Hydrometallurgy 187 (2019) 168–186

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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Reducing agents in the leaching of manganese ores: A comprehensive review T

Manish Kumar Sinha , Walter Purcell
⁎

Department of Chemistry, University of the Free State, Bloemfontein 9300, South Africa

ARTICLE INFO ABSTRACT

Keywords: Manganese is a strategically important metal that is widely used in industrial applications such as steel, catalysts,
Manganese and batteries. Manganese generally presents as manganese dioxide (MnO2) in most of the ores. As MnO2 is stable
MnO2 in acid or alkaline oxidizing conditions, manganese extraction must be performed under reducing conditions to
Reductive leaching convert the insoluble Mn(IV) to soluble Mn(II) in aqueous medium. In this regard, two processes are followed
Reducing agents
viz. reduction roasting followed by leaching and reductive leaching. The major disadvantage of the reduction
Hydrometallurgy
Extraction
roasting process is the intensive energy consumption, high investment and operating costs as well as the oc-
casional release of harmful gases. The hydrometallurgical reductive leaching method possesses the advantages of
energy conservation and one-step leaching process. The reducing agents used for leaching are either pure in-
organic or organic chemicals or sometimes new kinds of reducing agents such as agricultural and biomass
wastes. The present review summarizes the process developed for extraction and recovery of manganese from
ores using different kinds of reducing agents. The parameters affecting the leaching of manganese and reactions
involved are reviewed and discussed.

1. Introduction Major manganese minerals include pyrolusite (MnO2), romanechite

The widespread industrial application of manganese, which ranges
from steel production to batteries, glass, non-ferrous alloys, catalysts,
animal feed, fertilizers, colourant or pigment, medicine, leather tan-
ning, matches/fireworks and chemical production, makes it a strategic
element (Pagnanelli et al., 2004b; Hagelstein, 2009). In fact after iron,
aluminium and copper it is the fourth most commonly used metal by
tonnage. Most of the world's manganese (~70%) originates from the
Kalahari District of South Africa with the rest found in Australia, China,
Gabon, and to a lesser extent in Brazil and Ukraine. In 2017, manganese
consumption came to about 19 million metric tons while approximately
20 million metric tons of manganese ore was produced globally in the
same year. The estimated demand for manganese in 2022 is forecasted
to reach 28.2 million metric tonnes whereas by 2022, manganese pro-
duction will decrease to 19.1 million metric tons (Statista, 2018). Ap-
parently, the widening gap between supply and demand in manganese
should lead to a healthy price increase over the next few years. The
rapid depletion in the grade of manganese ore due to ever-growing
demand of manganese metal is one of the reasons for this consumption
and production gap as well as for the price hike of both manganese ores
and alloys (Ghosh et al., 2018). At the same time, due to the complex
mineral nature and challenging beneficiation requirements, it is diffi-
cult to exploit low-grade manganese ores cheaply and effectively.
(BaMnMn5O16(OH)4), manganite (Mn2O3.H2O) and haussmannite
(Mn3O4), which are categorized in three grades according to their
manganese content as well as according to its iron and impurity con-
tent. The high- or metallurgical-grade ores contain 44–48% Mn while
medium-grade ores contain approximately 35–44% Mn and low-grade
ores contain 25–35% Mn (Xiong et al., 2018; Acharya et al., 2004).
Some commonly used manganese minerals with percentage manganese
composition are shown in Table 1. Manganese carbonate ore (rhodo-
chrosite) is recognized as the most valuable high-grade manganese ore.
However, due to the depletion of this source and limited distribution
worldwide, manganese oxide ores such as pyrolusite (accounting 60%
of world's total manganese reserve) are extensively used for manganese
and its alloys production. Considerable attention has been given to the
development of viable technologies to utilize medium- and low-grade
ores as well as other valuable secondary resources like mine tailings,
residues or spent batteries to meet the future demand of manganese
(Zhang et al., 2018a).
Mineralogical investigations have also revealed that Manganese
occurs in the minerals as higher oxides, mainly pyrolusite (MnO2).
Since MnO2 is stable in direct acid or alkali dissolution, the possible
reduction of the insoluble tetravalent manganese(IV) to soluble bivalent
manganese(II) is necessary to recover manganese from its ores. The
reduction of manganese from these oxide ore deposits can be processed

⁎
Corresponding author.
E-mail address: mksinhajsr@gmail.com (M.K. Sinha).

https://doi.org/10.1016/j.hydromet.2019.05.021
Received 27 February 2019; Received in revised form 14 May 2019; Accepted 24 May 2019
Available online 27 May 2019
0304-386X/ © 2019 Elsevier B.V. All rights reserved.
M.K. Sinha and W. Purcell Hydrometallurgy 187 (2019) 168–186

Table 1 sp. (Han et al., 2013), MnO2 ore bioleaching with Aspergillus niger
Manganese minerals with percentage composition (Baba et al., 2014; Neculita (Paponetti et al., 1989), Thiobacillus thiooxidans (Porro et al., 1990) and
and Rosa, 2018; http://webmineral.com/). Bacillus sp. (Das and Ghosh, 2018). Apart from this, other investigations
Minerals Chemical composition Mn (approx.%) report the reduction of MnO2 from mine tailings and residues (Li et al.,
2009; Mehta et al., 2010). The effect of different parameter on man-
Franklinite (Fe, Zn, Mn)O (Fe, Mn)2O2 10–20 ganese bioleaching has been reviewed by Ghosh et al. (2016). Despite
Manganian calcite (Ca, Mn)CO3 35.4
environmental friendlier processes, the bio-hydrometallurgical methods
Bementite Mn5Si6O15(OH)10 43.2
Rhodochrosite MnCO3 47.8 have not been commercialized, mainly due to the fact that the methods
Rhodonite MnSiO3 41.9 need to be adapted according to each type of element present and at the
Romanechite BaMnMn5O16(OH)4 51.7 same time these processes are kinetically slow (Baba et al., 2014; Peng
Cryptomelane KMn5O16 59.8
et al., 2018).
Manganite Mn2O3H2O 62.5
Pyrolusite MnO2 63.2
Hydrometallurgy has clear advantages over pyro- and bio-me-
Braunite Mn2Mn6SiO12 66.6 tallurgical process and has gained considerable attention of researchers
Haussmannite Mn3O4 72.0 over the years due to the high efficiency and low energy consumption of
Bixbyite Mn2O3 52.0 these processes. Above all, these processes are also well suited for lean,
Pyrochroite Mn(OH)2 61.7
low grade and complex ores, easy to control on each processing step,
Vernadite MnO2∙nH2O 30.4
Alabandite MnS 63.1 and feasible on small as well as industrial scale. Since the recovery of
Birnessite (Na,Ca)Mn7O14∙2.8H2O 50.9 manganese from its ores involving the reduction of manganese oxide,
Chalcophanite ZnMn3O7.3H2O 40.6 the type of reducing agent used in hydrometallurgical processes became
Lithiophorite LiAl2(Mn2 4+Mn3+)O6(OH)6 38.7
a key factor in the development of this kind of beneficiation process.
Hollandite Bax(Mn4+,Mn3+)8O16 42.5
Todorokite (Ca,Na,K)x (Mn4+,Mn3+)6O12∙3.5H2O 56.5
The advantage of the direct reduction leaching method is that reduction
and leaching steps are carried out in a single stage. A diverse range of
reductants has been used in the recovery of manganese from a variety
via pyrometallurgy, hydrometallurgy and bio-hydrometallurgy. The of ores and secondaries. The focus of this article is to provide a concise
influence of different metallurgical processes on the economic recovery review on the use of different kinds of reducing agents on the reductive
of manganese as chemical manganese dioxide (CMD), electrolytic leaching of manganese from its different ores. The review discusses the
manganese (EM) or electrolytic manganese dioxide (EMD) from variety chemistry and reactions involved in the reductive leaching of manga-
of resources has been discussed and reviewed (Zhang and Cheng, 2007). nese and focuses on key parameters that could potentially affect the
The conventional pyrometallurgical technique includes reductive leaching of manganese from ores or concentrates of different origins.
roasting of manganese oxide ores with carbon at about 700–900 °C
(Paixdo et al., 1995). The reductive roasting in a reverberating furnace,
1.1. Reduction chemistry of manganese oxide
rotary kiln or fixed bed using CO (Paixdo et al., 1995) or H2 (De Bruijn
et al., 1980; Jerez and Alario, 1982; El-Gawad et al., 2014) as reductive
In nature, manganese normally occurs in three oxidation states viz.
gasses have also been reported. In recent years, a number of reducing
II, III, and IV. The relative stability of each oxidation state in solution is
agents were used in the reductive roasting-leaching of manganese from
highly influenced by the oxidation potential (Eh) and the pH (Fig. 1).
a variety of ores. The reducing agents include bagasse at 500 °C for
When Eh-pH conditions are changed, manganese is transformed into
40 min (Long et al., 2013), cornstalk at 500 °C for 80 min (Cheng et al.,
the phase most stable under the new conditions if suitable thermo-
2009), ammonium sulphate at 450 °C for 30 min (Deng et al., 2018),
dynamically favourable reaction pathways exist. However, predicting
pure sulphur at 550 °C for 10 min (Zhang et al., 2013), SO2 at 500 °C for
the transformation rates requires a kinetic analysis (Martin, 2005).
60 min (You et al., 2015), ammonium sulphate at 550–575 °C for
From Fig. 1 it is clear that for an efficient transformation of Mn(IV)
55–60 min (Sahoo and Rao, 1989), pyrite (Chun et al., 2000), graphite
from manganese ore into Mn(II), reductive leaching should be per-
at 800 °C for 30 min (Welham, 2002), CO at 950 °C (Zhang et al., 2010),
formed in an acidic environment (lower Eh value). The reduction of
carbon at > 1100 °C (Akdogan and Eric, 1994, 1995; Ostrovski and
MnO2 under acidic conditions can be expressed by following equation:
Webb, 1995), and Na2S2O3 at 1100 °C for 100 min (Zhang et al.,
2017a). It is difficult to make useful comparisons between these pub-
lished reports on the reduction roasting processes (followed by leaching 2.2
using water or acids) due to the large variation in the chemical com- 1.8 MnO4-
position of manganese ores that were investigated. Despite high man-
ganese recoveries obtained with pyrometallurgical processes, dis- 1.4
MnO2
advantages rendered these processes unpopular. Disadvantages 1 MnO42-
included high investment and operating costs, high energy consump-
tion, long roasting time, insufficient heat and mass transfer, easy sin- 0.6
tering and environmental pollution (such as the release of considerable
E(V)

0.2
amount of smoke dust, SOx and NOx, by chemical plants). In addition,
these processes do not allow for the economical processing of low-grade -0.2 MnCO3
manganese ores.
-0.6 Mn2+
Considering less hazardous systems, the recovery of manganese
Mn(OH)2
from manganese ores using bio-hydrometallurgical processes with mi- -1
croorganisms have been reported. Acharya et al. (2002, 2003) in-
-1.4
vestigated the bioleaching of manganese ore with Penicillium citrinum, Mn (s)

which was isolated from the top soil of an active manganese ore mine. -1.8
Literature reports the bioleaching of low-grade manganese wad ore -2 0 2 4 6 8 10 12 14 16
with the heterotrophic microorganisms (Enterobacter agglomerans, E. pH
cloacae, Pseudomonas cepacia, and Bacillus coagulans) (Baglin et al.,
1992), pyrite-pyrolusite bioleaching using sulphur-oxidizing Thiomonas Fig. 1. Eh-pH stability diagram of manganese (approximate values) (Rincón-
Tomás et al., 2016; Freitas et al., 2013).

169
M.K. Sinha and W. Purcell
MnO2 + 4H+ + 2e Mn2+ + 2H2 O E o = 1.229V (1)
The redox energy potential for the decomposition and transforma-
tion of Mn(IV) to Mn(II) is calculated to be 20.80 at 25 °C and 16.85 at
85 °C, whereas the Eh value varies from 1.23 to 1.20 at the respective
temperatures. Thus, in order to reduce MnO2 from ore, reducing agents
must possess a lower redox energy potential than the basic decom-
position reaction of the manganese oxide (Sobianowska-Turek et al.,
2014; Amiliana et al., 2018). The formation of an inner-sphere complex
between the reducing agent and the oxide at the surface of the oxide is
postulated, but may not always be the case. When an electron is
transferred to a Mn(IV) oxide, a surficial Mn(II) ion locked inside an
oxide lattice is formed. Since Mn(II) oxide is more soluble than Mn(IV)
oxide, this process leads to the rapid Mn(II) depolymerisation and
eventually releases the Mn(II) into the aqueous phase (Stone, 1987;
Martin, 2005).
The mechanisms of reductive dissolution of MnO2 were describe by
three elementary processes viz. (i) surface precursor complex formation
between reductant molecules and oxide surface sites (adsorption of
reductant), (ii) electron transfer within this surface precursor complex
and (iii) breakdown of the successor complex and release of dissolved
metal ions (Stone, 1986; Luther et al., 1998). During the reduction
process, the Mn(IV) center remains incorporated within an oxide sur-
face and the subsequent flux of Mn(IV) from the surface into overlying
solution is negligible, due to the insignificant solubility of MnO2.
Therefore specific interaction between reducing agent and oxide sur-
face site is necessary before electron transfer occur and the ensuing
release of Mn(II) in the solution. A number of elementary reaction steps
were postulated for the reduction which include firstly the formation of
hydrated metal oxide surface sites (> MnIVOH) in solution that un-
dergoes analogous protonation/deprotonation reactions, which subse-
quently creates a distribution of positive, negative, and neutral surface
sites,
> MnIV OH + H+ > MnIV OH2+ (2)
> MnIV OH > MnIV O + H+ (3)
In the next step, the hydrated surface are displaced to allow the
reductant molecules to form complexes with the surface sites i.e. pre-
cursor complex formation (considering inner-sphere mechanism),
> MnIV OH + HA > MnIV A + H2 O (4)
(HA = reducing agent)
Finally electron transfer occur within this surface precursor complex
which releases the reduced Mn(II)
> MnIV A > MnII A (5)
> MnII A MnII (H2 O)62 + + A (6)
2. Reduction leaching of manganese ores by inorganic reductants
2.1. Sulphur dioxide
Despite the deleterious impact on the environment when not han-
dled properly, sulphur dioxide is a useful, effective and relatively in-
expensive reagent for the metallurgical industries (Ferron, 2008).
Owing to fast and selective dissolution kinetics and low temperature
requirement for the leaching process, aqueous SO2 has proven to be an
effective leachant. A bench scale investigation on the extraction of
manganese from low-grade Italian manganese ore (size: 20–60 mm) by
percolation leaching with aqueous solutions of sulphur dioxide has
been reported (Abbruzzese, 1990) in order determine its potential ap-
plicability to heap or in-situ leaching at mine area. A maximum of 98%
manganese was recovered from the ore with particle size in the order of
20 mm after fifteen days using the optimum condition of 6% SO2
(pH = 0.9) at percolation rate of 59.7 L h−1 m−2. However, the
170
Hydrometallurgy 187 (2019) 168–186
recovery was influenced by the change of SO2 concentration, flow rate
and particle size. Similar results were observed with different low-grade
ore fraction of the same region (Abbruzzese et al., 1990). The extraction
of manganese from high-grade Greek ore suggested that double of
stoichiometric amount of aqueous SO2 required for > 90% manganese
recovery at room temperature at a stirring speed of 270 rpm and 50 g/L
pulp density (Grimanelis et al., 1992). The high acidity of the aqueous
SO2 solution was beneficial for manganese recovery while increase in
temperature decreased the manganese recovery. Although the leaching
of MnO2 with SO2 was exothermic in nature, the temperature increase
also facilitated SO2 loss from the solution by volatilisation and conse-
quently decreased the SO2 concentration and solubility. The combina-
tion of a prolonged leaching time, high SO2 concentration and vigorous
stirring also decreased the Fe concentration in the leach solution by
expediting the oxidative hydrolysis of the soluble iron (II) phase. Freitas
et al. (1993) investigated the sulphation of manganese ore in a pyrex
column by using SO2 gas. The results obtained inferred that for a ~91%
sulphation of manganese ore, 20% SO2 had to be bubbled into the
manganese pulp with water (30%) for 6 h. The final pH of the solution
was 1.2. However, similar results were observed with 1 h leaching in a
10 wt% H2SO4 medium. Naik et al. (2000) also reported that the use of
double the stoichiometric SO2 quantity resulted in maximum manga-
nese recovery (95%) from Nishikhal manganese ore (Orissa, India). The
optimum condition for leaching manganese at room temperature was
determined using a factorial experimental procedure by changing SO2
concentrations, pulp densities, sulphuric acid concentrations and
leaching times with a constant ore size (150 μm) and stirring speed
(500 rpm). The stoichiometric amount of SO2 present in the solution
was the controlling factor for manganese recovery rather than initial
SO2 concentration. In another investigation, the same group reported
on the feasibility of manganese leaching at room temperature from low-
grade ore using sulphur dioxide gas as reducing agent (Naik et al.,
2003). The major phases present in the ore was identified as crypto-
melane (KMnO2), pyrolusite (MnO2), hematite (Fe2O3), goethite
(FeOOH), gibbsite (α-Al(OH)3) and illite ((K,H3O)Al2Si3AlO10(OH)2). It
was observed that the reaction temperature increased with an increase
in pulp density. The highest temperature recorded at a 10% pulp den-
sity was 59 °C, whereas the temperature rose to 99 °C at 50% pulp
density, which again confirmed the exothermic nature of Mn leaching
with sulphur dioxide. A maximum of 95.47% manganese was recovered
with a minimum amount of impurities at the optimum condition of 50%
pulp density and 150 min leaching time. Kinetics of the reductive dis-
solution of manganese dioxide in acidic sulphur dioxide media has been
investigated in detail (Miller and Wan, 1983; Petrie, 1995; Senanayake,
2004). In these studies, the leaching of manganese was proposed to be
controlled by different electrochemical reactions, which occurred at the
surface of the ores at particular conditions and followed the mixed
surface reaction kinetic model combined with a shrinking sphere
model. More recently, a lab-scale circulation process of electrolytic
manganese production with low-grade pyrolusite leaching (two-stage
continuous counter-current leaching) by SO2 was discussed in order to
explore the potential of industrial application of this process (Sun et al.,
2013). The circulation process was continually evaluated for 32 days by
the simultaneous monitoring of the SO2 absorption efficiency and the
Mn extraction rate. A maximum of 99.66% SO2 absorption efficiency
and 95.5% Mn extraction rate was obtained at the optimum condition
of 6.62% SO2 and 0.15 M H2SO4 concentration respectively. Industrial
electrolytic grade manganese was synthesized from the leach solution.
A summary of the reported parameters for efficient manganese leaching
from variety of manganese ore using SO2 is shown in Table 2.
2.1.1. Leaching mechanism
In an aqueous system, the SO2 behaves as a weak acid and readily
undergoes protonic dissociation and is considered to exist in the fol-
lowing equilibrium (Nan and Lawson, 1989; Grimanelis et al., 1992;
Petrie, 1995; Senanayake, 2004):
M.K. Sinha and W. Purcell Hydrometallurgy 187 (2019) 168–186

SO2 aq + H2 O = H2 SO3 HSO3 + H+ SO32 + 2H+ (7)

Abbruzzese, 1990, Abbruzzese et al.,

The speciation of the sulphur, which participates in the reductive
dissolution of MnO2 is important since S(IV) has a tendency to exist in
different forms. It has been postulated that SO2 is the predominant

Grimanelis et al., 1992

species at pH < 1.5, HSO3− in between pH 1.5–5.5 while SO32− is the

Freitas et al., 1993

dominant species at pH > 5.5 (Nan and Lawson, 1989; Petrie, 1995).

Naik et al., 2000

Naik et al., 2003

Sun et al., 2013
This is the reason why the proposed reductive dissolution of MnO2 with
SO2 should be carried out in an acidic range. The reductive dissolution
References

of MnO2 with SO2 in an acid medium is presented by following fun-

1990

damental chemical reaction:

2+ 2
MnO2(s) + SO2(aq) Mnaq + SO4( (8)
Mn Recovery (%)

aq)

However, apart from this reaction some intermediate and side re-
actions can also form part of the reduction process, depending upon the
95.97

95.47

pH of the medium (Sun et al., 2013; Senanayake, 2004; Grimanelis

91.4

95.5
98

96

et al., 1992):
SO2: 3.6 wt%, Pulp density: 20%, time 30 min, stirring speed: 490 rpm; temperature:

SO2: 20%, Pulp density: 30%, time: 6 h, Flow rate of SO2: 300 ml/min, temperature:
Percolation leaching: a. 6% SO2 at percolation rate of 59.7 L h-1 m-2, b. 6% SO2 at

MnO2(aq) + SO2(aq) + H2 O MnOOH (s ) + HSO3(aq) (9)

SO2: 3.5 wt%, Pulp Density (S/L): 1:20, time: 15 min; stirring speed: 500 rpm,

MnOOH (s ) + HSO3(aq) MnSO4(aq) + H2 O (10)

MnO2(aq) + 3SO2(aq) + H2 O Mn (SO3 )22 + 2H+ + SO3 (11)

SO2: 1 L/min, Pulp density: 50%, time: 150 min, room temperature,

2+ 2
MnO2(s) + 2SO2(aq) Mnaq + S2 O6(aq) (12)
2+ 2 2
2MnO2(s) + 3SO2(aq) Mnaq + SO4(aq) + S2 O6(aq) (13)
The rate and optimal condition for these reactions and the forma-
tion of specific species in solution has been studied in detail, with re-
SO2: 6.62%, H2SO4: 0.15 M, 400 rpm, 48-55 °C

gard to the thermodynamic parameters and molecule level interpreta-

percolation rate of 82 L h-1 m-2 in 15 days

tion (Petrie, 1995; Senanayake, 2004). It was determined that the

reductive leaching of MnO2 using aqueous SO2 is controlled and limited
by an electrochemical surface reaction, which takes place through the
formation of different intermediates. The formation of dithionate
(S2O62−) occurs due to the partial oxidation of the SO2 during the
Optimum condition(s)

leaching step. The mechanism, however, predicts that small amounts of

temperature: 29 °C

SO2 (3–8%) are likely to be converted into dithionate in acidic condi-

tions and that the newly formed sulphite species are thermo-
dynamically unstable under ambient conditions (Miller and Wan,
1983).
30 °C

45 °C

2.2. Ferrous sulphate, iron powder and other iron salts

b. MnO2: 27.55, Fe2O3: 2.43, Al2O3: 12.20,
a. MnO2: 24.5, Fe2O3: 2.43, Al2O3: 12.20,

MnO2: 79.2, Fe2O3: 4.19, SiO2: 2.01, Al2O3:

In 1947, treatment of manganese ore with acidified ferrous sulphate

MnO2: 51.43, Fe2O3: 23.59, Al2O3: 4.56

or pickling solution generated in the iron and steel industries was re-
MnO2: 40.74, Fe2O3: 0.84, SiO2: 48.70

Mn: 23.5, Si: 19.71, Al: 5.14, Fe: 3.52

ported for the first time and ever since has continuously been explored.
A summary of a few studies is given in Table 3. Das et al. (1982) in-
vestigated ferrous sulphate leaching of low-grade manganese ore. They
observed that > 90% Mn was extracted along with minor amounts of
Mn: 25, Fe: 25·6, Al: 3·3

iron in 1 h using stoichiometric amounts of FeSO4 at 90 °C and 100 g/L

Major element (%)

pulp density. However, in the presence of H2SO4, manganese extraction

SiO2: 33.71
SiO2:33.71

increased from 91% to 96% while iron extraction increased 4-fold.

These results were compared with manganese recovery from untreated
and pre-reduced manganese ore in the presence of only sulphuric acid
Reductive leaching of manganese using SO2.

4.34

or in the presence of pickle liquors. It was found that the addition of

sulphuric acid improved the manganese recovery and filtration process
Commercial pyrolusite, Guangxi, China.
Nishikhal manganese ore, Orissa, India

Rejected manganese ore, Orissa, India

by supressing the formation of gelatinous iron hydroxides. The pickle

Manganese ore, Province of Viterbo,

Manganese ore, Chalkidiki, Greece

liquor completely extracted all the manganese from both the untreated
manganese and reduced ore, but also introduced large amounts of iron
Carajas Manganese ore, Brazil

in the leach solutions. The kinetics of reductive leaching of manganese

ore with dioxide ore by ferrous sulphate in the presence of sulphuric
acid was examined (Zakeri et al., 2007). More than 95% Mn was re-
covered using ore particle sizes of −60 + 100 μm, Fe2+/MnO2 molar
Source of Mn

ratio of 1:3, H2SO4/MnO2 molar ratio of 1:2 and a reaction time of

Italy

20 min at room temperature. Results indicated that the dissolution of

Table 2

manganese from the ore was more strongly affected by the concentra-
tion of ferrous ion than the acidity of the solution. It was therefore

171
M.K. Sinha and W. Purcell Hydrometallurgy 187 (2019) 168–186

suggested that an excess Fe2+/MnO2 ratio be used for manganese dis-

Tekin and Bayramoǧlu, 1993

solution. A decrease in Fe2+ and H+ concentration resulted in an in-

Kholmogorov et al., 2000

crease in Fe3+ and Mn2+ products during the leaching process, which
also resulted in a decrease in mass transfer and consequently a decrease

Bafghi et al., 2008

Zakeri et al., 2007

Addai et al., 2016

Song et al., 2016
in the reaction rate. The kinetic data also concluded that the dissolution
Das et al., 1982

process was fundamentally controlled by the diffusion of Fe+2 and/or

References

Mn+2 through ash layers. The ash layers were supposed to be the in-
soluble minerals surrounding the unreacted core of ore particles. It was
also postulated that a thin film of Mn(II) and/or Fe(III) precipitate was
formed inside the pores of the ash layer before entering the solution as
Mn recovery (%)

Mn2+(aq.) and Fe3+(aq.) ions. A similar phenomenon was reported by

Villinski et al. (2003). The leaching of MnO2 ore with FeSO4 solution
can be expressed by following equation, depending upon the reaction
> 90

> 90
> 90

> 90

medium (Das et al., 1982): with neutral ferrous sulphate solution,

95

98

96

(14)
Metallic-Fe/MnO2 molar ratio: 0.8, Temperature: 20 °C, Particle size (ore/sponge iron): −250 + 150 μm,

Manganese carbonate (which contains FeSO4) to pyrolusite ratio: 5:1, time: 120 min, temperature: 70 °C,

MnO2 + 2FeSO4 + 2H2 O MnSO4 + Fe (OH ) SO4 + Fe (OH )3

H2SO4/MnO2 molar ratio: 2, Fe2+/MnO2 molar ratio: 3, Particle size: −250 + 150 μm, Temperature:

H2SO4: 2 M, Scrap-Fe: 1.5 g/L, Pulp density: 30 g/L, Temperature: 25 °C, time: 90 min, Stirring speed:

with ferrous sulphate solution and small amount of acid,

MnO2 + 2FeSO4 + 2H2 SO4 MnSO4 + Fe (OH ) SO4 (15)

FeSO4: Stoichiometric, H2SO4: 147 g/L, Pulp density: 100 g/L, temperature: 90 °C, time: 1 h

with ferrous sulphate solution and excess acid,

MnO2 + 2FeSO4 + 2H2 SO4 MnSO4 + Fe (SO4 )3 + 2H2 O (16)

FeS2/MnO2: 1, time: 4 h, temperature: 90 °C, Pulp density: 1:10, H2SO4: 1 M

The kinetics of the reductive leaching of MnO2 by FeSO4 in H2SO4

300 r/min, particles size: +150 mesh, Pulp density: 1:14, H2SO4: 200 g/L

solution was also evaluated by different investigators (Majima et al.,

1981; Dundua and Dobrokhotov, 1982; Tekin and Bayramoǧlu, 1993).
Fe : 0.02 M, H2SO4: 0.02 M, 900 rpm, particle size - 53 + 45 μm

In most of the studies, it was concluded that the leaching proceeded on

active sites present on the surface of MnO2 particles and controlled by
Fe 2+ ion diffusion. Tekin and Bayramoǧlu (1993) however, found that
stirring speed had a negligible effect on manganese leaching and the
manganese leaching reaction rate was controlled by a surface reaction
rather than the Fe2+ ion diffusion (through the liquid film around
MnO2 particles). The difference in the control of the leaching process
H2SO4/MnO2 molar ratio 3, time: 10 min

can be attributed to the dissimilarity in chemical composition of ore

and leaching conditions.
The effect of both Fe2+ and Fe3+ ions on the MnO2 leaching rate in
the presence of hydrochloric acid has been studied (Xueyi et al., 2003).
It was observed that an increase in Cl− and Fe2+ ions in the medium,
led to an increase in manganese leaching rates, whereas the increase in
Optimum condition

20 °C, time: 10 min

Fe3+ and Mn2+ content in the solution had an opposite effect on MnO2
dissolution.
The reductive leaching of manganese ore in the presence of dilute
750 rpm

sulphuric acid and powdered sponge Fe metal was investigated by the

2+

same research group (Bafghi et al., 2008). The dissolution efficiency

was studied using various parameters such as molar ratios of sponge
Fe: 8.06, Mn: 48.30, SiO2: 9.00, Al2O3:

Fe: 8.06, Mn: 48.30, SiO2: 9.00, Al2O3:

MnO: 61.38, SiO2: 4.90, Fe2O3: 14.50,

Mn: 41, Fe: 1.9, Al2O3: 13.4, SiO2: 21,

iron and sulphuric acid to manganese dioxide, temperature variation,

Mn: 4.18, Fe: 28.15, SiO2: 25.48,

particle size of sponge iron as well as ore particle size. It was found that
the rate of manganese dioxide dissolution was more sensitive (increase)
Reductive leaching of manganese using iron based reductants.

to the amount of sponge iron compared to sulphuric acid, which alike

A12O3: 5.50, CaO 9.10

with results in an earlier study. Additionally, the use of metallic iron

Major element (%)

Mn: 43.6, Fe: 4.9

was more beneficial than the direct use of ferrous ion. The authors
concluded that the ratio of the activity of ferrous ion to that of ferric ion
Al2O3: 3.35

in solution was relatively high, since metallic iron continuously gen-

CaO: 3.2

erated ferrous ion in the acidic medium. The free energy calculation
2.12

2.12

also supported their finding that reductive leaching of MnO2 with

–

metallic iron was more thermodynamically favourable compared to the

Manganese ore with Australian origin

Manganese ore with Australian origin

ferrous ion. The possible reactions of MnO2 with Fe-metal in the system
Manganese bearing gold-silver ore,

were expressed as:

Manganese concentrate, Russia

Reaction of MnO2 with Fe2+ ion,

Manganese ore, Orissa, India

Manganese Ore, Ghana

MnO2 + 2Fe 2 + + 4H+ Mn2 + + Fe3 + + 2H2 O (17)

ΔGo = −88,600 J/mol.

Reaction of MnO2 with metallic Fe,
Source of Mn

China
β-MnO2

MnO2 + 2Fe(s) + 8H+ Mn2 + + Fe3 + + 2H2 O + 2H2(g ) (18)

Table 3

o
ΔG = −258,000 J/mol

172
M.K. Sinha and W. Purcell Hydrometallurgy 187 (2019) 168–186

MnO2 + 2/3Fe(s) + 4H+ Mn2 + + 2/3Fe3 + + 2H2 O (19)

El Hazek et al., 2006a, 2006b

o
ΔG = −244,000 J/mol.
The dissolutions of MnO2 from manganese bearing gold-silver ore
was investigated in the sulphuric acid medium using scrap iron as re-
Jiang et al., 2003

Jiang et al., 2004

Qian et al., 2017

Nayl et al., 2011

Liu et al., 2013a

ductant (Song et al., 2016). More than 90% Mn was recovered within
90 min at room temperature when leaching was carried out using 2 M
References

H2SO4, 1.5 g/L iron scrap, 30% pulp density and constant agitation rate
of 750 rpm.
The use of pyrite as reducing agent for manganese was first reported
Mn recovery (%)

in 1925 and then re-investigated in the nineties (Clevenger and Caron,

1925; Qin, 1993; Nayak et al., 1995). The use of iron sulphide (pyrite)
for the reductive leaching of manganese from both mechanically and
95.73
> 95

> 97

non-mechanically activated manganese concentrate in sulphuric acid

98

92

90

has also been investigated (Kholmogorov et al., 2000). It was observed

that the leaching of manganese was highly dependent on the initial
H2O2: 0.8 M, H2SO4: 0.9 M, time: 2 h, stirring speed: 950 rpm, pulp density: 4 (w/w), temperature:

H2O2:1.28 M addition after 30 min, H2SO4: 2.16 M, Pulp density: 200 g/L, time: 2 h, stirring speed:
H2O2: 0.6 M, H2SO4: 0.9 M, temperature: 30 °C, stirring speed: 950 rpm, pulp density: 50 g/L, time:

FeS2:MnO2 ratio and acidity of the solution. At a FeS2/MnO2 ratio of 1:1

H2O2: 0.1 mL, H2SO4: 0.7 mL, wt. of ore: 0.4 g, time: 60 min, temperature: 90 °C, particle size:

almost 94%, Mn was recovered from the non-activated manganese

H2O2: 0.8 M, H2SO4: 4.0 M, Pulp density: 200 g/L, stirring speed: 350 rpm time: 90 min,

concentrate with 100 g/L pulp density at 90 °C, whereas a maximum of

98% Mn was recovered from the mechanically activated concentrate
H2O2: 0.4 M, HCl: 2 M, temperature: 60-95 °C, pulp density: ~85 g/L, time: 60 min.

after 2 h in the presence of 0.5 M H2SO4. However, the same percentage

of Mn was recovered from the activated concentrate at 70 °C after 4 h
using similar concentrations of H2SO4 and FeS2/MnO2 ratios. The
higher manganese recovery from the activated concentrate was attrib-
uted to the smaller grain size and possibly the opening of the mineral
grain's surface due to mechanical activation. Since the mechanical ac-
tivation of ores is an intricate and expensive process, the two-stage
leaching process of the non-activated concentrate is preferred and de-
clared as an economical alternative for industrial applications. A first
stage leaching step performed at low acid concentrations (final pH after
leaching 2.5–3.5) is recommended in order to avoid the build-up of
temperature: 40 °C, particle size: 44–37 μm

high iron concentrations in solution. The reductive leaching of MnO2

using FeS2 follows the following reactions:
FeS2 + H2 SO4 FeSO4 + H2 S + S o (20)

MnO2 + 2FeSO4 + 2H2 SO4 MnSO4 + Fe2 (SO4 )3 + 2H2 O (21)

Optimum condition

The generation of elemental sulphur was confirmed with X-ray

diffraction analysis performed on the leach residue after the first stage
of leaching. Thus, the overall reaction can be expressed as:
−74 μm

400 rpm
50 min.

MnO2 + FeS2 + 4H2 SO4 MnSO4 + Fe2 (SO4 )3 + 2S o + 2H2 O + 2H2 S

25 °C

(22)
Recently, a novel process was developed for the reductive leaching
Mn: 27.38, Zn: 11.46, Pb: 4.06, Fe: 4.41,

of high-grade pyrolusite ore in sulphuric acid medium by mixing it with

MnO: 51.32, MgO: 11.77, SiO2: 23.05
MnO: 11, SiO2: 16, Al2O3: 8.8, Fe2O3:

low-grade manganese carbonate ore in the presence of ferrous carbo-

nate, which acted as a precursor for the reductant (Addai et al., 2016).
Mn: 12.2, Fe: 4.74, Al: 3.24

Mn: 12.2, Fe: 4.74, Al: 3.24

During the process, the dissolution of manganese and ferrous carbo-

nates occurs according to the equations:
Reductive leaching of manganese using hydrogen peroxide.
Major element (%)

MnCO3 + H2 SO4 MnSO4 + H2 O + CO2 (23)

Mntot: 10.93

(24)
Al2O3: 2.81

FeCO3 + H2 SO4 FeSO4 + H2 O + CO2

The newly formed FeSO4 acted as reductant in the leaching of MnO2

20.08

present in the high-grade pyrolusite ore, as per Eq. (16). Results in-
dicated that a maximum of 96% Mn was recovered using an ore sample
Low grade Manganese Ore, Sinai, Egypt

Upgraded manganese ore, Cairo, Egypt

with mean particle size of blended ores −150/mesh at a leach tem-

Manganese–silver ore, Guangxi, China

Manganese–silver ore, Guangxi, China

perature 70 °C, pulp density of 1:14 and carbonate ore to pyrolusite

Manganese−Zinc compound ore

ratio of 5:1 in 2 h using 200 g/L sulphuric acid.

Low grade manganese ore

2.3. Hydrogen peroxide

Hydrogen peroxide is generally known as a good oxidizing agent

Source of Mn

with its high redox potential of 1.77 V in acid medium. However, hy-
drogen peroxide can also act as a reducing agent when reacting with
Table 4

very strong oxidizing agents such as manganese oxide. A number of

researchers used H2O2 as reagent in the recovery of manganese from

173
M.K. Sinha and W. Purcell
variety of resources (Table 4). To this effect, a process for recovering
manganese from ore was patented in 1989 using hydrogen peroxide in
acidic medium as a ‘green’ reductant (Allen and Corwin, 1989). The
simultaneous recovery of Mn and Ag from manganese–silver ore at
room temperature in the presence of hydrogen peroxide and sulphuric
acid was investigated (Jiang et al., 2003). Under the optimum leaching
conditions of 0.8 mol/L H2O2, 0.9 mol/L H2SO4, 2 h leaching time, 98%
Mn was recovered from ore with a particle size < 0.074 mm. In another
study, Jiang et al. (2004) found that the leaching of MnO2 from Mn-Ag
ores in sulphuric acid medium in the presence of H2O2 was diffusion
controlled. An insoluble layer composed of the associated minerals viz.
limonite, hematite, and quartz controlled the movement of reagents in
this process, hence the rate of the reaction. The apparent activation
energy value (4.45 ± 0.3 kJ/mol) as well as the effect of stirring speed
on the leaching kinetics confirmed the diffusion controlled hetero-
geneous reaction. The leaching rate increased with H2O2 concentration.
However, at higher concentration ranges the increase was minimal,
possibly due to the decomposition of H2O2. The decomposition of H2O2
takes place in basic media and is catalysed by transition metals and
compounds like MnO2.
Reductive leaching of low-grade manganese ore containing high Si
and Fe was successfully investigated using a hydrochloric acid/ hy-
drogen peroxide combination (El Hazek et al., 2006a, 2006b). Leaching
in the presence of 2 M HCl and 0.4 M H2O2 at 60–95 °C with ~85 g/L
pulp density and reaction time of 1 h, recovered almost 97% Mn with
minimal Fe whereas at ambient temperature, only 84% Mn was re-
covered. Nayl et al. (2011) performed a detailed study on the leaching
kinetics of pyrolusite from an upgraded manganese ore using H2SO4 as
a leachant and H2O2 as a reducing agent. The optimal leaching condi-
tions for maximum Mn recovery (92%) were an ore particle size of
44–37 μm, 4 M H2SO4, 0.8 M H2O2, pulp density of 200 g/L at 40 °C for
90 min. The leaching kinetics of MnO2 was chemically controlled at the
surface in the temperature range of 20–40 °C, while at higher tem-
peratures of 45–70 °C, diffusion controlled kinetic model was more
applicable. The feasible reason for this was the formation of metal
oxides in the matrix. The relatively high activation energy value of
49.5 kJ/mol obtained for the temperature range 20–40 °C and low ac-
tivation energy value of 10.6 kJ/mol obtained for higher temperature
range (45–70 °C) further confirmed the chemically controlled process
was followed by a diffusion controlled mechanism. The reductive acid
leaching of manganese from a manganese-zinc ore using hydrogen
peroxide and sulphuric acid was recently investigated by Qian et al.
(2017). A maximum of 95.73% of Mn and 99.18% of Zn were recovered
at room temperature after 2 h leaching time in the presence of 2.16 M
sulphuric acid and 1.28 M hydrogen peroxide, which was added after
30 min of leaching. A preliminary investigation on the leaching rate of
manganese from low-grade manganese ore using hydrogen peroxide
was also reported (Liu et al., 2013a). Hydrogen peroxide aqueous
chemistry can be summarized by the following reactions (Cotton and
Wilkinson, 1988):
as an oxidizing agent,
H2 O2 + 2H+ + 2e 2H2 O E o = 1.77V (25)
HO2 + H2 O + 2e 3OH E o = 0.87V (26)
HO2ˉ is the hydrolysis product of H2O2
H2 O2 H+ + HO2 (27)
the decomposition of H2O2 in absence of acid can be expressed by
following equation:
2H2 O2 2H2 O + O2 (28)
while in presence of strong oxidizing agent acts as a reducing agent via
following equation:
H2 O2 O2 + 2H+ + 2e E o = 0.68V (29)
174
Hydrometallurgy 187 (2019) 168–186
Thus, reduction of Mn4+ from MnO2 to Mn2+ in presence of H2O2
can be expressed as (Jiang et al., 2004):
MnO2 + H2 O2 + 2H+ Mn2 + + 2H2 O + O2 E o = 0.549V (30)
MnO2 + H2 O2 + H2 SO4 MnSO4 + 2H2 O + O2 (31)
3. Reduction leaching of manganese ores by organic reductants
3.1. Organic acids
Organic acids have emerged as both simple and efficient ‘green’
leachants and reductants for hydrometallurgical manganese beneficia-
tion due to their advantages in terms of less harmful gas emissions
during leaching and ease of leach liquor purification compared to in-
organic reductants. The use of organic acids as leachants as well as
reducing agents in the recovery of manganese along with other metal
ions from ores, batteries and other secondaries have been extensively
exploited (Sobianowska-Turek et al., 2014, 2016; Sayilgan et al., 2010).
Stone and Morgan (1984) investigated the reductive dissolution beha-
viour of manganese(IV) oxide using various organic acids (15 aromatic
and 12 nonaromatic). Oxalic acid for example, which is a relatively
cheap reagent, is a potential reducing agent in manganese recovery.
About 98.4% Mn along with 8.7% Fe was extracted from a low-grade
manganese ore (−150 + 105 μm) with 30.6 g/L oxalic acid, 0.543 M
sulphuric acid and 50 g/L pulp density at 85 °C in 105 min (Sahoo et al.,
2001). The experiment was conducted according a factorial design by
investigating the oxalic acid quantity, sulphuric acid concentration,
temperature and time as variables. It was observed that Mn recovery
was strongly affected by oxalic acid concentration followed by tem-
perature and sulphuric acid concentration. The leaching kinetics of
manganese was investigated in a sulphuric acid medium using po-
tassium oxalate as a reducing agent (Abdallah et al., 2015; Alaoui et al.,
2016). Again, oxalate concentration had a strong effect on Mn extrac-
tion followed by temperature and sulphuric acid concentration. Kinetic
analysis showed that the leaching process was controlled by the che-
mical reaction model and the calculated activation energy of 63.7 kJ/
mol further confirmed that the chemical reaction was the rate-con-
trolling step in this process. Manganese leaching from a gibbsite mi-
neral (particle size < 80–100 mesh) with 0.24 M oxalic acid as re-
ductant, 66 g/L pulp density and 0.5 M sulphuric acid resulted in about
98% Mn recovery in 105 min at 85 °C (El Hazek and Gabr, 2016). The
utilization of low-grade Mn ore for the synthesis of Mn-2-ethyl-hex-
anoate (environmentally safe alkyd paint drier) from a leach liquor
obtained from leaching of ore with sulphuric acid and oxalic acid was
investigated (Shaaban et al., 2017). The lower oxidation-reduction
potential of oxalic acid in standard conditions renders oxalic acid a
good reducing reagent for manganese oxide. Its half reaction can be
expressed as follows:
H2 C2 O4 2CO2 + 2H+ + 2e E o = 0.49V (32)
o
The redox energy potential (pE ) of the oxalic acid is calculated to
be −10.05 at 25 °C and 10.65 at 85 °C (Sobianowska-Turek et al.,
2014), which makes it a worthy reducing agent for Mn(IV). The re-
duction of MnO2 using oxalic acid in acidic medium can be expressed
as:
MnO2 + C2 H2 O4 + 2H+ Mn2 + + 2CO2 + 2H2 O (33)
The proposed dissolution mechanism occurs through the adsorption
of oxalate ion onto the oxide surface layers, followed by the reduction
reaction via electron transfer (Stone and Morgan, 1984; Godunov et al.,
2012a; Artamonova et al., 2013). A similar reaction and mechanism
between manganese(IV) oxide and citric acid was observed in the
presence of sulphuric acid (Godunov et al., 2012b).
Manganese recovered from low-grade pyrolusite was investigated
using formic acid as reductant in a sulphuric acid medium (Lu et al.,
M.K. Sinha and W. Purcell
2015a). Various leaching parameters were evaluated using single-factor
experiments. It was observed that ~90.08% Mn was extracted under
the optimal conditions of 15% H2SO4, 4 ml formic acid, 2 h reaction
time at 90 °C and a ~166 g/L pulp density. According to the surface
reaction mathematical model, the Mn leaching efficiency was affected
by the different parameters in the following order: volume of formic
acid > concentration of sulphuric acid > reaction temperature >
reaction time. The major reactions during this process are expressed as
follows:
HCOOH + MnO2 + H2 SO4 MnSO4 + CO2 + 2H2 O (34)
HCOOH + Fe2 O3 + H2 SO4 2FeSO4 + CO2 + 2H2 O (35)
2FeSO4 + MnO2 + 2H2 SO4 MnSO4 + Fe2 (SO4 )3 + 2H2 O (36)
A similar study used lactic acid as reductant in a sulphuric acid
medium (Ma et al., 2015). Almost 93.99% Mn was recovered after
3.47 h with the optimal experimental conditions of 12% sulphuric acid,
1.24 mL lactic acid, 100 g/L pulp density at 90 °C and 200 rpm stirring
speed. The oxidation product of lactic acid was acrylic acid, formic acid
and acetic acid. The reductive leaching of Mn from a low-grade deposit
was successfully investigated using malonic acid as reductant in the
presence of sulphuric acid (Lasheen et al., 2014). The optimum con-
ditions for ~97% Mn recovery from ore samples with −75 μm grain
size included 1 M H2SO4, 10% malonic acid, 80 °C in 90 min and 100 g/
L pulp density. The kinetics study revealed that the leaching process
was controlled by diffusion through a product layer in the 25–80 °C
temperature range. Citric acid was also used as a reducing agent for the
beneficiation of manganese from MnO2 ores. The optimum parameters
included sulphuric acid solution at a pH 2.3–2.4, 0.8 mol/L citric acid at
80 °C (Godunov et al., 2012b). An attempt was made to recover man-
ganese from low-grade ore using organic acids such as oxalic and citric
acid as both reducing agent and leachant (Das et al., 2012). In this
instance, a maximum of 66% Mn was recovered using 2 M oxalic acid
whereas only 40% Mn was recovered with citric acid after 6 days of
stirring at 150 rpm, room temperature and 20 g/L pulp density. It was
inferred that citric acid only acted as reductant while oxalic acid acted
as both reductant as well as complexing agent for manganese.
3.2. Glucose
Five different manganiferous ores were examined for the selective
extraction of Mn using an excess of glucose (C6H12O6) as reducing agent
in a sulphuric acid medium (Trifoni et al., 2000). More than 99% Mn
was leached from all the ore samples except for ores rich in Al and Fe
where respectively only 63.4% and 79.7% manganese was recovered in
4 h at 70 °C using 100 g/L pulp density, 20 g/L glucose and 3 N sul-
phuric acid. The reaction stoichiometry for MnO2 leaching with glucose
can be expressed as:
C6 H12 O6 + 12MnO2 + 12H2 SO4 12MnSO4 + 6CO2 + 18H2 O (37)
In another study, the same research group reported Mn extraction in
the presence of sulphuric acid, glucose as reducing agent and three
alcohols MeOH, EtOH, and n-BuOH (Trifoni et al., 2001). The re-
searchers proposed two different processes for Mn acid leaching using
glucose in either an alcohol-modified medium or the successive addi-
tion of alcohol to the leach liquor. It was found that alcohol decreased
the calcium concentration in leach liquor by changing the solubility
properties of the dissolved metal ions in solution (solventing out effect).
The effect was more pronounced with methyl alcohol addition after
leaching with glucose. Apart from Eq. (37), other possible chemical
reactions that may occur in the system due to the possible oxidation of
methanol, was expressed as:
3MnO2 + CH3 OH + 6H+ 3Mn2 + + CO2 + 5H2 O (38)
3MnO2 + CH3 OH + 2H+ 3Mn2 + + HCHO + 5H2 O (39)
175
Hydrometallurgy 187 (2019) 168–186
The leaching kinetics of manganese from manganiferous ore in acid
medium using glucose was reported by Veglio et al. (2001a). The re-
search group evaluated a standard mathematical model (shrinking-core
model) to describe the reductive acid leaching of MnO2 by glucose and
verified at low and high pulp density (10 g/L and 200 g/L). The results
obtained with low pulp density were used to refine the model para-
meters by nonlinear regression analysis. The same parameters were
then used at high pulp density in order to simulate the experimental
data. The experimental and calculated results were in good agreement
while analysing scatter diagrams obtained by the “constant activation
energy” model and the “variable activation energy” model.
Pagnanelli et al. (2004a) investigated manganese extraction from
low grade ore by using glucose as a reducing agent in nitric acid
medium. The influence of various leaching parameters was studied
using sequential factorial designs. The optimum leaching conditions
were a stoichiometric amount of nitric acid, −20% below stoichio-
metric amount of glucose, 200 rpm and 100 g/L pulp density at 90 °C
resulted in the complete recovery of manganese in ore particle sizes of
295–417 μm. In another study by Pagnanelli et al. (2004b), the com-
plete leaching of manganese in ore was achieved with MnO2 ore con-
taining 27–38% Mn using the optimized experimental conditions of
30 g ore in 100 mL solution containing a 30% stoichiometric excess of
acid and glucose at 70 °C and 6 h stirring. The purification of the leach
liquor entailed evaporation, precipitation, solvent extraction and ad-
sorption. Not all the processes produced the expected Mn recoveries
therefore hydroalcoholic leaching of ore was proposed at same condi-
tion. The addition of 30% methanol to the sulphuric acid solution was
proposed to supress Ca dissolution. Finally, the leach liquor was pur-
ified by adsorption of the impurities onto activated carbon followed by
evaporation to obtain the Mn concentrate solution.
Furlani et al. (2006) performed reductive leaching of manganese ore
using glucose as reducing agent to identify the oxidation pathway and
product of glucose reaction. Leaching was performed at 90 °C for 6 h
using 50 g/L pulp density, 2% H2SO4 and a stoichiometric amount of
glucose. The HPLC analysis suggested that glucose was oxidized via the
formation of mono-carboxylic poly-hydroxy acids and formic acid.
Formic acid was identified as the major oxidation product.
3.3. Sucrose
The reductive leaching of a terrestrial manganese ore was studied
using sucrose (C12H22O11) as reductive agent in the presence of sul-
phuric acid (Veglio and Toro, 1994a). Factorial experiments were
conducted to analyse the effect and cross-interactions of various para-
meters such as temperature, acid concentration, sucrose concentration
and ore concentration. A maximum of 95% Mn recovery was obtained
from an ore with < 75 μm size fractions at 90 °C using 1 M H2SO4 and
20 g/L of sucrose for 30 min. Acid concentration and temperature were
the main factors, which influenced the leaching process. The relatively
high effect of temperature pointed that the chemical reaction is the
limiting kinetic step. The possible chemical reactions involved in the
leaching process is as follows:
C12 H22 O11 + H+ C6 H12 O6 (Glucose) + C6 H12 O6 (Fructose ) (40)
nMnO2 + C6 H12 O6 + 2nH+ 3Mn2+ + P + H2 O (41)
where P* are the degradation products of glucose, which included
HCOOH and HCHO. The oxidation or degradation of sucrose and its
products (glucose and fructose), could go through various oxidative
levels until CO2 was formed/produced as final product. Sucrose is not
known as a reducing sugar, but can still act as a reducing source due to
the formation of hydrolysed products, such as glucose and fructose in
acid medium, which are themselves reducing sugars. The overall stoi-
chiometric reaction between MnO2 and sucrose in acid medium can be
shown as:
M.K. Sinha and W. Purcell
24MnO2 + C12 H22 O11 + 48H+ 24Mn2 + + 12CO2 + 35H2 O (42)
Fractional factorial experiments were used in by the same authors to
test the effects and interactions amongst the different factors for the
leaching of manganese from ore of two different size fractions (Veglio
and Toro, 1994b). The factors included acid and sucrose concentra-
tions, particle size, mixing conditions and temperature, but instead of
32 experimental runs for all combinations (25 full factorial design), 16
unreplicated tests were made to avoid confusion. The manganese yield
was evaluated for two time intervals after 50 and 150 min. Again,
temperature, sucrose concentration and acid concentration were found
to be the main factors influencing the leaching process. The kinetic rate
of the reaction was not controlled by mass transfer through the
boundary layer due to the insignificant influence of the mixing condi-
tions on Mn recovery.
In order to predict the rate controlling reaction step, a kinetic study
of manganiferous ore leaching in acid media with sucrose as reducing
agent was investigated using the mathematical activation energy model
(Beolchini et al., 2001). The trend of the experimental manganese ex-
traction yields versus leaching time was examined by using both a
“constant activation energy” model and a “variable activation energy”
model. The scatter diagram plot of the experimental manganese ex-
traction yields versus the calculated yields showed a good correlation
for the variable activation energy model.
The reductive leaching of Mn from semi-oxidized manganese ores
containing MnO2 and MnCO3 with sucrose in sulphuric acid medium
was reported by Wang et al. (2017). The readily acid soluble MnCO3
was leached much faster than the MnO2. Under the optimized condi-
tions of 0.035 M sucrose, 5 M sulphuric acid, a 60 min leaching time at
50 °C, 91.8% of Mn was recovered from the semi-oxidized ore. Kinetic
results suggested that the leaching of Mn from the ore followed a
mixed-controlled kinetic model i.e., controlled simultaneously by both
the chemical reaction and by diffusion in the temperature range of
50–90 °C. Sucrose as a reducing agent in sulphuric acid medium has
also been utilized to improve manganese recovery from low-grade
manganese-zinc compound ore (Mn: 27.38%) (Qian et al., 2017). At the
optimum conditions of 0.043 M sucrose, 2.16 M H2SO4, 400 rpm at
80 °C, 98.40% Mn along with 99.67% Zn was recovered after 2 h.
3.4. Lactose
The leaching of manganese from manganiferous ore using whey or
lactose in sulphuric acid solutions at 70 °C was investigated (Veglio
et al., 2000). Two experiments with different pulp densities (10% and
30% w/v) were studied, each including a variation in sulphuric acid and
lactose concentration. The experimental results were fitted to different
empirical models as part of a preliminary analysis, reaction simulation
and experimental procedure optimization. At low pulp density, the Mn
recovery was affected by both the acid and the carbohydrate con-
centration. At the higher ore concentration, the effect of lactose con-
centration was more dominant than that of the acid. The leaching of Ca
and Fe impurities were affected by the sulphuric acid concentration in
both pulp densities. In another study, Veglio et al. (2001b) developed a
kinetic model for Mn leaching from manganiferous ore using results
obtained from a variation in sulphuric acid concentrations and amounts
of lactose as reducing agent The effects of temperature, lactose and
sulphuric acid concentrations on Mn leaching were investigated for
three different ore size fractions. The best fit between the experimental
and theoretical model was obtained when the kinetic model applied
individually for each particle size fraction. The model was unable to
explain completely the effect of particle size on Mn yield. The lack of fit
of all the data was ascribed to MnO2 distribution on the ore. Trans-
formation of the ore particles during the leaching process was analysed
by scanning electron microscopy. After leaching, the ore particle sur-
face showed the presence large pores that were probably occupied by
MnO2, however, no considerable decrease in the surface area was
176
Hydrometallurgy 187 (2019) 168–186
noticed during the leaching process.
Low-grade manganese ore from Egypt was leached directly in sul-
phuric acid using lactose as reducing agent (Ismail et al., 2004). A
maximum of 90.5% manganese was obtained from ore particles with
−100 mesh particle size after 120 min, applying optimum conditions of
20% H2SO4, 90 °C, lactose/Mn ore ratio of 0.75 g/g and acid/MnO2
stoichiometric ratio of 1.8.
Low-grade manganiferous ore was studied for manganese extraction
using lactose as reducing agent and utilization of the solid waste pro-
duced after leaching for other applications (De Michelis et al., 2009a).
The results confirmed that manganese leaching did not significantly
depend on particle size. It was postulated that a stoichiometric excess of
H2SO4 and lactose was necessary to obtain high Mn recoveries, pro-
vided that acid was in lowest excess to prevent the high dissolution of
Fe. Some experiments were conducted using 40 g/L MnSO4 solutions
(mimicking the bleed solution of an electrolytic cell in an electro-
magnetic manganese dioxide production plant), but only 80% Mn was
recovered. In this case, a multistage cross-current leaching process was
proposed in order to reduce the acid consumption. De Michelis et al.
(2009b) investigated the iron removal from leach liquor and proposed a
two-stage leaching process (primary leaching followed by secondary
leaching using leach liquor of primary leaching) in order to increase the
manganese concentration in solution as well as reduction in chemical
consumption. The increase in pH without any loss in Mn recovery was
extremely beneficial in the second leaching step, which reduced the
NaOH consumption in the iron removal step.
The leaching of MnO2 in sulphuric acid medium in the presence of
lactose can be described as i) the hydrolysis of lactose to glucose and
galactose, ii) followed by the reduction of MnO2 as per Eq. (42). The
hydrolysis of lactose can be expressed as (Ismail et al., 2004):
C12 H22 O11 + H2 O
Acid
C6 H12 O6 (Glucose ) + C6 H12 O6 (Galactose ) (43)
A preliminary study the leaching of Mn from a low-grade manga-
nese ore using glucose, cellulose in presence of H2O2 and combination
of glucose and cellulose was reported (Liu et al., 2013b). The experi-
ment was conducted at 90 °C for 60 min using ~1.4 M H2SO4 and
~44 g/L pulp density. A maximum of 97.52% manganese was re-
covered with 0.13 ml H2O2 + 0.03 g glucose, whereas 95.06% Mn was
recovered with 0.10 ml hydrogen peroxide +0.11 g cellulose. When
0.03 g glucose and 0.15 g cellulose was combined, only 86.03% man-
ganese was leached from the ore. A summary of the results from studies
using organic reducing agents is reported in Table 5.
4. Reduction leaching of manganese ores by agricultural or
biomass reductants
Cellulose, hemicellulose and lignin are three major wastes or by-
products produced by the agricultural or biomass industry. Cellulose is
a linear polymer of glucose, which is associated with the polysaccharide
hemicellulose, and can act as a source of carbohydrates, either as a
purified solid product or as a waste (solid/liquid).
The kinetics and reductive leaching of manganese from a low-grade
manganese ore was studied using cellulose as reductant in dilute sul-
phuric acid solutions (Wu et al., 2014). Results indicated that > 90%
Mn was recovered within 150 min from the ore in the presence of
2.674 M H2SO4 and cellulose (30% of input sample weight) at 95 °C
keeping the pulp density of 200 g/L and constant stirring speed of
200 rpm. Kinetic results obtained from this study indicated leaching
was under mixed control (chemical reaction and ash layer diffusion) for
first 60 min, whereas after that the leaching process followed the ash
layer diffusion control mechanism. Leaching of low-grade pyrolusite
with lignin as reductant was successfully investigated (Xiong et al.,
2018). The optimal condition for > 91% Mn leaching efficiency was
identified as 2 M H2SO4, 20% lignin, at 80 °C for 180 min. The hetero-
geneous oxidation-reduction reaction between pyrolusite and organic
 Table 5
Reductive leaching of manganese using some selected organic reductants.
Source of Mn Major element (%) Optimum condition Mn recovery (%) References

Oxalic Acid
M.K. Sinha and W. Purcell

Manganese minerals, Singhbhum–Keonjhar–Bonai belt, Mn: 24.67, Fe: 28.39 H2SO4: 0.543 M, Oxalic acid: 30.6 g/L, Particle size: −150 + 105 μm, Pulp density: 50 g/ 98.4 Sahoo et al., 2001
India L, Temperature: 85 °C, time: 105 min.
Manganese Ore, Morocco MnO2: 56.31, SiO2: 21.16, Al2O3: H2SO4: 0.5 M, K2C2O4: 0.25 M; Particle size: 630 μm, Stirring speed: 750 rpm, 71 Abdallah et al., 2015
7.56, BaO: 3.92 Temperature: 40 °C, Pulp density: 50 g/L, time: 30 min
Gibbsite ore, Abu Zeneima MnO: 8.4, SiO2: 13.5, Al2O3: 27, H2SO4: 0.5 M, Oxalic acid: 0.24 M, time: 105 min, Temperature: 85 °C, pulp density: 98 El Hazek and Gabr,
Fe2O3: 12.3, CaO: 6.53, MgO: 4.66 ~66 g/L, particle size: 80–100 mesh 2016
Manganese ore, Um-Bagma, Egypt MnO2: 62.03, SiO2:5.45, Fe2O3: 15.85 H2SO4: 7%, Oxalic acid: 42.5 g/L, time: 60 min, Temperature: 65 °C, pulp density: 130 g/ 94 Shaaban et al., 2017
L, particle size: −200 + 125 μm

Glucose
Manganiferous ores, Italy and Greece Al rich: Mn: 38.8%, Si: 19.8%, Na: H2SO4: 3 N, Temperature: 70 °C, Glucose 20 g/L, Pulp density: 100 g/L, time: 4 h AI rich: 63.4, Trifoni et al., 2000
15.3, Fe: 1.23 OP 13-1: 94.8,
OP 13-1: Mn: 17.1%, Si: 18.6%, Na: OP 13-3: 99.7 SRD:
10.1, Fe: 0.63 79.7,
OP 13-3: Mn: 23.4%, Si: 17.7%, Na: AL poor: 100.0
11.5%, Fe: 0.64
SRD: Mn: 37%, Si: 16.8%, Na: 9.9%,
Fe: 11.83
Al poor: Mn: 17.1%, Si: 11.9%, Na:
5.4%, Fe: 1.76
Manganiferous ore, Italy Mn: 17.1, Fe: 1.76, Al: 11, Si: 11.9 H2SO4: 1.12 M, Pulp density: 30 g/L, Glucose: 16.74 g/L, MeOH: 15–30%, Temperature: 78 Trifoni et al., 2001
70 °C, time: 6 h
Manganiferous ore, Italy MnO2: 37.90, Fe2O3: 2.43, Al2O3: H2SO4 and Glucose: Stoichiometric amount, Pulp density: 10 g/L and 200 g/L, 85 (for 200 g/L) Veglio et al., 2001a

177
12.2, SiO2: 25.71 Temperature: 50 °C, Stirring speed: 220 rpm 98 (for 10 g/L)
Manganese ore, Italy Mn: 10.3, Si: 18.4, Al: 6.5, Fe: 2.7 HNO3: Stoichiometric, Glucose: −20% below stoichiometric, Pulp density: 100 g/L, 100 Pagnanelli et al.,
Temperature: 90 °C, Stirring speed: 200 rpm 2004a
Manganiferous ore, Italy MnO2: 27–38 H2SO4 and Glucose: 30% of stoichiometric excess, Pulp density: 300 g/L, Temperature: 100 Pagnanelli et al.,
70 °C, time: 6 h 2004b
Low grade Mn Ore Mn: 20 H2SO4: 2%, Glucose: stoichiometric, Pulp density: 50 g/L, Temperature: 90 °C, time: 6 h, 70 Furlani et al., 2006
Stirring speed: 200 rpm

Sucrose
Manganese ore, Viterbo province MnO: 37.9, Fe2O3: 2.43, Al2O3: 12.2, H2SO4: 1 M, Sucrose: 10 g/L, Temperature: 50 °C, time: 150 min, Stirring speed: 200 rpm 94 Veglio and Toro,
SiO2: 25.71, CaO: 2.67 1994a
Manganese ore, Viterbo province MnO2: 62.64, Fe2O3: 1.33, A12O3: H2SO4: 1 M, Sucrose: 20 g/L, Temperature: 90 °C, Pulp density: 100 g/L, Particle size: < 95 Veglio and Toro,
6.14, SiO2: 18.36, CaO: 2.02 75 μm, time: 30 min 1994b
Semi-oxidized manganese ore, China Mn: 25.61, SiO2: 37.70, Fe: 5.46, H2SO4: 5 M, Sucrose: 0.035 M, Temperature: 90 °C, time: 60 min 91.8 Wang et al., 2017
Al2O3: 3.49
manganese−zinc compound ore Mn: 27.38, Zn: 11.46, Pb: 4.06, Fe: H2SO4: 2.16 M, Sucrose: 0.0438 M, Temperature: 80 °C, Pulp density: 200 g/L, Stirring 98.40 Qian et al., 2017
4.41, Al2O3: 2.81 speed: 400 rpm, Particle size: < 0.074 mm

Lactose
Manganese Ore, Viterbo province, Italy Mn: 38.8, Al: 10, Fe: 1.23, Si: 19.8, Ca: H2SO4: 5 M, Lactose: 60 g/L, Pulp density: 300 g/L, Temperature:70 °C, Stirring speed: 90 Veglio et al., 2000
1.8 200 rpm, time: 4 h
Manganiferous Ore, North Latium, Italy MnO2: 37.90, Fe2O3: 2.43, Al2O3: H2SO4: 1 M, Lactose: 20 g/L, Pulp density: 30 g/L, Temp: 83.6 °C, Stirring speed: 200 rpm, 100 Veglio et al., 2001b
12.2, SiO2: 25.71 time: 2 h, Particle size: 210–297 μm
Pyrolusite Ore, Sinai, Egypt MnO2: 25.31, Fe2O3: 52.06, SiO2: H2SO4: 20%, H2SO4/MnO2 stoichiometric ratio: 1.8, Lactose/Mn ore ratio: 0.75 g/g, 90.5 Ismail et al., 2004
4.72, Al2O3: 2.70 Stirring speed: 200 rpm, Temperature: 90 °C, Particle size: −100 mesh, time: 120 min
Manganiferous Ore, Italy Mn: 15.84, Fe: 2.09, Si: 17.13 H2SO4: 0.75 M, Lactose: 5.2 g/L, Pulp density 10%; Temperature: 90 °C, time: 5 h, Stirring 84 De Michelis et al.,
speed: 200 rpm, Particle size: 180 μm 2009a
Manganiferous Ore, Italy Mn: 18.2, Al: 2.5, Fe: 6.3, Si: 19 H2SO4: 100% Stoichiometric excess, Lactose: 10% Stoichiometric excess, Pulp density: 76 De Michelis et al.,
300 g/L, Temperature: 80 °C, Stirring speed: 200 rpm, Particle size: 180 μm 2009b
Hydrometallurgy 187 (2019) 168–186
 Table 6
Reductive leaching of manganese using Agricultural/biomass waste.
M.K. Sinha and W. Purcell

Source of Mn Major element (%) Optimum condition Mn recovery (%) References

Sawdust
Pyrolusite ore, Sinai, Egypt
Manganese ore, Gujrat, India
Pyrolusite ore, Konya, Turkey
Manganese ore, Hunan Province, China
Low-grade manganese ore, Shandong
Province, China
Low-grade manganese ore, Liaoning
Province, China.
Manganese ore, Pakistan
Fe2O3: 52.06, MnO2: 25.31, SiO2: 4.72,
Al2O3: 2.70
Mn: 38.2, Fe: 4.9
MnO2: 57.66, CaO: 10, Fe2O3: 8.04,
SiO2: 7.08
Mn: 20.34, Fe: 10.46, Al: 8.38, SiO2:
37.22
MnO: 27.30, SiO2: 32.96 Fe2O3: 19.09,
CaO: 4.33
Mn: 25, Fe: 12.6, SiO2: 20.1
Mn: 24.05, Ca: 21.15, Si: 15.24, Al:
6.87, Fe: 29.44,
H2SO4: 30%, Temperature: 90 °C, time: 90 min, H2SO4/MnO2 stoichiometric ratio: 1.5, sawdust/ore 92.50 Ismail et al., 2004
weight ratio: 0.5 g/g, Particle size: −100 mesh
H2SO4: 5%, Sawdust: 5%, Pulp density: 100 g/L, Temperature: 90 °C, time: 8 h, Particle size: −100 μm 97.7 Hariprasad et al., 2007
H2SO4: 3 M, Sawdust: 0.25 g, Temperature: 70 °C, time: 120 min, Pulp density: ~3 g/L, Stirring speed: 96.05 Ekmekyapar et al., 2012
300 rpm, Particle size: 160 μm
H2SO4: 1.7 M, Swadust/MnO2 ratio: 4:10, Pulp density:200 g/L, time: 8 h Temperature: 95 °C, Stirring 97.57 Xue et al., 2015
speed: 400 rpm, Particle size: 63 μm
H2SO4: 3 M, Sawdust: 20%, Pulp density: ~166 g/L, Temperature: 90 °C, time: 90 min, Particle size: 98 Feng et al., 2016
−100 mesh
H2SO4: 1 M, Pulp density: 125 g/L, Sawdust to ore: 0.25, Stirring speed: 300 rpm, Temperature: 90 °C, 94.1 Sun et al., 2017
time: 180 min, Particle size: 75 μm
H2SO4: 5%, Pulp density: 100 g/L, Sawdust: 50%, Stirring speed: 300 rpm, Temperature: 120 °C, time: 88.93 Ali et al., 2018
60 min, Particle size: 74 μm

Molasses
Manganese ore, Bayi Manganese Mine, Mn: 22.5, Fe: 12.35, Si: 11.3, Al: 6.01 H2SO4: 1.9 M, Cane molasses: 60 g/L, Pulp density: 200 g/L, time: 120 min, Temperature: 90 °C, 97 Su et al., 2008
Guangxi, China Stirring speed: 200 rpm, particle size: −100 mesh
Manganese ore, Mugui Manganese Mine, Mn: 25.21, Fe: 13.58, Si: 8.47, Al: 5.36 H2SO4: 1.9 M, Molasses alcohol wastewater to pyrolusite ratio: 2 mL/g, Pulp density: 200 g/L, time: 93 Su et al., 2009
Guangxi, China 120 min, Temperature: 90 °C, Stirring speed: 200 rpm, Particle size: −100 mesh

178
Mn Ore of Um-Bogma area, Egypt MnO: 46.11, Fe2O3: 17, SiO2: 9.91, HNO3: 2.7 M, Molasses: 20% of ore weight, pulp density: ~83 g/L, Temperature: 95 °C, time: 2 h, 98 Lasheen et al., 2009a
CaO: 6.50, MgO: 5.01 Particle size: −74 μm
Manganese ore, Mugui Manganese Mine, Mn: 22.25, MnO2: 31.78, Fe: 12.35, H2SO4: 2 M, Temperature: 80 °C, Melanoidins: 30 g/L, Pulp density: 50 g/L, Stirring speed: 600 rpm, 90 Yi-Ju et al., 2011
Guangxi, China SiO2: 24.17, Al2O3: 11.36 Particle size: ~57 μm
Manganese ore, East Nusa Tenggara, Mn: 43.8, SiO2: 14.61, Al2O3: 2.74 H2SO4: 2 M, Molasses: 50%, Pulp density: 100 g/L, Temperature: 90 °C, time: 6 h 97.58 Amalia and Azhari, 2016
Indonesia
Manganese ores, Kupang, Indonesia Mn: 45.44, Fe: 9.21 H2SO4: 6%, Molasses: 100 g/L, Pulp density: 100 g/L, Temperature: 70 °C, Stirring speed: 200 rpm, 95.33 Sumardi et al., 2017
time: 6 h

Corncob
Manganese ore, Hunan, China MnO2: 25.3, SiO2: 31.9, Fe2O3: 3.7, H2SO4: 1.9 M, Corncob: 30%, Pulp density: 100 g/L, Temperature: 85 °C, time: 60 min, Particle size: 92.8 Tian et al., 2010
Al2O3: 8.4 75 μm
Manganese ore, Daweezi, Pakistan 60.7 Mn, 15.8 Ca, and 23.5 Si H2SO4: 1.9 M, Corncob: 40%, Pulp density: 100 g/L, Temperature: 90 °C, time: 60 min, Particle size: 92.48 Ali et al., 2016
75 μm
Low-grade manganese ore, Chaoyang, China Mn: 9.63, Mg: 1.42, Si: 17.03, Fe: Pretreated H2SO4 with cornstalk (2.5 g): 1.2 M, Pulp density: 100 g/L, Temperature: 80 °C, Stirring > 90 Yi et al., 2015
13.07, Al: 5.93, Ca: 5.05 speed: 400 rpm, time: 120 min, Particle size: 74 μm

Wastewaters
Low-grade manganese ore, China
Pyrolusite, Chengdu, China
Manganese Ore, Imini mine area, Morocco
Manganese Ore, Yunnan Province, China
Mn: 20.5% H2SO4: 80 g/L in presence of Xanthan gum waste water, Pulp density: 90 g/L, Stirring speed: 200 rpm, 94.9 Xiong et al., 2014
Temperature: 90 °C, time: 4 h.
Mn: 20.5, Fe: 9.06, Al2O3: 2.23, SiO2: H2SO4: 2 M, Cassava bioethanol wastewater: 30.3 g/L, Temperature: 90 °C, time: 90 min, Pulp density: > 99 Zhou et al., 2016
44.7 200 g/L, Stirring speed: 200 rpm
MnO2: 56.31, SiO2: 21.16, Al2O3: 7.56, H2SO4: 3 M, Olive Mill Wastewater: 23–25 g/L, Pulp density: 90–100 g/L, Stirring speed: 750 rpm, > 49 Alaoui et al., 2015
BaO: 3.92, CaO: 2.80 Temperature: 60 °C, time: 3 h
MnO: 29.41, Fe2O3: 2.83, SiO2: 48.37, H2SO4: 12 mL (conc.), Nitrocellulose wastewater: 100 mL, Pulp density: 100 g/L, Particle size: −200 97.4 Zhang et al., 2018c
Al2O3: 9.80 mesh, Temperature: 90 °C, Stirring speed: 160 rpm, time: 120 min
Hydrometallurgy 187 (2019) 168–186
M.K. Sinha and W. Purcell
reducing substances in wastewater can be expressed as:
(C Hx Oy )m + 2mMnO2 + 2mH2 SO4 2mMnSO4 + mCO2 + zH2 O
(44)
It is well known that acids disrupt the hydrogen bonding within
cellulose or lignin, making it amorphous in nature. De-crystallisation of
these products leads to its gelation with acid, which hydrolyses under
dilution and produces monomer-like glucose, which acts as good re-
ducing agents for MnO2. The following section reports the leaching of
Mn from ores using carbohydrates containing wastes. Table 6 sum-
marizes the results obtained for some of the studies that involved
agricultural or biomass reductants for manganese recovery.
4.1. Sawdust
Sawdust produced as by-products from wood processing is com-
posed of cellulose, hemicellulose and lignin, which can act as reducing
agents in different processes. Ziyadanogullari and Buyuksahin (1995)
reported the reductive leaching of Mn from two different ores, a low-
grade manganese ore (Mn, 36.98%) and manganese-silver ore (Mn,
27.11%) using papolar wood sawdust as a reducing agent. Almost 91%
Mn was recovered with a mixture of 1.8175 g sawdust, 9.1 mL 96%
H2SO4 and 15.7750 g pyrolusite at 200–240 °C and a reaction time of
3 h. On the other hand, 94% Mn was recovered from the manganese-
silver ores with a mixture of 73.8520 g pyrolusite sample, 9.9646 g
sawdust, 98.2 mL 96% H2SO4 and 98.2 mL water at 200–240 °C for
90 min. From the leach liquor, MnSO4 crystallized after Fe was removed
as the hydroxide.
A comparative study was performed on the reductive leaching of
low-grade Mn ore using sawdust and lactose as a reducing agent (Ismail
et al., 2004). Results obtained indicate a maximum of 92.5% Mn was
recovered within 90 min from the ore with a mesh particle size of −100
at 90 °C using 30% H2SO4, 1.5 H2SO4/MnO2 stoichiometric ratio,
sawdust/ore weight ratio of 0.5/1 g/g and at 700 rpm stirring speed.
Similar amounts of Mn were extracted using lactose as a reducing agent.
In another study, sawdust was investigated as reductant in sulphuric
acid leaching matrix for medium-grade high siliceous manganese ore
(Hariprasad et al., 2007). The manganese was successfully extracted
(97.7%) from ore samples with particle size < 100 μm after 8 h at 90 °C
in the presence of 5% H2SO4, 100 g/L pulp density and 5% sawdust.
Other manganese containing materials such as Indian Ocean Mn-nodule
and Mn-nodule leach residue were also evaluated for Mn recovery using
sawdust as reductant. Results indicated that ~98% Mn was dissolved
and recovered within 8 h irrespective of Mn content in the ore/residue.
Ekmekyapar et al. (2012) studied the acid leaching and recovery of Mn
from pyrolusite using sawdust as reducing agent. The effect of various
parameters on the leaching efficiency was investigated to optimize
leaching conditions. Results obtained in this study indicated that the
leaching rate increased with an increase in acid and sawdust con-
centration, temperature, time as well a decrease in pulp density and
particle size. The leaching kinetics indicated that the reaction rate was
controlled by the diffusion of Mn through the product/ash layer in the
40–80 °C temperature range. Bamboo sawdust was also investigated as
possible reductant in the leaching of Mn from low-grade manganese ore
(Ismail et al., 2013). After detailed characterization, it was reported
that bamboo sawdust was composed of cellulose (38.96%), hemi-
cellulose (26.95%) and lignin (25.86%). Celluloses is a linear poly-
saccharide with a β-1,4 linkage, which is easily hydrolysed under acidic
conditions to release soluble sugars such as glucose. The glucose can act
as a source of carbohydrates, which can be used for reductive leaching
applications.
The reductive leaching of MnO2 ore using black locust tree sawdust
as reductant in sulphuric acid solution was investigated (Xue et al.,
2015). The leaching efficiency of the manganese from ore particles with
63 μm particle size was 97.57% after 8 h using a weight ratio of black
locust tree to MnO2 ore of 4:10, 1.7 M H2SO4, 200 g/L pulp density with
179
Hydrometallurgy 187 (2019) 168–186
a stirring rate of 400 rpm at 95 °C. The leaching rate and mechanism
was determined and the results indicated the reaction to be diffusion
controlled through the ash/inert layer of the associated minerals. The
activation energy value of 17.81 kJ/mol further confirmed the same
mechanism. Manganese extraction from low-grade manganese ore
using pre-treated sawdust as a reductant in sulphuric acid was reported
by Feng et al. (2016). The sawdust was pyrolysis pre-treated in a shaft
furnace at 280 °C for 60 min under an N2 atmosphere in order to con-
vert the hemicellulose, cellulose, and lignin into laevoglucose, uronic
acid, acetic acid, wood vinegar and other low molecular weight organic
compounds, which facilitated the reductive leaching of manganese. The
low-grade pyrolusite ore was leached under conditions of 3 M H2SO4,
liquid/solid ratio of 6.0 mL/g with 20 wt% pyrolysis pre-treated saw-
dust at 90 °C for 90 min and 98% Mn was leached into the solution.
Similar experimental conditions were applied to three other low-grade
pyrolusite ores by varying the dosage of pyrolysis pre-treated sawdust
only. The results indicated recovery of 98–99% of Mn by reductive
leaching from low-grade pyrolusite ores using sawdust as reductant. A
recent study report on the kinetics of Mn leaching from low-grade
manganese ore using pre-treated sawdust (Sun et al., 2017). The
leaching efficiency strongly depended on temperature and acid con-
centration. Manganese leaching efficiency of 94.1% was obtained after
180 min under the optimal experimental conditions of 1 M H2SO4, li-
quid/solid ratio of 8:1, mass ratio of sawdust to ore 0.25:1, and a
stirring speed of 300 rpm at 90 °C. In contrast to other reports, the ki-
netic analysis in the temperature range of 60–90 °C indicated that the
reductive leaching of Mn was a chemically controlled reaction.
4.2. Molasses
Molasses is a product obtained from the sugarcane industry (re-
fining) and contains 25–35% cane sugar, 15–25% inverted sugars and
9–11% colloidal materials with extremely high chemical oxygen de-
mand (COD) (80,000–100,000 mg/L) and biochemical oxygen demand
(BOD) (40,000–50,000 mg/L). Manganese leaching from a low-grade
manganese ore using cane molasses as a reducing agent and dilute
sulphuric acid medium was investigated (Su et al., 2008). The optimum
leaching conditions were 1.9 M H2SO4 and 60 g/L cane molasses at
90 °C for 120 min, a pulp density of 200 g/L and 200 rpm stirring speed.
Under these conditions, almost 97% of the Mn in the mineral ore was
leached along with 21.5% Al and 32.4% Fe. In another study, molasses
alcohol wastewater was used with dilute sulphuric acid to extract
manganese from pyrolusite (Su et al., 2009). The molasses alcohol
wastewater was obtained after the fermentation of cane sugar molasses
to produce ethyl alcohol and contained high concentrations of carbo-
hydrates, reducing sugars, dissolved lignin, proteins, alcohols, waxes
and other organic compounds. It was estimated that 12–17 L of was-
tewater was generated per 1 L alcohol produced. Leaching experiments
recovered 93% Mn using a 2.0 mL/g ratio of molasses alcohol waste-
water to pyrolusite at above-mentioned experimental conditions. In
subsequent study by the authors (Su et al., 2010), reductive leaching
kinetics of Mn from low grade pyrolusite ore in dilute sulphuric acid
using molasses alcohol wastewater was investigated. It was suggested
that the reductive leaching of Mn from pyrolusite was controlled by the
diffusion through the ash/inert solid layer with apparently high acti-
vation energy value of 57.5 kJ/mol in the temperature range of 40-
90 °C. Lasheen et al. (2009a and 2009b) studied the leaching of man-
ganese oxide ore with molasses using nitric acid. About 98% Mn was
recovered at the optimized condition of 2.7 M HNO3 in the presence of
20% molasses (per ore weight) using a solid–liquid ratio of 1:12 at 95 °C
for 2 h. It was postulated that the molasses underwent a series of de-
gradation reactions to produce different organic compounds with
functional groups able to form metal ion complexes in solution and
thereby increasing their solubility. The Mn was recovered as Mn2O3
after iron removal at pH 7 using ammonium hydroxide followed by Mn
precipitation at pH 9 using sodium hydroxide. The hydroxide product
M.K. Sinha and W. Purcell
was then ignited 1000 °C for 1 h to obtain Mn2O3 (bixbyite). The ki-
netics study indicated that the leaching was diffusion controlled with an
activation energy of 25.7 kJ/mol in the temperature range of 25–95 °C.
The kinetics of manganese leaching from low-grade pyrolusite using the
“melanoidins” present in molasses alcohol wastewater, as reducing
agent in acidic medium was investigated (Yi-Ju et al., 2011). Mela-
noidins, caramel and phenolics are macromolecules with the molecular
weights between 2000 and 9000 and are considered the main reducing
agents of molasses alcohol wastewater. The results revealed that the
leaching rate increased with the increase of sulphuric acid concentra-
tion, melanoidins concentration and leaching temperature, as well as
with a decrease in pyrolusite particle size. As in previous studies, the
process was diffusion controlled. In another study, an Indonesian
manganese ore was used to investigate the reductive leaching of man-
ganese using molasses and sulphuric acid as reagents (Amalia and
Azhari, 2016). At the optimum condition of 2 M H2SO4 and 50% mo-
lasses concentration, 97.58% manganese was leached at 90 °C in 6 h. In
another study with Indonesian Mn ore, Sumardi et al. (2017) recorded a
maximum 95.33% Mn recovery using 6% sulphuric acid, 100 g/L mo-
lasses at 70 °C in 6 h, keeping 100 g/L pulp density and constant stirring
speed of 200 rpm.
4.3. Corn waste
Corncobs are easily hydrolysed to release glucose in acidic condi-
tions. Tian et al. (2010) developed a new leaching process using corn-
cobs in the presence sulphuric acid to extract manganese from low-
grade manganese dioxide ores. The proximate analysis of corncob in-
dicates that it composed of cellulose (36.5%), hemi-cellulose (18.3%)
and lignin (18.5%). In this study, 92.8% Mn was recovered along with
24.6% iron from ore particle sizes of 75 μm using 1.9 M H2SO4, 3%
corncob, 100 g/L pulp density at 85 °C for 60 min. Ali et al. (2016)
recovered 92.48% Mn from a high-grade manganese ore under similar
conditions by using 4% corncob as reducing agent at 90 °C. Cornstalk
was also used as reducing agent in the extraction of Mn from low-grade
manganese ores (Yi et al., 2015). The lignin present in cornstalk was
difficult to degrade and transform into monosaccharides, but an acid
pre-processing step (optimum, 2.5 g cornstalk +1.2 M H2SO4) con-
verted the lignin into ethanol and sugar reductants. In this study the
solution and residue was individually used to evaluate their ability to
act as reductants for leaching manganese. At the optimum condition of
80 °C, 100 g/L pulp density and a stirring speed of 400 rpm, the man-
ganese dissolved from the processed cornstalk solution (> 90%) was
more than the cornstalk residue solution (85%).
4.4. Wastewater
The disposal of wastewater (hazardous and non-hazardous) accu-
mulated from industrial processes such as the oil industry or any other
manufacturing plant is challenging and sometimes expensive.
Wastewaters with very high chemical oxygen demand and low bio-
chemical oxygen demand are generally treated using advanced oxida-
tion processes or incineration techniques, leading to high disposal costs.
The need for cheap, but effective wastewater treatment methods and
the safe disposal thereof is obvious. High chemical oxygen demand
values are usually characteristic of xanthan gum wastewater along with
appreciable concentrations of carbohydrates and other organic mole-
cules. The removal of the organic compounds from xanthan gum was-
tewater is necessary before disposal. The possible treatment of xanthan
gum wastewater by oxidants like pyrolusite have the potential to solve
the xanthan gum waste water treatment step by oxidative degradation
and simultaneous production of valuable Mn by means of reductive
leaching.
The reductive leaching of manganese from low-grade manganese
ore in dilute sulphuric acid in the presence of xanthan gum wastewater
was investigated by Xiong et al. (2014). Leaching efficiencies of 94.9%
180
Hydrometallurgy 187 (2019) 168–186
Mn was achieved at the optimized condition of 90 g/L pulp density,
80 g/L H2SO4, 200 rpm stirring speed at 90 °C for 4 h. The kinetics of
pyrolusite reductive leaching in this system was also investigated in the
temperature range of 40–90 °C (Zhao et al., 2014). The results showed
that the leaching process was controlled by both a chemical reaction on
the particle surfaces and by diffusion across the product layer. The use
of olive mill wastewater produced during different stages of oil pro-
duction, was also investigated as a possible reductant for pyrolusite
leaching (Alaoui et al., 2015). Olive mill wastewater is a mixture of
water (80–83%), organic compounds (15–18%) and inorganic com-
pounds (2%). The organic content includes polysaccharides, olive
polyphenols, cellulose and organic acids, which could be hydrolysed to
release glucose in the presence of acids, which in turn induce manga-
nese extraction. The study identified the optimal experimental condi-
tions for effective Mn leaching as 90–100 g/L pulp density, 3 M H2SO4,
23–25 g/L olive mill wastewater and 60 °C leaching temperature. After
3 h, 49% of the Mn was extracted from the ore.
The simultaneous treatment of Cassava bioethanol wastewater and
manganese leaching from low-grade pyrolusite as oxidant in sulphuric
acid solution was investigated by Zhou et al. (2016). Under the leaching
conditions of 2.5 M H2SO4, 200 g/L pulp density and 90 °C tempera-
ture, > 90% manganese was recovered in 90 min from 75 μm particle
size ore at a constant stirring speed of 200 rpm. Recently, the reductive
dissolution of low-grade manganese ore using nitrocellulose acidic
wastewater as a reductant was investigated (Zhang et al., 2018c). Ni-
trocellulose acidic wastewater is generated during nitrocellulose pro-
duction, a process usually used for manufacturing of explosives. The
wastewater usually contains sugar as well as high concentration of
mixed sulphuric and nitric acids with high chemical oxygen demand.
Under the optimal conditions of 100 g/L pulp density, 12 mL con-
centrated H2SO4, 100 mL nitrocellulose acidic wastewater, 90 °C reac-
tion temperature, a reductive leaching efficiency of 97.4% Mn was
reached for ore with particle size of −200 mesh keeping a constant
stirring speed of 160 rpm for 120 min.
4.5. Carbohydrate containing reductants
The study of manganiferous ore leaching using whey (waste from
cheese factories) as reducing agent in sulphuric acid solution was in-
vestigated by Veglio et al. (2000). Chemical analysis indicated the
presence of approximately 70% lactose content in the powdered whey.
More than 90% Mn was recovered at a leaching condition of 3 M H2SO4,
60 g/L lactose, 30% pulp density at 70 °C and stirring speed of 200 rpm.
It is well known that plant leaves consist of 15–20% cellulose and
80–85% hemicellulose, which also make it a potential reductant for Mn
leaching. Dried banyan tree leaves were used as a possible reductant for
manganese ore leaching by Hariprasad et al. (2009a). Almost all
manganese was recovered from ore with a particle size of −100 μm
under the following conditions, 5% H2SO4, 50% dried banyan leaves,
100 g/L pulp density at 95 °C for 8 h. The kinetics for the reductive
leaching of manganese from manganese ore in dilute sulphuric acid in
the presence of Phytolacca americana branch powder was investigated in
detail by Xue et al. (2016). The powder analysed for biomass con-
stituents, contained 12.64% cellulose, 14.24% hemicellulose and
30.78% lignin. Under optimum conditions of 1.7 M H2SO4, 40%
powder, 100 g/L pulp density at 90 °C for 8 h and stirring speed of
400 rpm, > 98% Mn was recovered from ore with particle size of
63 μm. The kinetic study in the temperature range of 60–90 °C sug-
gested that the leaching efficiency of manganese was controlled by
diffusion through the ash/inert solid layer. The relationship between
the reaction rate and particle size showed that the leaching kinetics
constant varied with the inverse square of initial particle size, thus af-
firming that the leaching of Mn with Phytolacca americana branch
powder was controlled by the diffusion of reactant through the ash/
inert solid layer.
Shredded newspapers were investigated as possible reagents for the
M.K. Sinha and W. Purcell Hydrometallurgy 187 (2019) 168–186

reductive leaching of Mn from medium-grade siliceous manganese ores

Hariprasad et al., 2009b

Hariprasad et al., 2009a
(Hariprasad et al., 2009b). Newspapers contain on average 37.1% fixed

Zhang et al., 2017b

Veglio et al., 2000 carbon, lingo-cellulose based material, which can be converted to a

Aripin et al., 2017

Tang et al., 2014

Tang et al., 2014

Xue et al., 2016

Sun et al., 2018

Cai et al., 2015
reducing agent. More than 90% Mn was recovered from ore with par-
ticle sizes of −100 μm while employing the following conditions, 5%
References

H2SO4, 50% newspaper, 100 g/L pulp density, at 95 °C for 8 h. The

study also compared reducing properties of processed paper like white
office paper, with that of newspapers. The results showed that only
Mn recovery (%)

82.29% Mn was recovered in 8 h while using white office paper. The

effect of newspaper as reductant was further examined with low-grade
Mn ore (15.83% Mn and 3.52% Fe). Results indicated complete Mn
recovery at the leaching condition of 100 g/L pulp density, 2.5% acid
98.57

91.32
> 90

> 95
99.9

99.8

92.8
100

100
90

and newspaper concentration at 90 °C after 8 h. Finally, the leach so-

lution was purified and evaporated and pure manganese sulphate was
H2SO4:1.7 M, Phytolacca Americana powder: 40%, Temperature: 90 °C, Stirring speed: 400 rpm,

H2SO4: 1.7 M, Banana peel: 40%, Pulp density: 100 g/L, Temperature: 80 °C, time: 6 h, Stirring

H2SO4: 25%, Biogas residual: 19% of pyrolusite mass, H2SO4 to pyrolusite ratio: 8:1, time: 2.5 h

H2SO4: 40 mL, Hull: 30 g/L, Pulp density: 200 g/L, Temperature: 90 °C, time: 5 h, Stirring speed:
H2SO4: 5%, Newspaper: 50%, Pulp density: 100 g/L, Temperature 95 °C, time: 8 h, Particle size:

H2SO4: 2.5 M, waste tea: 40% of ore mass, liquid-to-solid ratio: 7.5:1, Temperature: 95 °C, time:

H2SO4: 1.7 M, waste tea: 10% of ore mass, liquid-to-solid ratio: 7.5:1, Temperature: 95 °C, time:

H2SO4: 9%, Straw/ore: 0.3, liquid-to-solid ratio: 7.5:1, Temperature: 85 °C, time: 3 h, Stirring
H2SO4: 3 M, Whey: 60 g/L, Pulp density: 30 g/L, Temperature 70 °C, Stirring speed: 200 rpm

isolated. A similar study also reported good Mn recovery from different

H2SO4: 5%, Dried banyan leaves: 50%, Pulp density: 100 g/L, Temperature 95 °C, time: 8 h,

high-grade pyrolusite ore using newspaper as reducing agent (Su and

Naing, 2016).
The effect of shaddock peel as possible reductant for manganese
leaching in sulphuric acid was investigated from low-grade pyrolusite
(Qiong, 2013). Shaddock peel is rich in fibre and consists mainly of 72%
carbohydrates and 21% cellulose (Zain et al., 2014). Almost 92%
manganese was leached from pyrolusite with particle size range of
57–150 μm using shaddock peel (40 g/L) in 12% H2SO4, 100 g/L pulp
density for 90 min at 70 °C and stirring speed of 200 rpm. A preliminary
study on the use of banana peel as reductant for Mn leaching from
medium-grade manganese ore was reported by Aripin et al. (2017).
Banana peel contains around 25.52% hemicellulose. The leach residues
obtained while using different amounts of banana peel were examined
using X-ray diffraction and Fourier-transform infrared spectroscopy. X-
speed: 300 rpm, Particle size: 45–75 μm

ray diffraction suggested only SiO2 remained in the residue after

leaching whereas the Fourier-transform infrared spectroscopy of ba-
nana peels showed the disappearance of carbonyl stretching frequency
time: 8 h, Particle size: 63 μm

(of hemicellulose), which indicated that hemicellulose hydrolysed in

Particle size: < 100 μm

the acidic condition.

Optimum condition

The reductive leaching of manganese from low-grade pyrolusite ore

speed: 200 rpm

using biogas residues as reductant was investigated (Cai et al., 2015).

Biogas residues are the waste products isolated after anaerobic diges-
< 100 μm

200 rpm

tion of woody fibre biomass, such as straw. Biogas residues contains

about 55.12% fibres. The optimum condition for quantitative Mn re-
8h

8h

covery was determined as 25% H2SO4, 19% (of ore wt.) biogas residues
Reductive leaching of manganese using other carbohydrate containing reducing agents.

with volume-to-mass ratio of sulphuric acid to pyrolusite of 8:1 and

Mn: 21.43, SiO2: 36.36, Fe2O3: 8.11,

Mn: 23.4, Fe: 13.5, Ca: 4.5, SiO2: 23

MnO2: 41.11, CaO: 7.9, SiO2: 4.85,
Mn: 38.8, Al: 10, Fe: 1.23, Si: 19.8

Mn: 20.34, Fe: 10.46, SiO2: 37.22,

Mn: 20.34, Fe: 10.46, SiO2: 37.22,

reaction time of 2.5 h. The optimized condition was also applied for
Mn: 45.62, Fe: 2.75, SiO2: 10.78,

three other low-grade pyrolusites and similar results were observed.

Mn: 38.22, Fe: 4.9, Ni: 0.02

Mn: 38.22, Fe: 4.9, Ni: 0.02

The hydrolysis of fibre in acidic conditions and leaching of MnO2 was

expressed as:
Major element (%)

Mn: 48.5, Fe: 2.8

n (C6 H10 O5) + nH2 SO4 n (C6 H11 O5 ) HSO4 (45)

Al2O3: 8.38

Al2O3: 1.34

Al2O3: 7.79

Al2O3: 9.65

Al2O3: 8.38

n (C6 H11 O5 ) HSO4 + nH2 O n (C6 H12 O6 ) + nH2 SO4 (46)

MnO2 + n (C6 H12 O6 ) + nH2 SO4 MnSO4 + nCO2 + nH2 O (47)

The reductive leaching of manganese from two different ores,

Low-grade manganese ore, Liaoning Province, China

Gabonese and Xiangxi, using waste tea, was investigated (Tang et al.,
Manganese ore, western Hunan province, China

Ore from Guiyang Import Australia Manganese

2014). The tea contained 4.0% polyphenols, 7.9% polysaccharide,

Medium grade manganese ore, Gujrat, India

17.2% cellulose, 6.3% hemicellulose and 19.8% lignin. The optimum

Manganese ore, Viterbo province,Italy

conditions for quantitative recovery of Mn was determined as 2.5 M

Low-grade pyrolusite, Yunnan, China

H2SO4, 40% (of ore wt.) waste tea for Gabonese ore and 1.7 M H2SO4,
Medium grade ore, Gujrat, India

Gabonese manganese oxide ore

10% (of ore wt.) waste tea for Xiangxi ore, keeping the constant liquid-
Medium grade ore, Iindonesia

Chinese ores sample, Xiangxi

to-solid ratio of 7.5:1, 95 °C leaching temperature for 8 h for both the

ores. Leaching kinetics studies for both the ores indicated that the
processes were diffusion controlled. Characterization of the leached
residue by X-ray diffraction and scanning electron microscopy validated
Company
Source of Mn

the diffusion controlled kinetic model.

A process for the reduction leaching of pyrolusite using hull as a
Table 7

reducing agent was investigated (Zhang et al., 2017b). The fibre con-
tent in the hull was determined to be 35–40%. The optimum leaching

181
M.K. Sinha and W. Purcell Hydrometallurgy 187 (2019) 168–186

conditions for > 95% Mn recovery was reported as 40 mL H2SO4, 30%

Hariprasad et al., 2013

Hariprasad et al., 2014

Momade and Momade,

hull, 200 g/L pulp density at 90 °C for 5 h. In another study, the ex-

Jianhua et al., 2007

Zhang et al., 2018b

traction of manganese in dilute sulphuric acid medium from low-grade

Alaoui et al., 2013

Ding et al., 2016

Tian et al., 2012

Yaozhong, 2004
pyrolusite ore was investigated using oat straw as a reducing agent
(Man et al., 2014). Almost 96.1% Mn along with 46.8% Fe was re-

References
covered under the optimized experimental conditions, which included

1999a
150 g/L H2SO4, liquid-to-solid ratio of 9 mL/g, and mass ratio of oat
straw to pyrolusite ore of 0.3 at 90 °C for 60 min. Kinetic studies in-
dicated that the leaching process followed a chemically controlled

(1) 92.88; (2): 95.2;

model in the temperature range of 60–90 °C and the calculated acti-
vation energy value of 69.4 kJ/mol confirmed the mechanism.

Mn recovery
A combination of corn stalk and rice straw was used for the re-

(3) 98.9
ductive leaching of manganese from low-grade pyrolusite ore (Ding and

> 95

> 90

> 98

> 95
96.6
99

98

98
Luo, 2015). Excellent manganese recoveries were reported (97%) using
pyrolusite with particle size 109 μm, 3 M H2SO4, 1∶1.5 mass ratio of

Hydrazine Sulphate: 35%, Time: 30 min, Temp: 35 °C (3) H2SO4: 1%, Hydrazine Sulphate:
Mn-ore/Bi-ore ratio: 1.4/1, HCl: 4 M, Pulp density: 200 g/L, Temperature: 70 °C, time: 2 h,
H2SO4: 1.5 M, Na2SO3: 1 M, Pulp density: 75 g/L, Temperature: 40 °C, time: 10 min, Stirring
corn stalk to rice straw, 3∶10 mass ratio of reductant corn stalk and rice

H2SO4: 6.5–7.5%, NH3OHCl:15-16 g, Pulp density: 25–35%, Temperature: RT, time: 10-
(1) H2SO4: 3%, Hydrazine Sulphate: 55%, Time: 30 min, Temp: 35 °C (2) H2SO4: 2.5%,
Conc. H2SO4: 89% of ore, Na2SO3/ore ratio: 0.92, Pulp density: 200 g/L, Temperature:

H2SO4: 1–1.05× of stoichiometry, Sphalerite: 1–1.1× of stoichiometry, Pulp density:

EDTA: 0.37 M or EDTA-2Na: 0.52 M, Pulp density: 100 g/L, Temperature: 75 °C time:
straw to pyrolusite, and 100 g/L pulp density at 90 °C for 80 min. Re-

H2SO4: 0.3 M, Methanol: 40%, Pulp density: 20 g/L, Temperature: 160 °C, time: 2 h,
cently, pre-treated straw was investigated as a reductant for manganese

(NH4)2SO4: 3 M, Na2SO3: 1–1.05× of stoichiometry, Pulp density: 200–250 g/L,

in sulphuric acid medium (Sun et al., 2018). Straw mainly consists of
cellulose (37.6%), hemicellulose (21.3) and lignin (22.9). In the pre-
treatment process, concentrated sulphuric acid was used to hydrolyse
the straw into reducing sugars. A leaching efficiency of 92.8% was
achieved from the ore with a particle size of 45–75 μm under the fol-
lowing optimized conditions, sulphuric acid concentration of 9% (v/v),
reductant/ore mass ratio of 0.3, at 85 °C for 180 min keeping a constant
stirring speed of 300 rpm. A summary of investigations involving these
carbohydrate containing reductants is given in Table 7.

5. Miscellaneous reductants
30 °C, time: 2 h, Stirring speed: 500 rpm

200 g/L, Temperature: 95 °C, time: 4 h

Temperature: 100 °C, time: 45 min
The successful reductive leaching of Mn from manganese-silver ore

20%, Time: 30 min, Temp: 35 °C

60 min, Stirring speed: 400 rpm

in dilute sulphuric acid with sodium sulphite (Na2SO3) as reductant was
demonstrated by Tian et al. (2012). A maximum of 99% Mn was lea-

Stirring speed: 500 rpm

ched at 30 °C in 15 min when the experiment was carried out with
Optimum condition

sulphuric acid addition at 89% (weight ratio of 98% H2SO4 to ore),

speed: 500 rpm

Na2SO3/ore ratio of 1:0.92 and pulp density of 200 g/L. Since, Na2SO3
exists in solution mainly as SO32−, HSO3− and H2SO3 (i.e. SO2), the
sodium sulphite acts as SO2 donor for MnO2 reduction. The main re-

30 min
actions between MnO2 and SO32− is described by following equations:

SO32 + 2H+ SO2 + H2 O (48)

MnO2: 56.31, SiO2: 21.16, Al2O3: 7.56,

MnO2: 18.73, SiO2: 59.29, Al2O3: 6.51,

(1) Mn: 38.22, Fe: 4.9; (2): Mn:29.5, Fe:

MnO2: 38.92, SiO2: 28.20, Al2O3: 9.27
Mn: 31.3, Fe: 13.1, SiO2: 27.0, Al2O3:

Mn: 26.99, Fe: 10.43, Al: 5.08, SiO2:

Mn: 22.46, Fe: 7.46, Al: 3.5, SiO2:

MnO2 + SO2 MnSO4 (49)

3.37; (3): Mn: 15.38, Fe: 3.52

Mn: 39.5, Fe: 6.25, Zn: 0.02

The mechanism for the dissolution of low-grade manganese ore in

H2SO4/Na2SO3 solutions were evaluated and optimized using the ‘re-
sponse surface’ methodology and Box-Behnken designs (Alaoui et al.,
Major element (%)
Reductive leaching of manganese using miscellaneous reductants.

Mn: 27.6, Fe: 8.6

2013). Employing leaching condition of 1.5 M H2SO4, 1 M Na2SO3, and

75 g/L pulp density at 40 °C, recovered 95% Mn within 10 min. The
Fe2O3: 6.59
BaO: 3.92

kinetic study indicated that the dissolution rate of pyrolusite was dif-
fusion controlled and a semi-empirical mathematical model was pro-
19.41

14.89
7.1

posed. Leaching studies of low-grade pyrolusite with high silica content

using Na2SO3 and ammonium sulphate was reported (Jianhua et al.,
Medium and low grade Mn ores, Gujarat, and low
low-grade manganese ore, Hunan Province, China

2007). A reaction temperature of 100 °C, 3 M (NH4)2SO4, Na2SO3 in 1:-

Manganese–silver ore, Guangxi province, China

1.05 times of stoichiometric amounts, liquid-to-solid ratio of 4–5:1 and

a leaching time of 45 min was determined as the optimum leaching
Manganese ore, Hebei province, China

condition for > 90% Mn recovery from ore in neutral conditions. The
Low grade manganese ores, Ghana

chemical reaction takes place is as follows:

Low grade manganese ore, China

Medium grade ore, Gujrat, India

grade Mn ore Orissa, India

MnO2 + 4NH4+ + 2e Mn2+ + 2H2 O + 4NH3 (50)

Manganese Ore, Morocco

Das et al. (1998) investigated the reduction of MnO2 with ammo-

nium sulphite ((NH4)2SO3) in ammoniacal medium to determine the
nature of reduced species and the reduction kinetics. From the kinetics
Manganese ore
Source of Mn

study, they suggested that the (NH4)2SO3 was oxidized by MnO2 fol-
lowed a chemically controlled kinetic model. The ammonia and am-
Table 8

monium sulphate had no effect on the kinetics while the results also
indicated a mixture of reduced product, namely Mn2+, Mn3+ and

182
M.K. Sinha and W. Purcell
Mn4+.
The reduction leaching of silver-bearing low-grade manganese ore
by sphalerite concentrate was studied (Yaozhong, 2004). The probable
reaction was expressed as:
MnO2 + ZnS + 2H2 SO4 MnSO4 + ZnSO4 + 2H2 O + S 0 (51)
The optimum parameters for 98% Mn leaching from silver-bearing
low-grade manganese ore were determined as H2SO4 in 1–1.05 times of
stoichiometric amount, reducing agent in 1–1.1 times of stoichiometric
amount, and 200 g/L pulp density at 95 °C for 4 h. Similarly, manganese
reduction leaching from low-grade ores were investigated in hydro-
chloric acid medium using bismuthinite ore (Ding et al., 2016). The
most appropriate experimental conditions were determined as Mn-ore/
Bi-ore ratio of 1.4/1, 4 M HCl, 200 g/L pulp density, at 70 °C for 2 h and
stirring speed of 500 rpm. The maximum recovery of bismuth and
manganese was reported as 96.6% and 97.1%, respectively. The pos-
sible reaction for these reactions are as follows:
3MnO2 + Bi2 S3 + 12H+ 3Mn2 + + 2Bi3 + + 3S + 6H2 (52)
12MnO2 + Bi2 S3 + 27H+ 12Mn2 + + 2Bi3 + + 3HSO4 + 12H2 O (53)
Hydrazine sulphate (NH3NH2HSO4) was investigated for the re-
ductive leaching of different low- and medium-grade manganese ores
(Mn 15–39%) in acidic media (Hariprasad et al., 2013). Experimental
conditions applied in this study include 100 g/L pulp density, 3%
H2SO4 and 55% hydrazine sulphate. More than 90% Mn was recovered
from the medium-grade Mn ore at 35 °C in 30 min. On the other hand,
around 95% Mn was recovered from the low-grade Mn ore with 100 g/L
pulp density, 2.5% H2SO4 and 35% hydrazine sulphate at 35 °C for
20 min. With other low-grade ore, almost 98% Mn was recovered using
100 g/L pulp density, 1% H2SO4 and 20% hydrazine sulphate at 35 °C
for 20 min. Iron extraction varied between 18.76 and 50.25% for the
different ores. The reaction between hydrazine sulphate and MnO2 is as
follows:
MnO2 + NH3 NH2 HSO4 + H2 SO4 2MnSO4 + N2 + 2H2 O (54)
In another study, the dissolution of manganese from medium-grade
manganese ore using hydroxylamine hydrochloride (NH3OHCl) was
investigated (Hariprasad et al., 2014). A ‘Response surface’ metho-
dology was adopted while applying a central composite design for 24
factorial set of experiments and a statistical analysis was done to
evaluate interactive effects. The optimum conditions established for
maximum recovery of manganese (> 97%) were 200 g/L pulp density,
3% H2SO4, and 110 g NH3OHCl for 20 min. According to Response
surface methodology, the maximum condition for Mn extraction was
estimated as pulp density 25–35%, H2SO4 concentration (6.5–7.5% v/
v), NH3OHCl (15–16 g) and time (10–30 min). The reduction of MnO2
with hydroxyl ammonium chloride is described by the following
equations:
2MnO2 + 2NH3 OHCl + H2 SO4 MnSO4 + MnCl2 + N2 + 6H2 O (55)
2MnO2 + 3NH3 OHCl + H2 SO4 MnSO4 + MnCl2 + NH4 ClO4 + 2
NH4 OH + 1 2 O2 (56)
The use of aqueous methanol in sulphuric acid was investigated for
the reductive leaching of manganese oxide ore (Momade and Momade,
1999a). Experiments were performed at low (30–70 °C) and high
(120–170 °C) temperatures using varying concentrations of H2SO4 and
methanol. A maximum of 98% Mn was recovered at 160 °C in 2 h with a
methanol dosage of 40% and 0.3 M sulphuric acid. However, at 70 °C,
only 34% Mn was leached in 1 h with 50% methanol and 0.16 M sul-
phuric acid. Interestingly, negligible iron dissolution was observed
while leaching at high temperatures. The oxidation of methanol and
reduction of MnO2 is described as follows:
CH3 OH HCHO + 2H+ + 2e E o = 0.232V (57)
183
Hydrometallurgy 187 (2019) 168–186
CH3 OH + H+ CH3 OH2+ (58)
MnO2 + CH3 OH + H+ Mn2 + + HCHO + 2H2 O (59)
The same authors investigated the kinetics of manganese leaching in
an aqueous methanol–sulphuric acid mixture as well as the influence of
methanol, acid concentrations, temperature and particle size (Momade
and Momade, 1999b). They concluded that the rate of manganese ex-
traction during the first 30 min was controlled by protonated methanol
adsorption at the interface and after 30 min, the leaching reaction fol-
lowed the ash/product layer diffusion-controlled kinetic model.
Low grade pyrolusite leaching was studied in sulphuric acid using
methyl aldehyde as reductant (Lu et al., 2015b). Under the optimized
conditions of 2.75 M H2SO4, 2.4 mL methyl aldehyde solution, 125 g/L
pulp density at 86 °C for 2.22 h and constant stirring speed of 200 rpm,
94% Mn was recovered along with 77.78% iron. Reductive leaching of
manganese oxide ores by ethylenediaminetetraacetic acid (EDTA) or its
disodium salt (EDTA-2Na) in an aqueous medium was investigated
(Zhang et al., 2018b). More than 95% manganese was recovered using
0.37 M EDTA or 0.52 M EDTA-2Na, 100 g/L pulp density at 75 °C and
constant stirring speed of 400 rpm. Since, the leaching process did not
follow shrinking core kinetic models the ‘Avrami model’ was used to
explain successfully the kinetic data, which suggested that the initial
leaching rate was infinite, but continuously decreased with the time. A
summary of Mn recovery using miscellaneous reducing agents is given
in Table 8.
6. Discussion and conclusion
The hydrometallurgical reductive leaching of Mn from manganese
ore is a promising concept for technology development. It not only
overcomes the traditional process of high temperature reduction fol-
lowed by acid leaching into one single step, but also provides a process
for the clean production of manganese products and meets the low-
carbon (less pollution) economy requirements. A large number of re-
ducing agents which are efficient in acidic environment of the leaching
solution, have been explored and used for the effective recovery of
manganese from variety of ores. In this review the use, working me-
chanism and optimum parameters of various reducing agents for sus-
tainable recovery of Mn was discussed. The effectiveness of the dif-
ferent reductants is largely determined by their oxidation-reduction
potential, but kinetic parameters and reaction mechanism are equally
important. Inorganic reductants such as FeSO4, pyrite, and H2O2 were
beneficial for high Mn recoveries, but their relatively high prices as
reagents limited their commercial use. The problem associated with Fe
based reductants was the additional dissolution and hence contamina-
tion of iron in the leach liquor, which complicated the purification of
the leaching solution. The similar situation is valid when sphalerite and
bismuthinite concentrates are utilized for the reduction purpose. Some
inorganic reductants, such as SO2, may even be harmful due to their
toxicity and be difficult to maintain the required acidity and con-
centration levels due to their volatile nature. However, the relatively
cheap price and fast reduction kinetics even at lower temperature fa-
vour its commercial use. Hydrogen peroxide is another most common
and efficient reducing agent used in lab scale for the reductive leaching
of manganese, however it is worthy to mention that at higher hydrogen
peroxide concentration it may act as an oxidizing agent rather than a
reducing agent (Golmohammadzadeh et al., 2017). Carbohydrate based
organic reductants such as glucose, sucrose and lactose are considered
effective and environmentally friendly reagents. However, these re-
ductants are yet to find their commercial application due to the high
consumption rate in the process and again the expense of the reductant.
Cost-effectiveness of the process can be improved by using carbohy-
drate containing industrial wastes and agricultural or biomass wastes as
reductants like sawdust, molasses and crop wastes. Some biomass
wastes consist of complicated components that are difficult to convert
M.K. Sinha and W. Purcell
into monosaccharides and may require high acidity, temperature or
time for effective leaching (Sun et al., 2018). However, there is also a
concern over the limited annual output of renewable carbohydrates,
such as sawdust, corncob etc. which would make it difficult to meet the
mass production of manganese required by the global economy. Some
cane molasses contained high chloride ion concentrations, which may
cause serious corrosion to electrolytic anode plates or equipment (Xiong
et al., 2018). Based on significantly lower oxidation-reduction potential
in standard conditions (e.g. oxalic acid) and high Mn recovery, organic
acids have emerged as both simple and efficient green reductants. Apart
from choosing the best and cost-effective reductant for leaching, the
other crucial issue is the purification of leach liquors to obtain highly
concentrated and pure Mn products. The recovery of iron and other
metallic or non-metallic impurities (that may introduce in the system
when industrial wastes/agricultural/biomass wastes and waste waters
used as reductant) should be minimised during the leaching operations
to decrease the overall process expenditure. In future investigations,
pilot-scale reductive leaching tests and techno-economic aspects should
be addressed in order to determine the conditions that allow higher
manganese extraction with lower operating cost.
Acknowledgements
Authors thank University of the Free State, South Africa for funding
the Postdoctoral fellowship for Manish Kumar Sinha.
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