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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
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)
Chemical composition/wt-%
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
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
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
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
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.
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Gao et al. Kinetics of pre-reduction of manganese ore by CO
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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