An Investigation on Carbothermic Reduction of Different Grades of

Manganese Ores

A training report submitted for training attended in a summer internship at CSIR NML,
as the partial fulfilment of the requirement for the award of the Degree of

Bachelor of Technology
in
Chemical Engineering

By
Mr. Gaurav Maurya

Under the Supervision of

Mr. Krishna Kumar,

Scientist, MER Division
CSIR- National Metallurgical Laboratory, Jamshedpur
&

Working Institute

CSIR NML
Council of Scientific and Industrial Research
National Metallurgical Laboratory, Jamshedpur-831007

Registered University

National Institute of Technology, Rourkela

 ACKNOWLEDGEMENT

I would like to express my deep and sincere gratitude to my research mentor, Mr Krishna
Kumar, Scientist, CSIR-National Metallurgical Laboratory for giving me the opportunity to learn
and carryout various research activities and providing invaluable guidance throughout this
research. His dynamism, vision, sincerity and motivation have deeply inspired me. He has taught
me the methodology to carry out the research and to present the research works as clearly as
possible. It was a great privilege and honour to work and study under his guidance. I am incredibly
grateful for what he has offered me. I would also like to thank him for his friendship, empathy,
and a great sense of humour.

Besides my mentor, I would like to thank Mr. Ammasi A, scientist- metal extraction and recycling
division, for providing me with the required support under the project to carry out my various
R&D activities. I would also like to thank Mr Jayant Konar and Mr Manish Kumar for their
insightful comments and encouragement and for their careful and precious guidance which were
extremely valuable for my study both theoretically and practically.

My sincere thanks also go to Mr Rohit Mohanty, Chemical Analyst CSIR NML and Ms. Leepika,
Chemical Analyst CSIR NML who provided me with an opportunity to join their team as an intern,
and who gave access to the laboratory and helped me to do analysis of the samples.

Last but not the least, I would like to thank Dr Indranil Chattoraj, Director’ CSI-NML and training
coordinator Dr. K.L Hansda, who in spite of being extraordinarily busy with their duties, took time
out to hear, guide and keep me on the correct path and allowing me to carry out my research at
their esteemed organization during the training.

Finally, my thanks go to all the people who have supported me to complete the research work
directly or indirectly to a fruitful stage.
 Table of Contents

List of Tables
List of Figures
Synopsis
1. Introduction ................................................................................................................................1
1.1 Manganese Reserves ............................................................................................................1
1.2 Application of Manganese as metal .....................................................................................1
1.3 Manganese extraction and recovery from various resources..............................................2
2. Literature Review ......................................................................................................................2
2.1 Manganese ore reduction studies by other investigators ...................................................3
2.2 Research Gap and Objectives ..............................................................................................5
3. Raw Material Characterization .............................................................................................. 6
3.1 Chemical Analysis of raw material .....................................................................................6
3.2 X-ray Diffraction (XRD) Analysis .......................................................................................7
3.2.1 XRD analysis of Low Grade (LG) manganese ore .....................................................8
3.2.2 XRD analysis of Low Grade (LG) manganese……… ........................................……9
4. Experimentation ....................................................................................................................... 9
4.1 Thermodynamic Analysis of Manganese Ore Reduction ...................................................9
4.2 Stoichiometric calculation for reduction of Manganese ore by coke .............................12
4.2.1 Calculation of required carbon for reduction of MnO2 to MnO .............................12
4.2.2 Calculation of required carbon for reduction of Fe2O3 to Fe……… .............……12
4.3 Experimental Procedure .....................................................................................................13
4.3.1 Pelletization of Manganese ore fines ........................................................................13
4.3.2 Drying of Manganese ore pellets ..............................................................................14
4.3.3 Resistance heating for reduction of pellets ...............................................................15
5. Results and Discussion.............................................................................................................17
5.1 General visual Observations ..............................................................................................17
5.2 Chemical Analysis……………….………………………………………...……………..17
5.3 Reduction index/O2 loss ratio ...........................................................................................18
5.4 XRD Analysis of reduced samples .....................................................................................20
5.5 Comparison of reduction behavior ………………………………………………………28
6. Conclusion ...............................................................................................................................33
7. Future Scope ............................................................................................................................33
References ....................................................................................................................................34
 List of Tables
Table Title Page
No. No.
1 Composition of Ore 7
2 Chemical Analysis of coke 7
3 Chemical Analysis of Bentonite 7
4 Composition of pellets 14
5 Experimental conditions with sample ID 15
6 Chemical analysis of reduced high grade Manganese ore with C in 18
7 Chemical
Percentageanalysis of reduced low grade Manganese ore with C in 18
8 Comparison
Percentage of reduction index of ores 19
 List of Figures
Figure Title Page
No. No.

1 Bruker D8 Discover XRD Machine at CSIR NML 8

2 XRD pattern of high-grade Manganese ore 8
3 XRD pattern of low grade Manganese ore 9
4 Ellingham diagram for Manganese Ore reduction 10
5 Ellingham Diagram for the reduction of Fe2O3 to Fe 11
6 The gas-phase equilibrium diagram of equation (3), (4) and (5). 11
7 A schematic drawing showing the different states of water-particle system 13
8 Picture of ore fines 14
9 Disk pelletizer at CSIR-NML 14
10 Pellets From pelletizer 14
11 Hot air oven at CSIR-NML 15
12 Pellets after drying 15
13 Muffle furnace (1100oC) used for reduction experiments 16
14 Isothermal and Non-Isothermal weight loss Vs time of High-grade Manganese 17
15 ore pattern of HG ore at 1000℃ for 30 minutes in isothermal condition (M1)
XRD 20
16 XRD pattern of HG ore at 1000 for 120 minutes in isothermal condition(M2) 21
17 XRD pattern of HG ore at 700℃ for 30 minutes in isothermal condition(M3). 21
18 XRD pattern of HG ore at 700℃ for 120 minutes in isothermal condition (M4) 22
19 XRD pattern of HG ore at1000℃ for 120 min in non-isothermal condition (M5) 23
20 XRD pattern of HG ore at 700℃ for 120 min in non-isothermal condition (M6) 23
21 XRD pattern of LG ore at700℃ for 30 minutes in isothermal condition(LM1) 24
22 XRD graph of LG ore at 700℃ for 120 min in isothermal condition (LM2) 25
23 XRD pattern of LG ore at 1000℃ for 30 minutes in isothermal condition(LM3) 25
24 XRD pattern of LG ore at 1000℃ for 120 minutes in isothermal 26
condition(LM4).
25 XRD pattern of LG ore at 1000℃ for 120 min in non-isothermal condition 27
(LM5).
26 XRD pattern of LG ore at700℃ for120 min in non-isothermal condition(LM6). 27
27 Comparative study of isothermal reduction at 700℃ and 30 min 28
28 Comparative study of isothermal reduction at 700℃ and 120 min 29
29 Comparative study of isothermal reduction at 1000℃ and 30 min 30
30 Comparative study of isothermal reduction at 1000℃ and 120 min 30
31 Comparative study of reduction of high-grade ore at 1000℃ and 120 min 31
32 Comparative study of non-isothermal reduction at 700℃ and 120 min 31
33 Comparative study of non-isothermal reduction at 1000℃ and 120 min 32
 Synopsis
Manganese ores are primarily contained of MnO2 alongwith Fe2O3 and SiO2. It occurs as
silvery-grey in colour and is very hard and brittle in nature. Based on quality of ores, Indian FeMn
alloy producers have two grades to work with, namely High Grade and Low grade ores. The
reduction of Manganese ore (high and low grade) mainly includes indirect reduction and direct
reduction. The reduction index is usually expressed by the ratio of the removed oxygen to the total
oxygen in the Mn/Fe oxides. However, natural manganese ores contains metal oxides besides some
amount of crystal water. In the process of reduction, the evaporation of crystal water will cause
the decrease of the quality. Therefore, the determination detected by the mass loss in the reduction
process actually cannot exactly express the reduction index of the manganese ore. The another
aspect of Fe/Mn ratio alone may also not helpful in deciding the reducbility and reduction behavior.
The content of SiO2 is comparatively high in low grade ores than high grade, which causes extra
amount of slag formation during the arc processes. The presence of SiO2 causes low reducibility
as well the enhanced power consumptions due to viscous and high melting slag formation. Also,
these leads to lower the productivity and unstable the downstream smelting processes. Producers
of manganese alloys are forced to use ores of different grades in the submerged-arc furnaces in
India. Because the ores from different sources and mineralogy differ in their reducibility, an
understanding of the reducibility of the ores becomes crucial for controlling the operation and
optimizing the smelting process parameters. The assessment of reducibility/reduction behavior
will help to develop suitable process parameters to reduce the ore inside the SAF. Assessing the
reducibility of different manganese ores will help the operator to understand the influence of each
ore type on the process-efficiency and adopt appropriate operational procedures. This optimization
can reduce the power consumption and increase the productivity with minimal fluctuations in the
SAF. In present study, investigations of reduction behavior of low grade (~ 45%MnO2) and high-
grade (~70% MnO2) manganese ores with coke (80% C) for various conditions has been carried
out. The O2 loss parameter doesn’t yield the actual reduction behavior, whereas the X-ray
diffraction studies have revealed the high levels of reduction of high grade Mn ore i.e. formation
of lower oxidation phases are prominent in high grade ores than the lower grades ore.
1. Introduction

Manganese ore is an important material in iron and steel metallurgy, where it is used both in
the ore form as such and as ferro-manganese. Manganese improves strength, toughness,
hardness and workability of steel, acts as a deoxidiser and desulphuriser and also helps in
getting ingots free from blowholes. About 90 to 95% world production of manganese ore is
used in metallurgy of iron and steel [2-3]. Silico-manganese (63%) and ferromanganese (30%)
industries together accounted for about 93% consumption followed by iron & steel (6%).

1.1. Manganese Reserves

Manganese occurs as silvery grey in colour and is very hard and brittle in nature. It is
always available in combination with iron, laterite and other minerals. Indian manganese ore
deposits [1] occur mainly as metamorphosed bedded sedimentary deposits associated with
Gondite Series (Archaeans) of Madhya Pradesh (Balaghat, Chhindwara & Jhabua districts),
Maharashtra (Bhandara & Nagpur districts), Gujarat (Panchmahal district), Odisha
(Sundergarh district) and with Kodurite Series (Archaeans) of Odisha (Ganjam & Koraput
districts) and Andhra Pradesh (Srikakulam & Visakhapatnam districts). According to Mineral
Year Book 2017 (GoI), The total reserves/resources of manganese ore in the country as on
1.04.2015 have been placed at 495.87 million tonnes as per NMI database, based on UNFC
system. Out of these, 93.47 million tones are categorized as reserves and the balance 402.40
million tonnes are in the remaining resources category. Grade wise, Ferro-manganese grade
accounts for 7%, Medium grade 11%, BF grade 28% and the remaining 54% are of Mixed,
Low, Others, Unclassified, and Not known grades including 0.17 million tonnes of
battery/chemical grade. Classification of manganese ore is done as ferruginous manganese ore,
siliceous manganese ore, dioxide manganese ore, and manganiferrous iron ore, which is laid
down by BIS vide specification no. IS: 11895- 2006 (Reaffirmed 2008).
1.2. Application of Manganese as metal
Manganese is one of the most important and strategic alloy elements for improving
the mechanical properties of steels [2]. More than 90% of manganese ores are used to produce
manganese-rich slags or manganese alloys, which are consumed in the steel industry finally
[3,4]. Manganese-rich slag, desirable burdens for Fe-Mn and Si-Mn alloy, is just intermediate
product in the manganese alloy production. The technology of hot metal pretreatment and less
slag steelmaking are mature increasingly since 1990s. The basic theory and industrial
application of direct alloying by manganese ore under the condition of less slag steel- making

1|Page
were researched systematically and deeply, by the main steel enterprises and research institutes
in Japan [5-8].
1.3. Manganese extraction and recovery from various resources
In China, however, due to the condition restriction of hot metal pretreatment and the
less slag steelmaking, the yield of manganese fluctuates in 5% - 25% generally, so that the
economic benefits is not obvious. Therefore, the new technology of direct alloying by
manganese ore in converter needs to be explored. During industrial production of ferroalloy-
or silicomanganese, an important part of the reduction process takes place in the upper parts of
the furnace, where carbon monoxide generated in the melting zone ascends and reacts with
solid ore particles. Higher manganese oxides of the ore are reduced to the divalent oxide;
further reduction is not thermodynamically feasible. Among other important gas-solid
reactions taking place are the reduction of iron oxides, the Boudouard reaction, the
decomposition of carbonates, and the cyclic reactions of alkalis. Together, these reactions have
a big impact on the carbon and energy consumption of the process [9]. In order to investigate
the behavior of a furnace charge mixture, a natural first step is to provide knowledge about how
each type of solid reacts under relevant conditions. In the literature, information may be
collected about the Boudouard reaction [10] and the decomposition of carbonates [11]. Gaseous
manganese oxide reduction is also described to some extent [12,13,14,] but the results of
different investigators vary considerably and no convincing conclusions have been made on
the reduction above 500 ℃.

2. Literature review
Following the variations in Mn ores due to different genesis and origins, the manufacturers
of manganese ferroalloys frequently face the problem of unstable furnace operations due to
the variation in the reducibility of manganese ores, which are usually imported. The ores are
usually procured mainly on the basis of the Mn/Fe ratio and the type of ore-oxide, silicate etc.
However, different ores, that have the same specifications with respect to these two parameters
do not perform identically during smelting reduction in the submerged-arc furnace. This not
only leads to erratic operations but also in low recoveries. The manufacturers are also faced
with the challenge of having to take rapid decisions on the purchase of imported ores where
they have hardly a day’s time between the receipt of quotation and the placement of order.
During this period, the ore sample has to be quickly assessed and an informed decision has to
be arrived at on the procurement. This is not feasible at present. Traditionally, for assessment

2|Page
for their suitability in processes/operations, following properties of ores are to be given
importance, majorly.
a) Mn/Fe should be high
b) Phosphorus content should be minimum
c) Mineralogy and composition

From another important perspective of researchers, the extent of slag formation affects the
kinetics and determines the reduction rate and MnO recovery level that can be achieved in a
furnace at a specific reaction temperature. T. Coetsee et al [15], had shown that the extent of
slag formation determines the reduction rate and MnO recovery level that can be achieved in a
furnace at a specific reaction temperature. Slag formation slows reduction by forming diffusion
barriers at the monoxide reaction interface within the reduced ore. It has been observed that
ore bulk chemical composition (total manganese and iron content) is likely to be a poor
indicator of ore reducibility. Phase equilibria, and specifically slag formation, must be
considered to predict the relative reduction rates of manganese ores. Additions made to the ore
to manipulate chemical composition to limit liquid silicate formation would be expected to be
effective in reaction systems such as pellets in which close proximity of reactants promote
homogenization. This would not be the case in mixtures of fine ore and reductant in a packed
bed; in such a mixture the ore would likely react according to its inherent chemical composition
and not respond to additives. An increase in temperature might not always remedy the problem
of slow reaction rates. In some cases, the reduction rate might even decrease upon increasing
temperature, due to excessive slagging.
Tao Jiang et. al.[16] has been studied the effect of iron and silicon on the metallurgical
properties of four type of manganese ore. They showed that if ore contains high Fe and low
silicon or high Fe and high silicon then ore has good reducibility and low melting temperature.

2.1. Manganese ore reduction studies by other investigators

Lindstad and Lars-Arne Stalheim [17] have been studied the kinetics of gaseous
reduction of Mn3O4 to MnO in a thermo-balance apparatus. They performed reduction
experiments in laboratory scale at different conditions; with and without feed gas, with
different ores and cokes, varying coke/ore ratios, size ranges and temperatures. There results
show that the chemical reaction in the ore to a great extent controls the total reaction rate for
the reduction of Mn3O4 to MnO and The reaction can be described by the shrinking core
reaction model for the manganese oxide.

3|Page
 K.L. Berg and S.E. Olsen [18] have been studied the kinetics of the reduction of higher
manganese oxides to MnO by carbon monoxide in the temperature range 700 ℃ to 1100 ℃.
According to Them the reduction rates of these minerals are controlled by gaseous diffusion in
the range 700 ℃ to 1100℃, and the reaction follows a single shrinking core pattern and Product
shell diffusion will be the governing rate-limiting process as soon as the thickness of the
manganosite shell is in the order of a millimeter.
Ho-Sang Sohn et. al.[19] studied reduction kinetics of manganese oxide in basic oxygen
furnace type slag. To improve manganese yield during the reduction of manganese ore, the
reduction rate of MnO was promoted for the slag of low basicity and high contents of FeO.
R.H. Eric and E. Burucu [20] have been studied the kinetics of reduction of the
manganese ore from Mamatwan mine in South Africa by thermogravimetric analysis (TGA),
X-ray diffraction analysis (XRD), optical microscopy, Scanning Electron Microscopy (SEM)
and energy dispersive analysis of X-rays (EDAX) between 1100℃ and 1350℃ with graphite
as the reductant under argon atmosphere. They observed that the rate and degree of reduction
increased with increasing temperature and decreasing particle size.
Rankin [21] studied the reduction of MnO under argon atmosphere from 1200℃ to
1425°C by graphite. He concluded that the reduction product is Mn5C2 and the activation
energy for the reaction is 240.6kJ and gasification of the graphite is the rate controlling step.
Tereyama and Ikeda [22] studied the effect of temperature, particle size and amount of
carbon on reduction rate of MnO under helium atmosphere between 1070℃ and 1200°C. They
also concluded that the overall rate is controlled by the rate of oxidation of carbon with an
activation energy of 217kJ. However, their reduction product was Mn7C 3. They stated that
reaction between MnO and carbide to yield manganese occurs at the interface of the two solid
phases in the later stages of reduction:
Mn7C3(s) + 3MnO(s) = 10Mn(s) + 3CO(g) (1).
The activation energy for this reaction was 259 kJ. When excess carbon was used the above
reaction was not observed.
Bo Zhang and Zheng-Liang Xue [23] studied the kinetics of direct reduction of
manganese ore pellets containing carbon. Their experimental results showed that, the reaction
rate in the earlier stage was controlled by the chemical reactions between FeO, MnO and carbon
reductant, and the activation energy was 28.85 KJ/mol. In the later stage, as the carbon
reductant replaced by CO, the reaction rate was controlled by CO-diffusing in solid products,
and the cor- responding activation energy was 86.56 KJ/mol and reaction rate of the later stage
was less than the earlier one.
4|Page
 R. A. Muriana et. al.[24] studied the kinetics of carbothermic reduction of manganese ore
from Ka’oje (Nigeria) deposit. Their results showed that Carbothermic reduction could
transform the higher oxide paramagnetic Ka’oje manganese ore-mineral to lower oxide
ferromagnetic mineral. Reaction kinetic evaluation of the reduction processes showed apparent
activation energy value of 19.99 KJ/mole for diminishing area condition, while 29.56 KJ/mole
and 36.28 KJ/mole are apparent activation energy values for diffusion controlled condition
using Ginsthing-Brounshtein and Jander equations respectively.
H. M. Long et. al. [25] studied the reduction kinetics of carbon containing pellets made
from metallurgical dust and they stated that the rate determining step of the reduction of the
pellets is the interfacial or local reaction with the activation energy 111.66 kJ/mole and the
reduction rate can be expressed by the McKewan equation (2) :
1─ (1─ R)1/3 = kt (2).

2.2. Research Gap and Objectives

Manufacturers of manganese ferroalloys frequently face the problem of unstable
furnace operations due to the variation in the reducibility of manganese ores, which are
usually imported. The ores are usually procured mainly on the basis of the Mn/Fe ratio and
the type of ore-oxide, silicate etc. However, different ores, that have the same specifications
with respect to these two parameters do not perform identically during smelting reduction
in the submerged-arc furnace. This not only leads to erratic operations but also in low
recoveries. The manufacturers are also faced with the challenge of having to take rapid
decisions on the purchase of imported ores where they have hardly a day’s time between
the receipt of quotation and the placement of order. During this period, the ore sample has
to be quickly assessed and an informed decision has to be arrived at on the procurement.
The available methods for assessment of Mn ore assessment are not found reliable due to
unpredicted troubles in downstream operations causing losses.
At present, there is not any standard reducibility test for Mn ores as like Fe ores, available
for industries. Some BIS standards are there which describes the nature of Mn ore for
various purposes, but all the standards are lacking the standard reducibility test for Mn ores.
This study is envisaged to develop understanding of reducibility and reduction behavior of
the various kinds of Mn ores and outcome of this investigation may enable the development
of protocol for reliable assessment of reducible nature and reducibility index for manganese
ores.

5|Page
3. Raw Materials Characterizations
3.1.Chemical analysis of raw material

Methods of chemical analysis of manganese ore are gravimetric, volumetric method, and
atomic absorption method. The gravimetric and volumetric methods are suitable for
determination of silica, barium oxide, manganese, iron, phosphorus, sulphur, alumina and other
elements in manganese ores and concentrates. The following standard methods and their
principle is used for analysis of manganese ore.

1. Determination of gangues (silica and alumina) in Mn ore

The sample is decomposed with hydrochloric acid and taken to fumes with sulphuric
acid and filtered. The residue is extracted with ammonium acetate to remove lead,
ignited and then fused with sodium carbonate. The fused mass is extracted with
hydrochloric acid and silica, in the residue, determined by hydrofluorization.
2. Determination of total manganese by Volhard’s method:
This method is based on the oxidation of divalent manganese with potassium
permanganate in a hot (not less than 80°C) solution neutralised with zinc oxide and
containing a little excess of the latter. The endpoint is indicated by the persistent pink
colour.
3. Determination of iron by the dichromate method:
Iron is precipitated as hydroxide from the solution of the sample, dissolved by boiling
with hydrochloric acid. To the boiling solution, stannous chloride is added in slight
excess to reduce ferric iron, the excess stannous chloride is oxidized by mercuric
chloride and the reduced iron is titrated with standard potassiumdichromate solution
using diphenylamine sulphonate as indicator.
4. Determination of alumina by the oxine method:
Iron and manganese are precipitated by passing hydrogen sulphide in the ammoniacal
solution of the sample in presence of tartaric acid which keeps alumina and titania in
solution. After boiling off hydrogen sulphide from the solution, aluminium is
precipitated in the acetate medium and weighed as oxinate. Necessary correction for
titanium is made.

6|Page
The raw material composition is shown in following tables:

Table 1: Composition of Ore

Component MnO2 Fe2O3 P Al2O3 MgO CaO SiO2
High Grade Mn Ore 71.97 12.57 0.08 7.9 0.37 1 1
Low Grade Mn Ore 45.71 8.14 0.24 4.7 0.45 1.3 27.8

Table 2 : Chemical Analysis of coke

Component Fix C Moisture content Volatile Matter Ash GCV(in cal/gram)
%Composition 80.01 0.54 2.63 16.82 6545

Table 3 : Chemical Analysis of Bentonite

Component SiO2 Al2O3 MgO CaO LOI
%Composition 60 18 0.25 0.94 20.81

3.2. X-ray Diffraction (XRD) Analysis

X-ray powder diffraction (XRD) is a rapid analytical technique primarily used for phase
identification of a crystalline material and can provide information on unit cell dimensions. X-
ray diffraction is based on constructive interference of monochromatic X-rays and a crystalline
sample. These X-rays are generated by a cathode ray tube, filtered to produce monochromatic
radiation, collimated to concentrate, and directed toward the sample. The interaction of the
incident rays with the sample produces constructive interference (and a diffracted ray) when
conditions satisfy Bragg’s Law (nλ=2d sin θ). Figure (1) shows X-Ray diffraction machine
installed in CSIR-NML.

XRD powder Sample Preparation:

1. At first, the raw sample was crushed to 150 mess.
2. The sample holder was washed with ethanol to remove any suspended particles.
3. Crushed sample was placed on the top of the holder and was evenly distributed.
4. Extra material was removed from the holder and was placed carefully on the plateform.
5. System was set for graph generation and scan for 10-900 2 theta was set for 40 minutes.
6. Graphs were analyzed using EVA-Diffrac software with search-match mechanism.

7|Page
 Figure 1. Bruker D8 Discover XRD Machine at CSIR NML

3.2.1. XRD analysis of Low Grade (LG) manganese ore

Figure 2 depicts the XRD pattern of high grade Mn ore and it shows that the phase of
manganese; pyrolusite (MnO2), manganese silicate (MnSiO3) and manganese iron
aluminum oxide (MnFeAlO3) are present in the sample. The phase of iron; hercynite
(Fe2AlO4) and aluminum iron oxide (Al3Fe5O11) are present in the sample. SiO2 content is
comparatively low in high-grade ore. Chemical analysis confirms the presence of MnO2
>70%.

Figure 2. XRD pattern of high-grade Manganese ore

8|Page
 3.2.2. XRD analysis of Low Grade (LG) manganese ore
Figure 3 depicts the XRD pattern of low grade Mn ore and it shows that the phase
of manganese; pyroximangite (MnSiO3), pyrolusite (MnO2) are present in the
sample. The phase of iron; iron manganese oxide (FeMnO3) is present in the
sample. And also quartz (SiO2) is present prominently. Mn rich phases are found
to be low in comparison of high grade Mn ore. Chemical analysis also confirms
the same.

Figure 3. XRD pattern of low grade Manganese ore

4. Experimentation
4.1.Thermodynamic Analysis of Manganese Ore Reduction

The reduction of Manganese ore (high and low grade) mainly includes indirect reduction and
direct reduction. High valence state Mn-oxides can be reduced by C/CO at low temperature,
and low valence state Mn/Fe oxides are mainly reduced by solid carbon at higher temperature
[ 16]. The standard Gibbs free energy equations of reduction of Mn/Fe-oxides are presented in
Equation(3-11), below.

2MnO2 + CO → Mn2O3 + CO2 ΔG° = −197950−24.72T, J/mol (3)

3Mn2O3 + CO → 2Mn3O4 + CO2 ΔG° = −175030−0.56T, J/mol (4)
Mn3O4 + CO → 3MnO + CO2 ΔG° = −55390−28.19T, J/mol (5)
MnO + CO → Mn + CO2 ΔG° = 99990+14.98T, J/mol (6)
MnO + C → Mn + CO ΔG° = 270690 - 159.52T, J/mol (7)
3Fe2O3 + CO → 2Fe3O4 + CO2 ΔG° = − 26520 −57.03T, J/mol (8)

9|Page
 1/4Fe3O4 + CO → 3/4Fe + CO2 ΔG° = −3256 + 4.21T, J/mol (9)
FeO + CO → Fe + CO 2 ΔG° = − 17490 + 21.13T, J/mol (10)
FeO + C → Fe + CO ΔG° = 158970 -160.25T, J/mol (11)

An Ellingham diagram is plotted (Fig. 4) and (Fig. 5) of ΔG° versus temperature for oxides
of manganese and carbon using Factstage ( version 6.4 ) software. Since ΔH° and ΔS° are
essentially constant with temperature unless a phase change occurs, the free energy versus
temperature plot can be drawn as a series of straight lines, where ΔS° is the slope and ΔH° is
the y-intercept. The slope of the line changes when any of the materials involved melt or
vaporize.

400

200

0
ΔG° ( KJ )

-200

-400

-600

-800
300 500 700 900 1100 1300 1500 1700 1900 2100
Temperature ( in K )

Figure 4. Ellingham diagram for Manganese Ore reduction

The Gibbs equations (3) ~ (5) and Ellingham diagram show that the reduction of MnO2 →
MnO is very easy, However, MnO can’t be reduced by CO as presented in equation (6), while
equation (7) reveals the starting temperature of the reduction of MnO by solid carbon is very
high, that is, T=1423°C [16]. Therefore, the MnO2 of the ores can only be reduced to MnO in
the reducibility testing experiment as the reduction temperature is below 1423℃. The reduction
process of MnO2 is MnO2→Mn2O3→Mn3O4→MnO→Mn. Both Fe2O3 and MnO2 are
reduced step by step. Both Fe2O3 and MnO2 are reduced step by step [16]. Fe2O3 experiences
reduction of Fe2O3→ Fe3O4→Fe when the temperature is less than 570 oC, while it experiences
Fe2O3→Fe3O4→FeO→Fe when the temperature is higher than 570 oC [16]. The gas-phase
equilibrium diagram of Fe2O3 under various CO-CO2 atmospheres is plotted in Fig. 6. The

10 | P a g e
reduction temperatures and CO contents required for the stepwise reduction of MnO2 are
different.

300

200

100

0
ΔG° ( KJ )

-100

-200

-300

-400
C+O2=CO2
-500

-600
300 450 600 750 900 1050 1200 1350 1500 1650 1800 1950
Temperature (in K)

Figure 5. Ellingham Diagram for the reduction of Fe2O3 to Fe

While using carbon as a reducing agent, a minimum ratio of CO to CO2 will be required
to reduce a given oxide of Mn/Fe. The harder the oxide is to reduce, the greater the proportion
of CO needed in the gases. The ratio pCO/pCO2 is calculated using equation (12). Figure 6, below
depicts the ratio pCO/pCO2 at different temperatures for equations (3 -5), depicted for free energy
above.

ΔG° = RT ln K, where K = pco/pco2 (12).

0.0008

0.0006
PCO / PCO2

0.0004

0.0002

0
300 800 1300 1800 2300
-0.0002
Temperatute ( in K )

Equation 4 Equation 5 Equation 3

Figure 6. The gas-phase equilibrium diagram of equation (3), (4) and (5).

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 4.2. Stoichiometric calculation for reduction of Manganese ore by coke
4.2.1. Calculation of required carbon for reduction of MnO2 to MnO

Carbon Required for Reduction of 100 g of Ore:-

Step 1 : 2MnO2 + C → Mn2O3 + CO

Carbon for high grade ore = 4.963634 g
Carbon for low grade ore = 3.152727g
Temperature for reduction by Ellingham diagram = < 300 K
Step 2 : 3Mn2O3 + C → 2Mn3O4 + CO
Carbon for high grade ore = 1.654544 g
Carbon for low grade ore = 1.050909g
Temperature =< 300 K
Step 3 : Mn3O4 + C → 3MnO + CO
Carbon for high grade ore = 3.30911 g
Carbon for low grade ore = 2.101811g
Temperature = 551 K
Carbon for high grade ore = 4.963634 g + 1.654544 g,+ 3.30911 g = 9.93 g
Carbon for low grade ore = 3.152727g +1.050909g + 2.101811g = 6.30499g

4.2.2. Calculation of required carbon for reduction of Fe2O3 to Fe

Carbon Required for Reduction of 100 g of Ore:-

Step1: 3Fe2O3 + C → 2Fe3O4 + CO

Carbon for high grade ore = 0.31428g
Carbon for low grade ore = 0.20357g
Step2: Fe3O4 + C → 3FeO + CO
Carbon for high grade ore = 0.628569g
Carbon for low grade ore = 0.40713999g
Step3: FeO + C → Fe + CO
Carbon for high grade ore = 1.88570g

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 Carbon for low grade ore = 1.22141g
Total Carbon for high grade ore = 12.455784g
Total Carbon for low grade ore = 8.111299g
If coke has 80% Carbon then,
Coke required for high grade ore = 12.455784/0.8 g = 15.94375 g ~ 16 g
Now, We are taking Coke in excess of 20% .
Then , total Coke for high grade ore = 16 + 16*0.2 = 16+3.2
= 19.2 g ~ 20 g
Total Coke for low grade ore = 12.16694g ~ 12.2g
4.3. Experimental Procedure
4.3.1. Pelletization of Manganese ore fines

In the pelletizing process, the production of good quality green balls is essential, because
the subsequent drying and firing procedures cannot make good fired balls from poor quality
green balls. In 1958 Newitt and Conway-Jones [26] investigated the theory of ball formation
and paid particular attention to the water-particle system occurring in the balling process. Based
on the work of Hanies [27] and Fisher [28] in the field of soil mechanics, the identified three
states of the water-particle system:
1. The Pendular state, when water is present at points of grain contact only and surface
tension holds the particles together;
2. The funicular state, when some pores are fully occupied by water;
3. The capillary state, when all the pores are filled but the surface is not covered by a
coherent water film.

These three phases are present at during the production of pellets.

Figure 7. A schematic drawing showing the different states of water-particle system

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Pellets (Figure 10) were made in the machine called Disk-pelletizer (Figure 9). Composition
of pellets is shown in the table 4.

Table 4. Composition of pellets

Ore type Ore ( in grams ) Coke ( in grams ) Bentonite ( in grams)

High Grade 1000 200 5
Low Grade 1000 122 5

Figure 8. Picture of ore fines, Figure 9. Disk pelletizer at CSIR-NML, Figure 10. Pellets From pelletizer

4.3.2. Drying of Manganese ore pellets

Drying is basically governed by the principles of transport of heat and mass. When a
moist solid is heated to an appropriate temperature, moisture vaporizes at or near the solid
surface and the heat required (sensible heat and the heat of vaporization) for drying is usually
supplied by a hot gas (exceptions: microwave drying, freeze drying, etc.). As soon as some of
the surface moisture vaporizes, more moisture is transported from inside the solid to its surface.
Moisture can move within a solid by a variety of mechanisms depending upon the nature and
type of the solid and its state of aggregation. The mechanism of moisture transport in different
solids may be broadly classified into (1) transport by capillary forces, (2) liquid diffusion, (3)
pressure induced transport, and (4) vapour diffusion. The mechanism that dominates depends
on the nature of the solid, its pore structure and the rate of drying. Drying of pellets is done in
the hot air oven (Figure 11) at 105℃ and time duration of drying was 3-4 hours.

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 Figure 11. Hot air oven at CSIR-NML Figure 12. Pellets after drying

4.3.3. Resistance heating for reduction of pellets

The manganese ore grains were ground to -100μm collected from the mine. Chemical analyses
of the unreduced manganese ore are. Pellets were prepared in the disk pelletizer with tilt angle
of 30-40 degree. Then pellets were heated at 105℃ in the hot-air oven for 3 hours to remove
free moisture. Reduction experiments were carried out in muffle furnace. In the isothermal
reduction, when the predetermined temperature reached, pellet samples were put in crucible
with known sample weight. The reaction temperature was set as 1000℃ and 700℃, and
reaction time was set as 30min, 60 min, 90 min, 120 min and 150 min. In the non-isothermal
reduction, pellet samples were kept in furnace from the starting of the furnace. The initial and
final weight of sample are measure for reduction calculation. The process and reduction
conditions are shown in Table 5.

Table 5 : Experimental conditions with sample ID

S.No. Experimental condition
ID Ore type Temperature, ◦C Time( in mins.)
1 M1 High grade 1000 Isothermal 30
2 M2 High grade 1000 Isothermal 120
3 M3 High grade 700 Isothermal 30
4 M4 High grade 700 Isothermal 120
5 M5 High grade 1000 Non -isothermal 120

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 6 M6 High grade 700 Non -isothermal 120
7 LM1 Low Grade 700 Isothermal 30
8 LM2 Low Grade 700 Isothermal 120

9 LM3 Low Grade 1000 Isothermal 30

10 LM4 Low Grade 1000 Isothermal 120

11 LM5 Low Grade 1000 Non -isothermal 120

12 LM6 Low Grade 700 Non -isothermal 120

Figure 13. Muffle furnace (1100oC) used for reduction experiments

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5. Results and Discussion
5.1.General visual Observations

The reduction of high-grade Mn ore is performed in muffle furnace at 700 and 1000 ◦C
isothermally and non-isothermally for 30min, 60 min, 90 min, 120 min and 150 min. The
percentage of weight loss of high-grade Mn ore is shown in Fig 14.

29

27

25
%weight loss

23
1000℃( isothermal)
21

19

17

15
0 50 100 150 200
Time in min.

Figure 14. Isothermal and Non-Isothermal weight loss Vs time of High-grade Manganese ore

We observed that maximum weight of high-grade Mn ore is 28.76% at 1000℃ for 150 min in
isothermal condition for the reduction to manganite (MnO). The change in weight lost may be
due to reduction of reduction of MnO2, iron oxide and burning of coke, which is admixed in
pellets as reducing agent. Here we did not confirm that reduction of iron oxide is occurred
according to XRD and Chemical analysis, which show that no iron metal and FeO have
detected in the reduction product of high-grade and low grade manganese ore. It is observed
that, in case of isothermal reduction of high-grade Mn ore pellets, cracking of pellets are
occurred because of thermal sock or because of moisture present in pellets. On the other side,
in the non-isothermal reduction of high-grade Mn ore pellets did not crack. From the graph of
% weight loss vs time, weight loss is increasing with time, this means degree of reduction is
increasing with time.

5.2.Chemical Analysis

All the samples M1-M6 and LM1-LM6 were analyzed using conventional wet techniques
stated above (in sec. raw material characterization) and ICP-OES. The carbon analysis was
done using Leco machine at CSIR NML. Table 6 depicts the chemical analysis of M1-M6

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 i.e. high grade Mn ore reduced with carbon. Table 7 depicts the chemical analysis of LM1-
LM6 i.e. low grade Mn ore reduced with carbon.

Table 6 : Chemical analysis of reduced high grade Mn ore with C in Percentage

Component M1 M2 M3 M4 M5 M6
TMn 48.73 52.16 49.28 47.8 51.38 48.86
TFe 13.3 12.42 12.8 12.48 12.47 11.11
FeO 0 0 0 0 0 0
Fe2O3 19.01 17.76 18.30 17.84 17.83 15.88
Carbon 8.31 2.03 5.31 3.23 0.05 1.73

Table 7 : Chemical analysis of reduced low grade Mn ore with C in Percentage

Component LM1 LM2 LM3 LM4 LM5 LM6
TMn 19.73 20 19.94 18.89 20.92 21.5
TFe 8.67 9.73 8.55 9.57 10.28 9.537
FeO 0 0 0 0 0 0
Fe2O3 12.39 13.91 12.22 13.68 14.70 13.63
Carbon 7.29 3.90 4.59 1.77 0.05 0.77

5.3. Reduction index/O2 loss ratio

The reducibility of the Mn ore is a key factor to the energy consumption in the metallurgical
process. The reduction index is xpressed by the ratio of the removed oxygen to the total oxygen
in the Mn/Fe oxides. However, natural manganese ores contain metal oxides besides some
amount of crystal water. Determination of reduction of Mn ore using mass loss does not give
the exact reduction because it involves chemical and physical change in the sample. Therefore,
we are used the data of chemical analysis to measure the reduction index / O2 loss ratio.

ξ = [(WC.O. Mo ─ WC.T . MT) 16/12] / MO. WO.O (13)

Where, MO and MT are the weight before and after the reaction, respectively, WC.0, WC.T are
carbon content in the sample before and after the reaction, respectively, and WO.0 is oxygen
content of the sample before the reaction and ξ is reduction index or O2 loss ratio.

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The pellets of high grade and low grade Mn ore with coke reducing agent, which is admixed
in the pellets, are placed in the furnace after attained pre –determined temperature of 700 and
1000 ◦C for 30min, 60 min, 90 min, 120 min and 150 min. Then composition and phases are
determined for isothermal reduction of low and high grade. We have observed that reduction
index of both high grade, low-grade ore are higher at 1000℃ than 700℃ for 30, and 120 min
of reduction time as mentioned in Table 8. Reduction time is playing very important role in
reduction of Mn ore for low-grade ore as at 700℃ for 120 min reduction index show 36.85 %
while 32.95 % for low-grade ore at 1000℃ /30 min. Chemical analysis and XRD analysis of
reduced low-grade ore show that there is no formation of metallic and FeO in reduction process
as in high-grade Mn ore. However, in reduction of low-grade ore pallets did not crack because
of high percentage of gangue minerals such as SiO2, MgO, Al2O3, CaO etc. The reduction of
low grade and high grade Mn ore with different reduction condition are shown in table 8. In
the table 8, it can be seen that in the condition of 700℃ and at 30 minutes, reduction index of
high grade Mn ore is less than low grade Mn ore and in the other condition, reduction index of
low grade Mn ore is higher.

We used equation (13) to determine the reducibility index of high ore from the chemical
analysis of reduced pellets. The chemical analysis of reduced high-grade Mn ore is shown in
Table 6.

Table 8: Comparison of reduction index of ores

Reduction Reduction Reduction Index ( R. I. )
Temperature(℃) Time( in mins.) High Grade Low Grade
Isothermal 700 30 0.155788831 0.096217926
Reduction 700 120 0.268350328 0.36859561

1000 30 0.199060934 0.329570088

1000 120 0.241362216 0.504996977

Non-isothermal 700 120 0.269757037 0.564133605

Reduction
1000 120 0.300554625 0.607387414

From this mechanism, the information obtained for reducibility is not reliable. Equation 13,
yields the results as HG Mn ore reducibility is less than the LG Mn ore reducibility, which is
unconventional. The O2 loss mechanism and the results are to be verified further.

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 5.4. XRD Analysis of reduced samples
X-ray diffraction analysis was done for all product samples (procedure described in sec. raw
material characterization) for analyzing the different phases present in the sample, which may
lead towards the reduction behavior of the ores under various conditions. HGMn ore samples
basically were having the lower oxidation state Mn phases, while the LGMn ore samples
produced were having high amount of silicate phases alongwith SiO2. MnO was found much
prominent in M1-M6, than the LM1-LM6. The results among isothermal and non-isothermal
reductions were comparable and beside physical strength of pellets, the phases of Mn, Fe, SiO2
and C were alamost similar. Futher analysis of each XRD analysis with phases observed are
given below.

Figure 15 shows that after reduction of high grade ore for 30 minutes at 1000℃ (M1), the
phase of manganese; manganosite (Mn0.95O), Hausmannite (Mn3O4), Manganese oxide
(Mn2O3) and Manganese carbide (Mn5C2) are present in the sample. The phase of iron; iron
oxide (Fe2O3), ferrous manganese oxide (FeO MnO), ahrensite (Fe2SiO4) are present in the
sample. Also Silicon oxide (SiO2) and calico-olivine (Ca2SiO4) are present in the sample.

Figure 15. XRD pattern of HG ore at 1000℃ for 30 minutes in isothermal condition (M1).
Figure 16 shows that after reduction of high grade ore for 120 minutes at 1000℃ (M2),
the phase of manganese; manganosite (Mn0.95O), hausmannite (Mn3O4), manganese carbide
(Mn5C2) are present in the sample. The phase of iron; iron oxide (Fe2O3) is present in the
sample. The phase of silicon; manganese silicate (MnSiO3), Tephroite (Mn2SiO4) and calcium
silicon oxide (CaSiO3) are present in the sample.

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Figure 16. XRD pattern of HG ore at 1000 for 120 minutes in isothermal condition(M2)
Figure 17 shows that after reduction of high grade ore for 30 minutes at 700℃ (M3), the phase
of manganese; Manganese dioxide (MnO2), hausmannite (Mn3O4), manganese oxide (Mn2O3),
manganese carbide (Mn11C2) are present in the sample. The phase of iron; iron oxide (Fe2O3)
and magnetite (Fe2.946O4) are present in the sample. The phase of silicon; calcium silicon oxide
(CaSiO3) and calico-olivine (Ca2SiO4) are present in the sample.

Figure 17. XRD pattern of HG ore at 700℃ for 30 minutes in isothermal condition(M3).

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 Figure 18. XRD pattern of HG ore at 700℃ for 120 minutes in isothermal condition (M4)

Figure 18, above shows that after reduction of high grade ore for 120 minutes at 700℃
(M4), the phase of manganese; Manganese oxide (MnO), hausmannite (Mn3O4), Bixbyte
(Mn2O3), manganese carbide (Mn5C2 and Mn7C3) are present in the sample. The phase of iron;
iron oxide (Fe2O3) and magnetite (Fe3O3.99) are present in the sample. The phase of silicon;
calcium silicon oxide (CaSiO3), Pyroxmangite (MnSiO3) and calico-olivine (Ca2SiO4) are
present in the sample.

Figure 19, below shows that after reduction of high grade ore for 120 minutes at 1000℃
(M5) in non-isothermal condition, the phase of manganese; manganese oxide (MnO),
hausmannite (Mn3O4), Bixbyte (Mn2O3), jacobsica (MnFe2O) and manganese carbide (Mn5C2)
are present in the sample. The phase of iron; iron oxide (Fe2O3), iron silicon oxide (Fe2.3Si0.7O4)
and magnetite (Fe3O4) are present in the sample. The phase of silicon; calcium silicon oxide
(CaSi2O4), calcium silicate (Ca2SiO4) are present in the sample.

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Figure 19. XRD pattern of HG ore at 1000℃ for 120 min. in non-isothermal condition (M5)
Figure 20 shows that after reduction of high grade ore for 120 minutes at 700℃ (M6)
in non-isothermal condition, the phase of manganese; manganese oxide (MnO),
manganese(Ⅳ) oxide(MnO2) hausmannite (Mn3O4), Bixbyte (Mn2O3), bixbte ferrian
(FeMnO3), manganese iron oxide(Mn2.7Fe0.3O4) and manganese carbide (Mn5C2 and MnC8) are
present in the sample. The phase of iron; hematite (Fe2O3) and magnetite (Fe3O4) are present
in the sample. The phase of silicon; calcium silicon oxide (Ca3SiO), calico-olivine (Ca2(SiO4))
are present in the sample.

Figure 20. XRD pattern of HG ore at 700℃ for 120 min in non-isothermal condition (M6)

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 Figure 21 shows that after reduction of low grade ore for 30 minutes at 700℃ in
isothermal condition, the phase of manganese; manganese(Ⅳ)oxide (MnO2) ,hausmannite
(Mn3O4), Bixbyte (Mn2O3), pyroxmangite (MnSiO) and manganese carbide (Mn7C3) are
present in the sample. The phase of iron; hematite (Fe2O3), iron carbide (Fe7C3), clinoferrosilite
(FeSiO3) are present in the sample. The phase of silicon; quartz (SiO2), calcium silicate
(Ca2SiO4) are present in the sample.

Figure 21. XRD pattern of LG ore at 700℃ for 30 minutes in isothermal condition (LM1).

Figure 22, below shows that after reduction of low grade ore for 120 minutes at 700℃
in isothermal condition, the phase of manganese; manganese(Ⅲ) oxide(Mn2O3), hausmannite
(Mn3O4), manganese iron oxide (Mn0.176Fe1.824O3), rohodonite (MnSiO3) and manganese
carbide (Mn7C3) are present in the sample. The phase of iron; hematite (Fe2O3), iron carbide
(Fe3C), ahrensite(Fe2SiO4) are present in the sample. The phase of silicon; quartz (SiO2),
Calcio-olivine (Ca2(SiO4)) are present in the sample.

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 Figure 22. XRD graph of LG ore at 700℃ for 120 min in isothermal condition (LM2)

Figure 23 shows that after reduction of low grade ore for 30 minutes at 1000℃ in
isothermal condition, the phase of manganese; manganosite (MnO), hausmannite
(Mn3O4),tephroite (Mn2SiO4), rohodonite (MnSiO3) and manganese carbide (Mn5C2 ) are
present in the sample. The phase of iron; hematite (Fe2O3), iron carbide (Fe2C), di-iron silicate
(Fe2(SiO4)), magnetite (Fe2.9O4) are present in the sample. The phase of silicon; quartz (SiO2),
calcium silicate (Ca2(SiO4)) are present in the sample.

Figure 23. XRD pattern of LG ore at 1000℃ for 30 minutes in isothermal condition (LM3).

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Figure 24 shows that after reduction of low grade ore for 120 minutes at 1000℃ in isothermal
condition, the phase of manganese; manganosite (MnO), hausmannite (Mn3O4), tephroite
(Mn2(SiO4)), rohodonite (MnSiO3) and manganese carbide (Mn7C3) are present in the sample.
The phase of iron; hematite (Fe2O3), magnetite (Fe3O4), iron carbide (Fe2C), ferrosilite
(FeSiO3), iron oxide silicate (Fe7(SiO4)) are present in the sample. The phase of silicon; quartz
(SiO2), calcium silicate (Ca2(SiO4)), tophroite (MnFe(SiO4)) are present in the sample.

Figure 24. XRD pattern of LG ore at 1000℃ for 120 minutes in isothermal condition (LM4).

Figure 25 shows that after reduction of low grade ore for 120 minutes at 1000℃ in non-
isothermal condition, the phase of manganese; manganosite (MnO), hausmannite (Mn3O4),
tephroite (Mn2(SiO4)), rohodonite (MnSiO3) are present in the sample. The phase of iron;
hematite (Fe2O3), clinoferrosilite (FeSiO3), braunite (Mn6.98Fe0.02(SiO4)O8) are present in the
sample. The phase of silicon; quartz (SiO2), calcium silicate (Ca2(SiO4)), are present in the
sample.

26 | P a g e
Figure 25. XRD pattern of LG ore at 1000℃ for 120 min in non-isothermal condition (LM5).

Figure 26 shows that after reduction of low grade ore for 120 minutes at 700℃ in non-
isothermal condition, the phase of manganese; hausmannite (Mn3O4), manganese(Ⅲ)oxide
(Mn2O3) tephroite (Mn2(SiO4)), manganese carbide (Mn7C3) are present in the sample. The
phase of iron; hematite (Fe2O3), iron carbide (Fe3C), wadsleyite (Fe2.33Si0.67O4) are present in
the sample. The phase of silicon; quartz (SiO2), calcium silicate (Ca2(SiO4)), are present in the
sample.

Figure 26. XRD pattern of LG ore at 700℃ for 120 min in non-isothermal condition (LM6).

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 5.5.Comparison of reduction behavior between High Grade Mn (HGMn) and Low Grade
Mn (LGMn) ore with carbon at varying conditions with XRD analysis

Figure 27 shows the comparison of reduced ore samples M3 and LM1 under isothermal
conditions at 7000C and 30 minutes. It is evident that under isothermal conditions HGMn ore
is reduced better than the LGMn ore. The formation of lower oxidation states of Mn i.e MnO,
Mn3O4, Mn2O3 are observed in HG Mn ore, while in LG Mn ore the presence of these phases
are negligible, specially MnO. Some peaks of Mn3O4 can be found but not prominent. On the
other hand the Mn-Si-O alongwith SiO2 itself is prominently present in reduced LGMn Ore
samples. Some of the carbides of Mn and Fe are also present, which may be due to reaction
among high concentration of Mn and Fe in the system.

Figure 27. Comparative study of isothermal reduction at 700℃ and 30 min

Figure 28 shows the comparison of reduced ore samples M4 and LM2 under isothermal
conditions at 7000C and 120 minutes. This case is similar to that of earlier case, where oxidized
phases of Mn can be easily observed, but there is not much change with respect to increase in
time i.e 30 to 120 minutes. The phases once developed at 30 minutes are still present at the end
of 120 minutes. It may be concluded that the effect of time in this case is not prominent after
30 minutes.

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 Figure 28. Comparative study of isothermal reduction at 700℃ and 120 min

Figure 29 shows the comparison of reduced ore samples M1 and LM3 under isothermal
conditions at 10000C and 30 minutes. It is evident that under isothermal conditions HGMn ore
is reduced better than the LGMn ore. The formation of lower oxidation states of Mn i.e MnO,
Mn3O4, Mn2O3 are observed in HG Mn ore, while in LG Mn ore the presence of these phases
are negligible, specially MnO. Some peaks of Mn3O4 can be found but not prominent. On the
other hand the Mn-Si-O alongwith SiO2 itself is prominently present in reduced LGMn Ore
samples. Some of the carbides of Mn and Fe are also present, which may be due to reaction
among high concentration of Mn and Fe in the stsytem. The increased and prominent peaks of
Mn-O as compared to 7000C can be observed. On higher temperature oxidation of MnO2 is
better and high. Whereas, in low grade ore too, some peaks of lower oxidation states of Mn are
present, which is due to high temperature conditions. The reducibility of available Mn in ore is
enhanced due to high temeprature.

Figure 30 shows the comparison of reduced ore samples M4 and LM2 under isothermal
conditions at 10000C and 120 minutes. This case is similar to that of earlier case, where
oxidized phases of Mn can be easily observed, but there is not much change with respect to
increase in time i.e 30 to 120 minutes. The phases once developed at 30 minutes are still present
at the end of 120 minutes for 10000C too. It may be concluded that the effect of time in this
case is not prominent after 30 minutes and high temperature and longer durations have not any
synergistic effect.

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 Figure 29. Comparative study of isothermal reduction at 1000℃ and 30 min

Figure 30. Comparative study of isothermal reduction at 1000℃ and 120 min

Figure 31 shows the comparison of reduced ore samples of high grade ore, M2 and M5
under isothermal non-isothermal conditions at 10000c and 120 minutes. Both under isothermal
and the non-isothermal conditions HGMn ore is reduced. The formation of lower oxidation
states of Mn i.e MnO, Mn3O4, Mn2O3 are observed in HG Mn ore. The non-isothermal
conditions shows some presence of MnO2, which shows the presence of unreacted feed ore.
The carbide phase of Mn is also observed, which attributes to the reaction of Mn with C, rather
than Oxygen in the sample with C.

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 Figure 31. Comparative study of reduction of high-grade ore at 1000℃ and 120 min

Figure 32 shows the comparison of reduced ore samples M6 and LM6 under non-
isothermal conditions at 7000C and 120 minutes. It is evident that under non isothermal
conditions also HGMn ore is reduced better than the LGMn ore, like in isothermal conditions.
The formation of lower oxidation states of Mn i.e MnO, Mn3O4, Mn2O3 are observed in HG
Mn ore, while in LG Mn ore the presence of these phases are negligible, specially MnO. On
the other hand the Mn-Si-O alongwith SiO2 itself is prominently present in reduced LGMn Ore
samples.

Figure 32. Comparative study of non-isothermal reduction at 700℃ and 120 min

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 Figure 33 shows the comparison of reduced ore samples M5 and LM5 under non-
isothermal conditions at 1000℃ and 120 minutes. It is evident that under non isothermal
conditions HGMn ore is reduced better than the LGMn ore. The formation of lower oxidation
states of Mn i.e MnO, Mn3O4, Mn2O3 are observed in HG Mn ore, while in LG Mn ore the
presence of these phases are negligible, specially MnO. On the other hand the Mn-Si-O
alongwith SiO2 itself is prominently present in reduced LGMn Ore samples. It is also observed
that the increase in temperature for non-isothermal reduction enhances the amount of reduction
in pellets to some degree but formation of MnO phase is not that much as in isothermal case.
In other side, for low grade ore Mn3O4 and Mn2O3 phases were present. It may be stated that,
high temperature is beneficial for low grade ores.

Figure 33. Comparative study of non-isothermal reduction at 1000℃ and 120 min

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6. Conclusion:
The carbothermic reduction of high grade and low grade ore was studied in temperature
region 700℃ and 1000℃ for 30 and 120 minutes respectively. Carbothermic reduction could
transform the higher oxide paramagnetic manganese ore-mineral to lower oxide ferromagnetic
mineral. The pellets had to be preheated to remove the moisture prior to reduction studies. The
O2 loss mechanism was not found suitable to predict the reducibility of high and low grade
manganese ores. The O2 loss in this case couldn’t count the synergetic effect of reduction of
Fe2O3 and MnO2 in the sample. It may need to modify it for Mn-Fe system in ores. XRD
analysis of products obtained from different conditions show that HGMn ores are easi;y
reducible with C/CO that he LG Mn ores. The formations of MnO, Mn2O3 and Mn3O4 were
prominent with high grade Mn ore. The amount of calcium silicate and other forms of silicate
lower grade was pretty high, which might be retarded the reduction of MnO2 in LG ores. The
effect of increasing time was not there on constant temperatures i.e. 700 and 10000C, but with
increase in temperature the reduction was enhanced, as seen in XRD analysis. The products in
non -isothermal reduction was found similar as isothermal reduction and there was not any
significant effect on Mn-phase development in non-isothermal reduction. High grade i.e. high
Mn/Fe ratio may yield better reduction but SiO2 can adversely affect the reduction.

7. Future Scope

The mechanism of measuring reducibility of Mn ore based on their composition is need to

be quantified as RI (reducibility index). The effects of the composition and formation of slag
i.e. presence of silica are need to explored further. A design of experiments i.e. statistical
approach may be used to find out relation among various parameters like concentration of SiO2,
Mn/Fe, C/CO, temperature and time, which will be helpful in designing the reducibility index
for natural Mn ores.

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References
[1] Indian Minerals Year Book, Part- III: Mineral Reviews: Manganese Ore, 2017, 56.

[2] Z.Z. Tan, “Metallurgy of Manganese”, (Chang Sha, HuNan, Central South University
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