diagram, good reproducibility, which is mainly attributed to the
as shown in Fig. 2, and the reactions involved in this uniformity in chemical and physical properties of sample
reduction process are particles used in this work and the rigorous control of
experimental conditions and procedures.
Mn3 O4 zCO~3MnOzCO2 (1)

3Fe2 O3 zCO~2Fe3 O4 zCO2 (2)


Results and discussion
XRD test results
As for this equilibrium diagram, while the equilibrium
constants at various temperatures for CO reduction of The XRD results for the original manganese ore, the
MnO2 to Mn2O3 and that of Mn2O3 to Mn3O4 are so calcined sample, and particles reduced at 550uC for
60 min, which is sufficient to complete the reaction,
large that the corresponding equilibrium lines approxi-
are shown in Fig. 4. The major phase of manganese
mately overlay the baseline with 0 vol.-%CO, the
contained in the original ore is MnO2, and the iron exists
equilibrium constant for the reaction of MnO to Mn
as Fe2O3 and FeO(OH). Besides, considerable amounts
by CO is so small that its equilibrium line lies essentially
of SiO2 and Al2SiO5(OH)4 were also detected by XRD.
on the line marked with 100 vol.-%CO.
As a result of calcination, the MnO2 phase was de-
The chemical phases contained in the original manga-
composed to Mn3O4, while iron remained as Fe2O3,
nese ore, the calcined sample, and reduced particles were
and all other phases were also converted to oxide forms
identified by X-ray diffraction (XRD). Scanning elec-
that are not reduced by CO. The sample particles were
tron microscopy (SEM) was employed to observe the
composed of MnO, Fe3O4, SiO2 and Al2O3 after
microstructures of calcined and partially reduced sample
reduction at 550uC by a mixture of CO and CO2 (CO/
particles. The weight of the sample was continuously
CO2: 30 : 70). It is indicated by Fig. 4 that SiO2 and
recorded by the Cahn-balance system during the reduc-
Al2O3 did not change chemically during the reduction,
tion, and the data were further converted to reduction
extent by the following equation
Wi {Wt
X~ |100% (3)
Wi {Wf
where, X is reduction extent, Wi and Wf refer to the
initial weight of the calcined sample and the weight of
the final reduced particles respectively, and Wt is the
specific sample weight at certain time.

Table 1 Chemical composition of LP manganese ore

Chemical composition/wt-%

T-Mn T-Fe SiO2 Al2O3 CaO P2O5 MgO

36.6 12.7 11.7 4.01 0.12 0.17 0.11


3 Reproducibility test result of reduction extent at 550uC

110 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) 2012 VOL 121 NO 2
Gao et al. Kinetics of pre-reduction of manganese ore by CO

6 Timereduction extent curves for the reduction of sam-


ples at different particle size ranges
4 XRD test results for different samples
through the boundary layer above the sample [because
and thus the weight loss was due entirely to the this effect is usually much smaller than that of pore
reduction of manganese oxide and iron oxide. diffusion (Szekely et al., 1976)] as well as between the
particles was negligible. This assures that the observed
Effect of bed depth rates represent intrinsic kinetics.
The effect of bed depth was studied at 600uC with a Effect of particle size
mixture of CO and CO2 at the CO/CO2 of 30 : 70, the
particle sizes of the sample used in these tests were in the The effect of particle size was investigated at 600uC,
range of 105150 mm. For these experiments, the bed using a mixture of CO and CO2 (CO/CO2: 30 : 70). The
depth, varying from 0?1 to 0?4 cm, was controlled by plots of reduction extent versus time for samples with
changing the amount of sample particles contained in different particle sizes are presented in Fig. 6. All the
the crucible. The reduction curves for different bed reductionversustime curves consist of two parts. The
depths are shown in Fig. 5. initial stage, during which the rate of reduction is very
fast, is followed by a longer stage, which is characterised
The experimental result shows that, although slight
by a marked decrease in the slope and thus the rate of
derivation occurs in the terminal part of reduction
reduction. These curves also indicate that the reduction
curves for different bed depths, up to 90% of reduction
rate increased with decreasing particle size. When the
extent, the reduction rate is essentially independent of
particle size decreased to around 150 mm, the effect
bed depth.
of particle size became smaller, and the initial stage
As stated in experimental procedures, the crucible
of reduction tended to be size independent when the
used in the study is very shallow, and the reducing gas is
particle size further decreased to 74 mm. This may be
allowed a good access to the sample layer. The results
caused by the microstructural changes in the particle
obtained in these tests indicate that the interior spacing
during reduction, and thus both the calcined and par-
between particles loaded in the crucible was sufficient
tially reduced particles were tested by SEM, and the
for the reducing gas to readily access the particles at
results are given in Figs. 7 and 8.
different depths, i.e. the reactant gas concentration
Although the calcined LP particles are dense as
throughout the entire bed was uniform. Thus, in this
shown in Fig. 7(14), it is clearly observed from the
case, the resistance from the diffusion of reducing gas
SEM images of partially reduced samples, as demon-
strated in Fig. 8(14), that cracks are formed during the
reduction, which is probably due to thermal stress. As
the reducing gas has access to the solid surface through
these cracks, it results in a decrease in the effective
particle size of the sample, and thus this accounts for the
result that the effect of particle size on the reduction rate
is not as strong as expected just from the overall size of
the particle.

Effect of temperature
The effect of temperature was studied in the range from
400 to 700uC, both non-isothermal and isothermal tests
were conducted in this work. The reducing gas was a
mixture of CO and CO2 with a molar ratio of CO/CO2
at 30 : 70. Sample particles in the range of 105150 mm,
in which there is little size effect, were used. The plots of
5 The effect of bed depth on the reduction (T: 600uC; CO reduction extent versus time obtained from isothermal
content: 30 vol.-%) tests are presented in Fig. 9.

Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) 2012 VOL 121 NO 2 111
Gao et al. Kinetics of pre-reduction of manganese ore by CO

7 Images (SEM) for sample particles, calcinated at 900uC

The effect of increased temperature is an increase in after a certain time. Moreover, a higher CO content
the rate of reduction. At 400uC the reduction rate is very resulted in a higher reduction rate. This effect was
slow. This is in good agreement with the test result of especially notable when the CO content changed from
non-isothermal reduction, which indicated that signifi- 10 to 30 vol.-%.
cant reduction does not start until the temperature
reached around 440uC, as shown in Fig. 10. Kinetics analysis
Figure 9 also shows that, in the temperature range of
450600uC, the rate of reduction increased distinctly as For samples that are approximately equi-dimensional
the temperature increased, and all the corresponding with uniform reactivity in different directions and are
curves tend to level off after a certain time. rate-controlled by chemical reaction, the reaction time
would be proportional to [12(12X)1/3] (Szekely et al.,
Effect of CO content 1976), where X is the reduction extent. If the reaction
To study the effect of CO content in the reducing gas, is controlled by pore diffusion, the reaction time would
experiments were conducted at four different CO/CO2 be proportional to [1z2(12X)23(12X)2/3] (Sohn and
ratios between 10 : 90 to 40 : 60. Reduction temperature Wadsworth, 1979; Levenspiel, 1972). If the rate is con-
was controlled at 600uC, and the sample particles were trolled by nucleation and growth, plots of the Avrami
sized between 105 and 150 mm. The effect of CO content term, {ln [2ln (12X)]} versus ln t, should be straight
on the reduction is shown in Fig. 11. lines (Sohn, 1978; Sohn and Emami, 2011). Since there
According to the results, all the reduction curves are many uncertainties for the terminal part of reduc-
obtained at different CO/CO2 ratios tend to level off tion, only the data below the reduction extent of 0?95

112 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) 2012 VOL 121 NO 2
Gao et al. Kinetics of pre-reduction of manganese ore by CO

8 Images (SEM) for partially reduced sample particles (T: 600uC; CO content: 30 vol.-%)

9 Timereduction extent curves for the isothermal reduc- 10 Timeweight loss curves for the non-isothermal reduc-
tion at different temperatures (CO content: 30 vol.-%) tion (CO content: 30 vol.-%)

Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) 2012 VOL 121 NO 2 113
Gao et al. Kinetics of pre-reduction of manganese ore by CO

13 Plots of [1z2(12X)23(12X)2/3] versus time at various


temperatures (CO content: 30 vol.-%)

11 Timereduction extent curves for the reduction at dif-


ferent CO contents (T: 600uC)

were used for plotting and analysis. The plots of


[12(12X)1/3] versus time, [1z2(12X)23(12X)2/3] ver-
sus time, and {ln [2ln (12X)]} versus ln t are present in
Figs. 1214 respectively.
According to these figures, this reduction process is
best described by the nucleation and growth rate
equation. In this case, considering that the size of
sample particle used in the isothermal reduction experi-
ments was as small as 105150 mm, the particle size is
probably not large enough for the formation of distinct
continuous interface between reactant layer and product
layer, which is required for the topochemical reduc-
tion mechanism. Besides, as shown in Fig. 8, cracks are
formed in the sample particle during the reduction. For 14 Plots of {ln [2ln (12X)]} versus ln t at various tem-
the particle with cracks, the reaction taking place within peratures (CO content: 30 vol.-%)
these cracks may also result in the formation of several
cores during the reduction progress for a single sample h p  m i
CO2
particle, and this is another reason why the topochem- kapp ~k pmCO { (5)
K
ical reduction mechanism is not suitable for this reduc-
tion process. Therefore, this reduction process is best in which k is rate constant, K is equilibrium constant, m
described by the nucleation and growth kinetics equa- is reaction order, pco and pCO2 refer to partial pressures
tion expressed by of CO and CO2 respectively, and could be calculated by
1 vol:-%
{ ln1{X n ~kapp t (4) p~0:85 atm| (6)
100
where X is reduction extent, n is a constant, kapp refers to where 0?85 atm (1 atm5101?3 kPa) is the local atmo-
apparent rate constant, which contains the effect of spheric pressure at Salt Lake City.
partial pressures according to Since the value of the equilibrium constant K (in this
case, K>1?7761021) is so large, the term of (pCO2 =K) is
negligible compared with the term of (pco)m, and
equation (5) is simplified as
kapp ~k(pCO )m (7)
Based on the plots of {ln [2ln (12X)]} versus ln t at
various temperatures, which are shown in Fig. 14, we
first obtained the slope of each line, and the average
value of the slope to be used as the value of n in
equation (4) was calculated, all of which are summarised

Table 2 Values of order parameter (n) at various tem-


peratures (pco: 0?255 atm)
Temperature/ 450 500 550 600 650 700 Average
12 Plots of [12(12X)1/3] versus time at various tempera- uC
Slope n 1.05 1.34 1.29 1.42 1.29 1.18 1.26
tures (CO content: 30 vol.-%)

114 Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) 2012 VOL 121 NO 2
Gao et al. Kinetics of pre-reduction of manganese ore by CO

17 Plots of ln kapp,co versus ln Pco at various CO con-


15 Modied plots of {ln [2ln (12X)]} versus ln t at var- tents (T: 600uC; kapp,co in min21)
ious temperatures

18 Arrhenius plot for kT (in atm21 min21)

16 Plots of {ln [2ln (12X)]} versus ln t at various CO be 1?0, indicating a first order reaction with respect to
contents (T: 600uC) CO partial pressure.
The values of ln kT for various temperatures can
further be calculated by equation (7), and the calculated
in Table 2. The slopes are in the range of 1?051?42, values of ln kT are given in Table 5. Figure 18 shows the
which gives an indication of one-dimensional nucleation Arrhenius plot, and the activation energy estimated
and growth. With the slope of each plot set at the from the slope is 66 kJ mol21.
average value 1?26, Fig. 15 shows the modified regres- Based on the above kinetics analysis, the final rate
sion line for various temperatures. The value of expression for this reduction process becomes
ln kapp,T, where kapp,T refers to apparent rate constant
1
at different temperatures, can be calculated from the { ln1{X n ~k(pCO )m t (8)
intercepts on Y axis, and the calculated values of
ln kapp,T are given in Table 3.
In a similar way, by linear regression of plots of Table 4 Values of ln kapp,co* at various CO contents (T:
{ln [2ln (12X)]} versus ln t at various CO contents, the 600uC)
values of ln kapp,co, where kapp,co refers to apparent rate CO/CO2 10 : 90 20 : 80 30 : 70 40 : 60
constant at different CO contents, can be calculated
from the intercepts on Y-axis of Fig. 16, and the pco/atm 0.085 0.17 0.255 0.34
obtained values of ln kapp,co are summarised in Table 4. ln kapp,co 23.39 22.76 22.38 21.95
According to equation (7), the value of m can be *kapp,co in min21.
determined by the slope of the plot of ln kapp,co as a
function of ln pco, as shown in Fig. 17, and it comes to
Table 5 Values of ln kT* at various temperatures (pco:
0?255 atm)
Table 3 Values of ln kapp,T at various temperatures (pco:
0?255 atm)* Temperature/uC 450 500 550 600 650 700

Temperature/uC 450 500 550 600 650 700 ln kapp,T 24.66 23.46 22.76 22.38 21.99 21.75
ln kapp,T 24.66 23.46 22.76 22.38 21.99 21.75 ln kT 23.27 22.07 21.37 20.99 20.61 20.36
*kapp,T in min21. *kT in atm21 min21.

Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C) 2012 VOL 121 NO 2 115
Gao et al. Kinetics of pre-reduction of manganese ore by CO

rate is not as strong as expected, largely because of the


cracks formed during the reduction. Based on the
experimental data as well as the physical nature of
sample particles used in this work, the nucleation and
growth rate equation with n51?26 best represents the
data. The activation energy was determined to be
66 kJ mol21. The complete rate expression for this
reduction process was developed. The rate is of first
order with respect to CO partial pressure.

Acknowledgements
This work was supported by Research Institute of
Industrial Science and Technology (RIST), Pohang,
Korea. The authors also would like to acknowledge
POSCO Co. for supplying the manganese ore.
19 Comparison of experimental data and calculated date
at different temperatures (CO/CO2: 30 : 70)
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