Minerals Engineering 163 (2021) 106748

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Minerals Engineering
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Leaching manganese nodules with iron-reducing agents – A critical review

Norman Toro a, b, *, Freddy Rodríguez b, Anyelo Rojas b, Pedro Robles c, Yousef Ghorbani d
a
Faculty of Engineering and Architecture, Universidad Arturo Prat, Almirante Juan José Latorre 2901, Antofagasta 1244260, Chile
b
Departamento de Ingeniería Metalúrgica y Minas, Universidad Católica del Norte, Av. Angamos 0610, Antofagasta 1270709, Chile
c
Escuela De Ingeniería Química, Pontificia Universidad Católica De Valparaíso, 2340000 Valparaíso, Chile
d
MiMeR—Minerals and Metallurgical Engineering, Luleå University of Technology, SE-971 87 Luleå, Sweden

A R T I C L E I N F O A B S T R A C T

Keywords: The accelerated growth in global demand for Manganese coincides with the continuing depletion of high-grade
Marine nodules ores on the earth’s surface. This element is essential for diverse markets such as steel production, dietary ad­
MnO2 dissolution ditives, fertilizers, cells, fine chemicals, and some chemical reagents. Interestingly, there are large mineral re­
Iron reducer
serves in the ocean’s depths, where marine nodules are an attractive option due to their high manganese content
Submarine resources
(between 16 and 24%). The dissolution of MnO2 from manganese nodules needs a reducing agent. Iron is a
feasible alternative with a low cost and can even be recycled from scrap or industrial waste like smelting slag,
tailings, or scrap steel. This paper provides a comprehensive review of Manganese acid-reducing processes from
marine nodules using different iron-reducing agents that include FeS2, Fe2+, Fe0, Fe2O3, and Fe3O4. Fe0 has
displayed the best performance in terms of dissolution kinetics and Mn extraction. This review further confers the
chemistry and reactions involved in the reductive leaching and stresses the critical parameters that could be
considered for optimization. In this sense, the concentration of reducing agent and temperature are highlighted
as the most influential, making other parameters (e.g., particle size, stirring speed, acid concentration, and
leaching time) almost irrelevant. Finally, it is concluded that the best way to extract Mn from marine nodules is
to reuse steel scraps, working with high Fe0/MnO2 ratios (2/1), low concentrations of sulfuric acid (0.1 mol/L),
and short times (5 min), achieving extractions of 90%.

1. Introduction Xie et al., 2013; Corathers, 2019; Haghshenas et al., 2007).

Significant efforts have been made to extract Manganese from low-
Nowadays, there is a constant depletion of available mineral deposits grade pyrolusite minerals1; however, this is insufficient to meet the
on the earth’s crust (Biswas et al., 2009; Sen, 2010). Manganese (Mn) is required production levels (Su et al., 2010). It is estimated that the
one of the twelve most abundant elements (it comprises approximately largest reserves of cobalt, nickel, and Manganese are located in the
0.1% of the earth’s crust (Baba et al., 2014)), and can be associated in seabed (COCHILCO, 2016; Toro et al., 2020a). Three mineral-rich re­
different ways, finding oxides, sulfides, carbonates, and silicates with sources are found in the ocean’s depths: marine nodules, ferromanga­
greater abundance (Nordberg et al., 2007). However, these minerals are nese crusts, and polymetallic sulfides (Sharma, 2015), being the former
widely disseminated, and high-grade deposits are scarce (Toro et al., an attractive option due to their high manganese content (between 16
2020b). Besides, Manganese is found in the sea’s depths, in the form of and 24%) (Sharma, 2017).
nodules, micro concretions, coatings, and crusts (Post, 1999). Corathers Marine nodules, also known as manganese nodules, are rock con­
(2020) reported that global demand for Manganese is increasing. This is cretions formed by concentric layers of iron and manganese hydroxides
of great importance in various industrial application such as alloy for around a core (Senanayake, 2011). These minerals are mainly composed
steel production, ferromanganese, non-ferrous alloys, preparation of of δ-MnO2 (hydrogenetic), diaganic 10 Å manganate, mostly containing
dietary additives, fertilizers, dry cell batteries, and inorganic fine Todorokite (formed by oxic diagenesis), and Vernardite (formed by
chemicals (Astuti et al., 2019; El Barbary and Division, 2018; Das et al., hydrogenic precipitation) (Sharma, 2017). Its formation occurs in
2012; Hariprasad et al., 2013; Ismail et al., 2004; Yang Sun et al., 2017; abyssal plains covered with sediments at water depths of 4000–6500 m,

* Corresponding author at: Faculty of Engineering and Architecture, Universidad Arturo Prat, Almirante Juan José Latorre 2901, Antofagasta 1244260, Chile.
E-mail address: [email protected] (N. Toro).
1
Pyrolusite is a mineral consisting essentially of manganese dioxide (MnO2) and is important as an ore of manganese

https://doi.org/10.1016/j.mineng.2020.106748
Received 31 August 2020; Received in revised form 15 December 2020; Accepted 19 December 2020
Available online 19 January 2021
0892-6875/© 2021 Elsevier Ltd. All rights reserved.
N. Toro et al. Minerals Engineering 163 (2021) 106748

Table 1 Table 1 (continued )

The typical leaching processes of Mn(II) ores. Type of leaching Brief description References
Type of leaching Brief description References process
process
o In the absence of oxygen,
Reductive leaching This approach is mainly Das et al., 1982; Dundua Fe(II) can be used as a
with a ferrous iron based on the treatment of and Agniashvili, 1999; Vu reductant in the
solution Mn ore or Mn bearing et al., 2005 following leaching
slimes with acidified process.
ferrous sulfate or pickle Leaching with In a simultaneous leaching Jiang et al., 2003
liquors hydrogen peroxide process for extraction of Mn
Reductive leaching Reductive leaching of Mn Petrie, 1995; Das et al., and Ag by one-step leaching
with sulfur dioxide nodules and low-grade Mn 1998; Grimanelis et al., using H₂SO₄ in hydrogen
or sulfite oxide ores using SO2 or 1992; Partenov et al., 2004; peroxide attendance,
Solutions sulfite SO2- is an effective Ward et al., 2004 hydrogen peroxide plays
reductant for higher Mn dual roles in the process: as
oxide minerals such as an oxidizing agent for
MnO2 and Mn nodules. native silver and a reducing
Reductive leaching Reductive leaching of Sawdust (Sanigok and agent for Mn dioxide.
with organic manganiferous ores Bayramoglu 1988), glucose, Leaching with a The process applies the Kholmogorov et al. 1998; Li
reductants containing tetravalent Mn sucrose (Veglio’ and Toro, hydrochloric acid chloride ions as the 2000; Lu and Zou 2001;
could be performed using 1994a, Veglio and Toro, solution reductant at high acidity Abdrashitov et al., 2001;
organic reductants. 1994b), lactose (Ali et al., and the Cl2 product as the Kuh et al. 2001; Naik et al.
2002; Ismail et al., 2004), oxidant to precipitate the 2002; Yaozhong 2004
glycerine (Arsent’ev et al., reduced Mn as MnO2 in
1991), oxalic acid, citric alkaline conditions.
acid, tartaric acid, formic Leaching with The process is involved Dean et al., 1942; Drinkard
acid (Sahoo et al., 2001; nitrogen dioxide leaching of the Mn ore with and Woerner,1997
Rodriguez et al., 2004), and and nitric acid NO2 and decomposing the
triethanolamine and solutions subsequent Magnesium
thiosulfate (Yavorskaya nitrates (Mn(NO3)2)
et al., 1992). solution. Mn(NO3)2 could
Bio-reductive Reductive biological Vegliò et al., 1997; be removed by bleeding and
leaching treatment that commonly Elsherief, 2000; Acharya re-crystallization.
uses heterotrophic et al., 2003; Das and Ghosh, Acid leaching of Mn Mn carbonate and silicate Comba et al., 1991;
microorganisms under 2018 (II) carbonate and minerals are soluble in Arsent’ev et al., 1992
direct (the bacteria are silicate ores and acids (e.g., in H2SO4 or
adept at using the MnO2 as slags HCl).
a final acceptor of electrons
in the respiratory chain of
their metabolism, instead of where the sediment accumulation rates are low (González et al., 2012).
oxygen) and indirect (the The coverage of marine nodules is about 50% in large areas of the
reductive process is allied
abyssal Pacific seabed and the central Indian Ocean basin (Hein and
with the formation of
reductive compounds, Koschinsky, 2013).
causing from their The dissolution of MnO2 from manganese nodules is possible by a
metabolism) bioleaching leaching process that works at low potential values, using a reducing
mechanism. The biological agent (Randhawa et al., 2016) such as coal (Kanungo and Das, 1988;
process happens in the
presence of organic carbon
Zhang et al., 2017), H2SO3 (Han and Fuertenau, 1986; Khalafalla and
and energy sources. The Pahlmann, 1981), pyrite (Feng et al., 2014a, 2014b; Kanungo, 1999a,
bioleaching mechanism was 1999b), methanol (Momade and Momade, 1999), organic acids like
primarily indirect through EDTA and oxalic acid (Pankratova et al., 2001; Sahoo et al., 2001),
organic acids’ production
sulfur dioxide (Abbruzzese et al., 1990; Grimanelis et al., 1992; Miller
(i.e., mainly oxalic acid and
citric acid in the leaching and Wan, 1983; Naik et al., 2003; Gamini Senanayake, 2004), hydrogen
medium), which reduced peroxide (Jiang et al., 2004; Nayl et al., 2011), cane molasses (Su et al.,
Mn oxides. 2008), glucose (Furlani et al., 2006; Muthalib et al., 2018), phytolacca
Simultaneous In the leaching process of Kholmogorov et al., 1998; americana (Xue et al., 2016), biomass from residual tea (Tang et al.,
leaching Mn(IV) Mn oxides and sulfide Li, 2000; Lu and Zou, 2001;
oxide and sulfide minerals (e.g., galena, Naik et al., 2002; Yaozhong,
2014), residual water from alcohol manufacture from molasses (Su
minerals sphalerite; or zinc matt, 2004 et al., 2009, 2010), the ear of corn (Tian et al., 2010), sponge iron
pyrite; nickel matte, pyritic- (Bafghi et al., 2008), sucrose (Wang et al., 2017), biomass (sawdust and
ferrous lignite) straw) (Sun et al., 2018), magnetite from flotation tailings (Toro et al.,
simultaneously using an
2019a), and tannic acid (Prasetyo et al., 2019) (Table 1 shows the
acid medium, H2SO4 or
HCl, the sulfide minerals typical leaching processes of Mn(II) ores). Among the reducing agents
function as reductants mentioned, iron is a viable alternative for manganese extraction due to
while the Mn oxides as its low cost and abundance (Toro et al., 2018). This article offers a
oxidants. In comparison comprehensive review of Manganese acid-reducing processes from
with other sulfides, pyrite
concentrate offers some
marine nodules using different iron-reducing agents. The review dis­
benefits: cusses the chemistry and reactions involved, emphases on critical pa­
o The iron introduced can rameters that could conceivably affect Manganese’s leaching from
be simply removed as marine nodules.
iron oxides or hydroxides
in the presence of
oxygen; and 2. Fundaments

The reductive leaching of MnO2 in the presence of iron is an efficient

2
N. Toro et al. Minerals Engineering 163 (2021) 106748

Fig. 1. Potential–pH diagram for Mn–Fe–H2O system at 25 ◦ C and unit activity (based on HSC Chemistry 5.1).

process, which may reach high Mn extractions in short periods (Toro on active sites existing on the surface of MnO2 particles and controlled
et al., 2020b; Toro et al., 2020c). Several studies have assessed the effect by Fe2+ ion diffusion. Nonetheless, a study by Tekin and Bayramoǧlu
of iron as a reducing agent on leaching in acidic media of marine nodules (1993) indicated that stirring speed had an insignificant effect, and the
(Bafghi et al., 2008; Kanungo, 1999a, 1999b; Pérez et al., 2020; Saldaña leaching reaction rate was controlled through a surface reaction. The
et al., 2019; Toro et al., 2018; Toro et al., 2019a; Toro et al., 2019b; dissimilarity in the leaching process’s control can be ascribed to the
Torres et al., 2019; Zakeri, 2007), reporting that the maximum man­ differences in the ore’s chemical composition and the conditions of
ganese extraction occurs by increasing the amounts of Fe in the Mn/Fe leaching assays (Bafghi et al., 2008; Xueyi et al., 2003).
ratio and at low acid concentrations (Bafghi et al., 2008; Toro et al.,
2018). As shown in Fig. 1, for Mn’s dissolution from marine nodules,
using a reducing agent (in this case, Fe) is necessary to decrease the 2.1. Studies with Fe reducing agents
system’s potential value.
Naturally, Manganese typically occurs in three oxidation states (II, 2.1.1. Pyrite
III, IV). The comparative stability of each oxidation state in solution is Kanungo (1999a, 1999b) studied hydrochloric acid (HCL) leaching
exceedingly affected by the Eh and the pH. Once Eh-pH conditions are at different temperatures with pyrite as a reducing agent. Kanungo
changed, Manganese is transmuted into the phase utmost stable under 1999a indicated that by adding FeCl3 to the pyrite solution, H2SO4 is
the new conditions if appropriate and thermodynamically approving consequently generated as expressed by Eq. (1). Reaction (1) suggests
reaction pathways extant. Nevertheless, forecasting the conversion rates that pyrite’s oxidation rate should be inhibited due to decreased pH.
entails a kinetic analysis (Amalia and Azhari, 2017; Baba et al., 2014; However, the increase in the initial concentration of acid leads to the
Martin, 2005). Reductive leaching should be conducted within acid higher dissolution of ferric ions from the sample of manganese nodules.
circumstances (lower pH value) in order to efficiently convert Mn(IV) Furthermore, the generated extra FeCl3 causes an increase in pyrite’s
from manganese ore into Mn(II). Treatment of manganese ore with oxidation (see Eq. (2)). The MnO2 reduction rate is much faster than the
acidified ferrous sulfate or pickling solution was reported for the first pyrite oxidation rate. Eq. (3) shows the formation of S0, which can occur
time in 1947 and ever since has continuously been explored. A summary at low acidity (pH) and low oxidation potential (Eh), which fits into the
of relevant studies was presented in a review paper by Sinha and Purcell appropriate pH and Eh ranges for acid-reducing leaching of MnO2.
(2019).
FeS2 + 14FeCl3 + 8H2O = 15FeCl2 + 12HCl + 2H2SO4 (1)
In a study by Zakeri (2007), more than 95% Mn was extracted using
ore particle sizes of − 60 + 100 μm, Fe2+/MnO2 molar ratio 1/3, H2SO4/ MnO2 + 2FeCl2 + 4HCl = MnCl2 + 2FeCl3 + 2H2O (2)
MnO2 molar ratio of 1/2, and a reaction time of 20 min at room tem­
perature. The outcomes oriented that the dissolution of Manganese was FeS2 = Fe 2+ 0
+ 2S + 2e (3)
more affected by the concentration of Fe2+ ion than the solution’s
acidity. Thus, it was recommended that a surplus Fe2+/MnO2 ratio be
used for manganese leaching. A drop of Fe2+ and H+ concentration Table 2
caused Fe3+ and Mn2+ products. That also led to a decline in mass Thermodynamic information of the reactions with FeS2 like reducing agent
transfer and, accordingly, lessening the reaction rate. (based on HSC Chemistry 5.1).
The kinetics of reductive manganese leaching is controlled by Reaction ΔG◦ (kJ/ Equation
diffusion through the insoluble layer of the associated minerals and mol)
primarily limited by the diffusion of Fe2+ and/or Mn2+ through ash 3FeS2 + 4H2SO4 = 3FeSO4 + 4H2O + 7S − 187 4
layers (Baba et al., 2014; Villinski et al., 2003; Dundua and Dobrokho­ 6FeSO4 + 4H2SO4 = 3Fe2(SO4)3 + 4H2O + S − 27.8 5
tov, 1982). Most previous studies (e.g., Bafghi et al., 2008; Dundua and 2FeS2 + 4H2SO4 = Fe2(SO4)3 + 4 H2O + 5S − 133,9 6
15MnO2 + 2FeS2 + 14H2SO4 = Fe2(SO4)3 + 15MnSO4 2987,7 7
Dobrokhotov, 1982; Majima et al., 1981) stated that the leaching ensued
−
+ 14H2O

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N. Toro et al. Minerals Engineering 163 (2021) 106748

In an acidic medium (pH 1.5), the ferrous ions (Fe2+) and ferric ions Table 4
(Fe3+) ratio remain constant until 50 min, above which the ratio tends to Comparison between the results obtained when working with ferrous ions and
increase exponentially. From this, it is suggested that the reduction of sponge iron for the dissolution of manganese nodules (modified from Bafghi
MnO2 by ferrous ions occurs faster than the oxidation of pyrite gener­ et al., 2008).
ating ferric ions (Kanungo, 1999a). Experimental Condition Zakeri (2007) Bafghi et al. (2008)
Recently, Torres et al., 2019 carried out leaching tests of manganese Iron-reducing agent Fe2+
Fe0
nodules using sulfuric acid (H2SO4), adding pyrite at 60 ◦ C. They pro­ Temperature (◦ C) 20 20
posed a series of chemical reactions presented in Table 2 that explains Particle Size of the solid (ore/Fe0) (µm) − 250 + 150 − 250 + 150
the dissolution of MnO2. H2SO4/MnO2 molar ratio 3 3
Fe/MnO2 molar ratio 2.4 0.8
Eq. (4) shows pyrite (II) dissolution in an acidic environment where Mn extraction (10 min) (%) 80 98
ferrous sulfate (II) formation begins. This reaction is spontaneous ac­
cording to the Gibbs Free Energy calculated using HSC 5.1 software.
Ferrous sulfate will fulfill the function of reducing Manganese (IV) from
Table 5
marine nodules. Ferrous sulfate oxidizes spontaneously but slowly in an
Reactions for dissolution of MnO2 from marine nodules using Fe2O3 and Fe2O4 in
acidic environment. The formation of ferric sulfate (III) is given in Eq.
an acidic medium (Modified from Toro et al., 2019b).
(5). The direct solution of pyrite to ferric (III) sulfate in an acid medium
Reaction ΔG◦ (kJ) Equation
expressed by Eq. (6) is a spontaneous reaction slower than Eq. (1). Eq.
(7) shows the overall reaction, where the reducing solution of manga­ Fe2O3(s) + 3H2SO4(aq) = Fe2(SO4)3(s) + 3H2O(l) − 163.37 17
nese (IV) oxide to manganese (II) sulfate and the oxidation of pyrite (II) Fe3O4(s) + 4H2SO4(l) = FeSO4(aq) + Fe2(SO4)3(s) + 4H2O − 261.30 18
(l)
to ferric (III) sulfate occurs in a swift and spontaneous reaction.
2FeSO4(aq) + 2H2SO4(aq) + MnO2(s) = Fe2(SO4)3(s) + − 199.52 19
2H2O(l) + MnSO4(aq)
2.1.2. Ferrous ions
For the use of ferrous ions, Zakeri (2007) indicated that the increase
in temperature from 20 to 60 ◦ C together with a decrease in the man­
Table 6
ganese nodule’s particle size improves the dissolution rate of MnO2. The Comparison between foundry slag and tailings, as a reducing agent in the
authors mentioned that it is necessary to work on molar ratios of Fe2+/ dissolution of marine nodules.
MnO2 and H2SO4/MnO2 in excess of stoichiometric, allowing high
Experimental conditions Toro et al. Toro et al.
extraction of Mn2+ in short periods (5 min) and room temperature. (2018) (2019a)
Zakeri (2007) proposed the following series of chemical reactions:
Temperature (◦ C) 25 25
MnO2 + 4H+ + 2e− = Mn2+ + 2H2O (8) The particle size of Mn nodules and slag/ − 75 + 53 − 75 + 53
tailings (μm)
2Fe2+ =2Fe3+ + 2e− (9) H2SO4 concentration (mol/L) 1 1
MnO2/Fe2O3 ratio 1/2 1/2
MnO2 + 2Fe2+ + 4H+ = Mn2+ + 2Fe3+ + 2H2O (10) Mn dissolution rate at 5 min (%) 68 67
Mn dissolution rate at 40 min (%) 70 77
The overall reaction shows that the molar amounts of ferrous ions
(Fe2+) and acid protons in the solution, regarding the stoichiometric
amounts represented in Eq. (10), could affect the MnO2 dissolution re­ Fe2+. The authors indicated that sponge Fe delivers better results than
action. The authors concluded that the optimal operating conditions ferrous ions under the same operating conditions, obtaining Mn ex­
were a Fe2+/MnO2 molar ratio of 3.0, an H2SO4/MnO2 molar ratio of tractions of 98% at room temperature and short leaching periods (see
2.0, and a mineral particle size of − 60 + 100 Tyler mesh. Extractions of Table 4). It is because the Fe metal produces a high activity ratio through
95% Mn were obtained in less than 20 min at 20 ◦ C. the regeneration of ferrous ions. Bafghi et al. (2008) proposed the
following chemical reactions in Table 4.
2.1.3. Sponge iron
Bafghi et al. (2008) experimented similarly to Zakeri (2007) but 2.1.4. Slags
using sponge Fe in an acid medium. In Table 3, Gibbs free energy values Slag from a smelting plant was used in the study of Toro et al. (2018),
are presented, calculated from standard reduction potential values. The taking advantage of the high concentration of Fe2O3. In Table 5, the
reactions 14, 15, and 16 involve the use of Fe0, which are thermody­ reactions for the dissolution of marine nodules with the use of sulfuric
namically favorable concerning those that consider Fe2+ (Eq. (13)). acid and tailings are presented, where the primary reducing agent is
Subsequently, Bafghi et al. (2008) compared their results when ferrous sulfate, generated from the leaching of hematite (Eq. (17)) and
working with Fe0 with respect to Zakeri (2007) when working with mainly magnetite (Eq. (18)) (majority component in tailings) when
reacting with sulfuric acid. Then, this reducing agent (FeSO4) allows
reducing MnO2 to (Mn4+), obtaining a manganese sulfate (Mn2+) (Eq.
Table 3 (19)).
Thermodynamic information of the reactions with Fe0 like reducing agent
(based on HSC Chemistry 5.1). 2.1.5. Tailings
Reaction ΔG◦ (J/ Equation Toro et al. (2019a) used the tailings obtained by the copper flotation
mol) from smelting slags with high Fe2O3 and Fe3O4 contents. These tailings
Fe(s) + 2H+ (aq) = Fe2+(aq) + H2(g) − 84,900 11 samples contained a higher amount of magnetite and hematite than
Fe(s) + 2Fe3+(aq) = 3Fe2+(aq) − 234,000 12 typical slags. In the study, over 77% of extractions were achieved with a
MnO2(s) + 2Fe2+(aq) + 4H+ (aq) = Mn2+(aq) + − 88,600 13 MnO2/Fe2O3 ratio of 0.5, 1 mol/L of H2SO4 in 40 min, being higher than
2Fe3+(aq) + 2H2O(l)
that obtained with slags under the same operational conditions (see
MnO2(s) + 2Fe(s) + 8H+ (aq) = Mn2+(aq) + 2Fe3+(aq) − 258,000 14
+ 2H2O(l) + 2H2(g) Table 6). The authors concluded that tailings from the flotation process
MnO2(s) + Fe(s) + 4H+ (aq) = Mn2+(aq) + Fe2+(aq) + –322,000 15 were a better additive for reducing MnO2 than foundry slags. This is
2H2O(l) probably because the tailings were previously exposed to chemical re­
MnO2(s) + 2/3Fe(s) + 4H+ (aq) = Mn2+(aq) + 2/ − 244,000 16
agents during the flotation process.
3Fe3+(aq) + 2H2O(l)

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N. Toro et al. Minerals Engineering 163 (2021) 106748

Table 7 dissolution of Mn from marine nodules using FeS2 is of first-order

Effect of the addition of FeS2 on the maximum concentrations of Fe II, Fe III, and regarding the initial concentration of acid and the concentrations of
Fe for acid-reducing leaching of manganese nodule in the presence of pyrite at Fe2+ and Fe3+, and second-order to pyrite concentration.
75◦ C, Solid/Liquid 1/5, particle size − 153, +105 mm (Modified from Kanungo Zakeri (2007) analyzed the effect of ferrous ions to dissolve MnO2 in
1999b). an acidic medium, working on Fe2+/MnO2 molar ratios of 2.0, 2.4, and
Pyrite added (% [Fe3+]m [Fe2+]m [Fe]T [Fe2+]m/ [Fe3+] 3.0 (1, 1.2, and 1.5 times the stoichiometric amount, respectively), at
by wt. of mmol/L mmol/L mmol/L [Fe3+]m m/[Fe]T 20 ◦ C, H2SO4/MnO2 = 2.0, and a mineral particle size between 60 and
nodule)
100 Tyler mesh. The researchers observed that Mn extractions for molar
10.0 4.70 0.142 4.842 0.030 0.9707 ratios of 2.0 and 2.4 were similar, but when going from 2.0 to 3.0, the
15.0 5.40 0.250 5.650 0.046 0.9558
increase was close to 30%, achieving extractions greater than 90% in 10
20.0 6.20 0.300 6.500 0.048 0.9538
25.0 7.10 0.480 7.580 0.068 0.9367 min. The authors suggested that the gangue’s presence around the larger
MnO2 particles may hinder the diffusion speed. The loss of the reagents
(Fe3+ and Mn2+) concentrations reduced the driving force for mass
3. Operational variables transfer, decreasing the reaction speed.
Subsequently, Bafghi et al. (2008) evaluated the dissolution of ma­
3.1. Effect on reducing agent concentration rine nodules at different concentrations of sponge Fe (molar ratio of iron
to MnO2 of 0.67, 0.8, 1.0, and 1.2), H2SO4 concentrations (molar ratios
There is a consensus by various researchers about the positive effect of acid to MnO2 of 2.0, 2.4 and 3.0), and particle size of mineral and
of increasing the Fe/Mn ratio on the dissolution of manganese nodules sponge iron between 250 and 150 μm at 20 ◦ C. When working at Fe0/
(Kanungo 1999a, 1999b; Zakeri, 2007; Bafghi et al., 2008, Toro et al., MnO2 molar ratios of 0.67 and 0.8, Mn’s maximum extraction was 80%.
2018; 2019a; 2019b, Saldaña et al., 2019, Perez et al., 2020). Working at However, by increasing the reducing-agent beyond these levels, the
high concentrations of an iron-reducing agent allows increasing the extraction increased significantly by 97% when the H2SO4/MnO2 molar
concentration and activity of ferrous ions. This favors the dissolution of ratio was 2.4. This may be because, with the sufficiency of H2SO4, the
MnO2, decreasing the leaching times significantly, and avoiding Fe oxidation reaction of ferrous ions to ferric ions in the presence of MnO2
precipitates formation through oxidation–reduction reactions. occurs at a high rate. Bafghi et al. (2008) finally concluded that the ef­
Kanungo 1999b evaluated the dissolution of manganese nodules at ficiency in dissolving MnO2 is more sensitive to the amount of Fe0 than
75 ◦ C by adding FeS2, HCl at 1 mol/L, and particle size (nodule) of − 153 the concentration of H2SO4.
+ 105 μm. The author observed that the MnO2 dissolution increased as Toro et al. (2018) worked at 25 ◦ C with different slag/MnO2 ratios,
FeS2 increased from 10 to 25 wt% concerning the marine nodule sample. particle size of − 200 +270 Tyler mesh, and sulfuric acid concentration
The Fe2+/Fe3+ ratio increases, while the Fe3+/Total Fe ratio decreases of 1 mol/L. The authors concluded that Mn’s extraction times reduces at
slightly at their maximum concentrations as the pyrite content increases high slag/MnO2 (2/1) ratios and 1 mol/L H2SO4, achieving extractions
(Table 7). By increasing the concentration of FeCl3, the amount of Cl- close to 70% in 5 min. Pérez et al. (2020) continued this investigation by
ions increases considerably. Therefore, stable Fe3+ chloride complexes testing higher slag concentrations (slag/MnO2 ratio of 3/1) at different
were formed, resulting in a decrease in pyrite’s oxidation rate. However, concentrations of sulfuric acid (0.1, 0.3, 0.5, and 1 mol/L). The authors
this did not happen when pyrite was incremented since HCl’s chloride found that the optimal ratio of slag/MnO2 is 2/1 and indicates that the
ions were limited. The resting potential of FeS2 was practically not acid concentration was irrelevant, achieving practically the same results
altered since there were large amounts of pyrite. Kanungo 1999b when working at 1 mol/L or 0.3 mol/L H2SO4. For the use of tailings, the
concluded that pyrite’s order represents the Fe2+/Mn4+ molar ratio studies carried out by Toro et al. (2018, 2019a; 2019b) indicated that an
since MnO2 does not react directly with pyrite. Therefore, the optimal tailings/MnO2 ratio was 2/1; however, the authors mentioned

Fig. 2. Effect of the potential and pH in solution at different MnO2/Fe2O3 ratios (25 ◦C, 600 rpm, − 75 + 53 µm, acid concentration of 0.1 mol/L) (Modified from:
(Toro et al., 2019b)).

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N. Toro et al. Minerals Engineering 163 (2021) 106748

Fig. 3. Effect on MnO2/reducing agent ratio at 25 ◦ C, 0.1 mol/L H2SO4 and 600 rpm (Reducing agent: FeS2 (a), Fe2+ (b), FeC (c) and Fe2O3 (d)). (Modified since:
(Torres et al., 2019)).

that a concentration of 0.1 mol/L sulfuric acid is enough with high stoichiometric amount, respectively). As the sulfuric acid concentration
concentrations of reducing agents. This is because the FeSO4 reduces the increases, there was an increase in Mn extraction. The extraction effi­
system’s potential in values that favor the dissolution of MnO2; besides, ciency increased by 10% when rising the ratio from 2.0 to 2.4. Working
low acid concentrations (0.1 mol/L) are enough to extract Mn (See at a ratio of 3.0, a significantly higher dissolution rate was achieved,
Fig. 2). which was attributed to the increase in mass transfer driving force.
Torres et al. (2019) analyzed Fe’s levels from different reducing Subsequently, Bafghi et al. (2008) studied an iron sponge under similar
agents, working at a low acid concentration (0.1 mol/L H2SO4). As conditions to those used in the study by Zakeri (2007). The authors
shown in Fig. 3, when working with Fe0, Fe2+, and tailings, the optimal indicated that the concentration of Fe0 is more critical for the dissolution
Fe/MnO2 was 2/1, where higher Fe concentrations do not obtain better of manganese dioxide than sulfuric acid. In the studies carried out by
Mn extractions. The best results were obtained with Fe0 since it allows Toro et al. (2018, 2019a; 2019b) with the use of smelting slags and
having a high activity ratio in the regeneration of ferrous ions, allowing tailings, both with high Fe2O3 and Fe3O4 contents, the authors
even better results compared to the direct use of Fe2+. The opposite concluded that the concentration of sulfuric acid is only relevant when
occurs when working with pyrite, where a progressive rise occurs with the concentration of reducing agent in is low. While working at Fe2O3/
increasing the amounts of this reducing agent. The authors concluded MnO2 ratios of 2/1 or higher, the concentration of sulfuric acid is
that it is possibly due to the low concentration of acid used that does not irrelevant to the dissolution of MnO2. Torres et al. (2019) evaluated the
favor dissolution kinetics. This was consistent with Kanungo (1999a), H2SO4 concentration comparing different iron-reducing agents under
who stated that a high initial concentration of acid is necessary to favor the same operational conditions (25 ◦ C, reducing agent/MnO2 ratio of
the formation of ferrous ions. 2/1, 600 rpm and a particle size between 75 and 53 μm), except when
working with pyrite where the temperature was 60 ◦ C (see Fig. 4). The
authors concluded that for the use of Fe2+, Fe0, and tailings in high
3.2. Acid concentration concentrations, the potential values were kept low (see Fig. 5). There­
fore, high Mn extractions were obtained despite working at a low acid
Kanungo (1999a, 1999b) indicated that for the leaching of marine concentration (0.1 mol/L). This did not occur when working with FeS2,
nodules using HCl and the pyrite, an accumulation of ferric and ferrous possibly due to the pyrite mineral’s refractoriness.
ions was generated initially up to a particular time. This reduced as the
medium’s acidity decreases, where the initial concentration of acid and
the system’s temperature were essential. 3.3. Temperature
For the use of ferrous ions, Zakeri (2007) highlighted the importance
of sulfuric acid concentration. The authors worked with a 3/1 M ratio of The effect of temperature on acid leaching of marine nodules has
H2SO4/MnO2, namely 2.0, 2.4, and 3.0 (1, 1.2, and 1.5 times the been investigated in many studies. The temperature positively affects

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N. Toro et al. Minerals Engineering 163 (2021) 106748

Fig. 4. Effect on acid concentration (reducing agent: (a) FeS2, (b) Fe2+, (c) Fe0 and (d) tails). (Modified since: (Torres et al., 2019)).

Fig. 5. Effect of potential and pH on the dissolution of marine nodules with different reducing agents (Modifiaco since: (Torres et al., 2019)).

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N. Toro et al. Minerals Engineering 163 (2021) 106748

Table 8 the recovery of elements of interest, selectivity, kinetics, and acid con­
Experimental values to statistical model (From: (Saldaña et al., 2019). sumption (Toro et al., 2020b).
Parameter/Value Low Medium High Kanungo (1999a, 1999b) evaluated the effect of temperature
(40–85 ◦ C) to dissolve marine nodules adding 15 wt% of pyrite and 1
Time (min) 5 10 20
Particle Size (µm) − 150 + 106 − 75 + 53 − 47 + 38 mol/L of HCl. As the temperature increases, the author found a faster
H2SO4 (mol/L) 0.1 0.3 0.5 reduction in MnO2, whereby the pH drops sharply, increasing the value
F2O3/MnO2 ratio 1/2 1/1 2/1 in the Fe2+/Fe3+ ratio. The dissolution kinetics of MnO2 increases
Stirring Speed (rpm) 600 700 800 sharply with increasing temperature from 10 to 60 ◦ C, but when working
Temperature (◦ C) 25 35 50
at 75 ◦ C, the increase was relatively slow.
Zakeri (2007) evaluated the effect of temperature on the leaching of

Fig. 6. Impact of the variables in the regression model (From: (Saldaña et al., 2019)).

Fig. 7. Contour plot of the independent variables Fe2O3/MnO2 ratio, Time (a); Temperature, Time (b); and Temperature, Fe2O3/MnO2 ratio (c) in Mn recovery (%)
(From: (Saldaña et al., 2019)).

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N. Toro et al. Minerals Engineering 163 (2021) 106748

particle size of − 600 + 250 µm and − 250 + 150 µm to avoid dissolving

so quickly that it prevents taking a sufficient number of samples before
the reaction is complete. 100% Mn extractions were obtained in just 3
min at 60 ◦ C. They concluded that despite the beneficial effect of tem­
perature, the dissolution rate of MnO2 adding high Fe concentrations is
fast, where at room temperature, complete dissolution was achieved in a
time of 10 min. Saldaña et al. (2019) fitted an analytical model for
manganese recovery, considering that first-order equations can describe
the system’s behavior. However, the proposed solution was an inverse
exponential model. Then, as the exponent determines the leaching ki­
netics, a multiple regression model was developed based on the inde­
pendent variables. This describes its variability and consequently
explains the recovery of Mn for the sampled domain. The operational
variables studied were decided based on previous studies’ results to
dissolve manganese nodules in acidic media and Fe reducing agents (See
Table 8).
Saldaña et al. (2019) discovered that, by interacting with all these
operational variables, only the reducing agent concentration and tem­
Fig. 8. Effect of the ore particle size on dissolution efficiency of manganese perature have a significant effect on the dissolution of MnO2 (see Fig. 6).
(20 ◦ C, Fe2+/MnO2 = 2.4, H2SO4/MnO2 = 2.0). (Modified from: At high concentrations of FeSO4 or high temperatures, a higher amount
(Zakeri, 2007)). of MnO2 solutions can be obtained in brief periods (Fig. 7 a and b).
Furthermore, the authors indicate no synergy between the reducing
marine nodules at 20, 40, and 60 ◦ C, under fixed conditions of Fe2+/ agent concentration and the temperature, showing Mn’s recovery as an
MnO2 = 2.4, H2SO4/MnO2 = 2.0, and mineral particle size of − 16 + 20 approximately linear function (See Fig. 7 c).
mesh. The authors found an increase in both speed and Mn extractions
with increasing temperature, where at 60 ◦ C, it was possible to extract
96% of the Mn in 60 min. 3.4. Effect on particle size
Bafghi et al. (2008) studied the same temperature ranges that Zakeri
(2007), but at lower molar concentrations of Fe0 (Fe0/MnO2 = 2.0) and Researchers have no consensus regarding the effect of particle size in
a higher concentration of sulfuric acid (H2SO4/MnO2 = 4.0) to avoid manganese nodules’ solution using Fe reducing agents. Some research
exhaustion of the reagents. Also, they worked at a reducing agent indicates that the particle size has a very positive effect on the dissolu­
tion kinetics of MnO2 (Zakeri 2007, Bafghi et al., 2008), while others
mention that the particle size was very little relevant (Kanungo 1999b,
Table 9 Toro et al., 2018, Saldaña et al. 2019).
Chemical analysis of the different sieve fractions of the two manganese nodule Regarding the positive effect on particle size, Zakeri (2007) indicated
samples (Modified from Kanungo 1999a). that the reaction rate increases considerably as the manganese nodule’s
Sieve fractions (B.S.S.) Size (mm) Mn (%) Fe (%) particle size decreases. They attributed this to control the internal mass
transfer speed, which was corroborated by kinetic analysis. In their
Sample 1 − 25, +36 − 600, +420 11.00 11.80
− 36, +44 − 420, +355 11.50 12.00 studies, the mineral’s MnO2 dissolution rate with a particle size of − 100
− 60, +100 − 251, +153 10.10 11.46 + 170 Tyler mesh was more significant than the size fraction of − 60 +
− 100, +150 − 153, +105 10.33 11.30 100 Tyler mesh (see Fig. 8). Bafghi et al. (2008) compared the effect of
− 150, +200 − 105, +76 9.37 11.43 particle size of manganese nodule ore and sponge iron under the same
− 200, +300 − 60, +53 9.63 11.37
Sample 2 − 60, +100 − 251, +153 20.20 9.49
operational conditions. The authors indicated that the sponge iron
− 100, +150 − 153, +105 20.10 10.02 particle size has a low effect on the dissolution efficiency of MnO2
− 150, +200 − 105, +60 19.56 10.03 compared to the particle size of the marine nodule, which does have a
− 240, +300 − 60, +53 19.85 10.22 positive effect on the dissolution rate. This may be explained because the

Fig. 9. Decrease in particle size over time from its initial size, until the leaching process is finished for samples 1 and 2 of manganese nodules (Modified from:
(Kanungo, 1999b)).

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N. Toro et al. Minerals Engineering 163 (2021) 106748

Table 10 surface or the edges. Reductive leaching of MnO2 also coincides with the
Experimental conditions for studying the effect of manganese nodule particle tiny particles’ surface through a mixed process of chemical diffusion and
size (Toro et al., 2018). dissolution. After a particular leaching time, the coarser grains’ di­
Parameters Values mensions no longer change due to silicate minerals within the ferro­
Sieve fraction (Tyler Mesh) − 100 + 140, − 200 + 270, − 320 + 400
manganese oxide layers. For the finer grains, the degree of release of the
Particle size (µm) − 150 + 106, − 75 + 53, − 47 + 38 ferromanganese oxide grains with respect to the other minerals that
Time (in min) 5, 10, 20, 30, 40 accompany the marine nodule helps Mn’s dissolution.
H2SO4 (M) 0.1, 0.5, 0.75, 1 Toro et al. (2018) analyzed the effect of particle size at different acid
MnO2/Fe (slag) 1/1
concentrations, keeping the other variables static (see Table 10). The
authors indicated that particle size did not positively affect MnO2
iron’s porous structure facilitates the reagents’ mass transfer, making its dissolution, obtaining similar results for the three size fractions studied
size irrelevant. (see Fig. 10). However, the tests were performed at high concentrations
Regarding the low relevance of particle size, Kanungo (1999b) of Fe/MnO2, so according to what was stated by Saldaña et al. (2019),
studied the effect of particle size for two samples of manganese nodules this could have made the effect on particle size irrelevant.
(see Table 9). The authors observed that for sample 1, Mn extractions
increased slowly for coarse size fractions (− 600) mm to (− 251, +153) 4. Conclusions and outcomes
mm, but with a slight increase in the finest size fractions (− 153, +100)
mm and (− 60, +53) mm. While in Sample 2, there was a uniform in­ The acid-reducing leaching of manganese from high MnO2 minerals
crease as the particle size decreased, except for the finer size (− 60, +53) is attractive for its high Mn extractions and rapid dissolution kinetics.
mm. However, it was concluded that this occurs due to the differences in This leaching type generates better results in Mn’s recovery than the
the samples’ iron contents. Because the physical changes that samples 1 traditional process, which involves reduction at high temperatures fol­
and 2 obtain during the reaction did not allow gaining much information lowed by acid leaching. It is also a sustainable process with the envi­
regarding the particle size’s impact. Kanungo (1999b) made a log/log ronment, which meets future standards of the low-carbon economy.
graph of time vs. initial average diameter for the different leachates Promising studies have been reported on various reducing agents for
fractional (see Fig. 9). For sample 1, the slopes’ values decreased for the the dissolution of manganese nodules in acidic media, presenting Fe as a
coarse size fractions. While in sample 2, the straight lines were almost possible alternative to be used widely in the extractive metallurgy in­
parallel to each other. The author concluded that this could be explained dustry. It has a low cost and can even be recycled from scrap or indus­
in the following way: First, when the samples are exposed to the reac­ trial waste smelting slag, tailings, or scrap steel. The relative stability of
tant, the quick dissolution of iron occurs mainly from the particles’ three oxidation states (II, III, IV) for Manganese in solution is

Fig. 10. Effect of particle size (manganese nodule) on Mn extraction (25 ◦ C, H2SO4: 0.1, 0.5, 0.75, 1 M). (A): − 150 + 106 μm, (B): − 75 + 53 μm, (C) − 47 + 38 μm)
(Modified from: (Toro et al., 2018)).

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N. Toro et al. Minerals Engineering 163 (2021) 106748

significantly affected by the Eh and the pH. Reductive leaching should Miner. Process. Extr. Metall. Rev. 30 (2), 163–189. https://doi.org/10.1080/
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times (5 min), reaching extractions over 90% of Mn. Feng, Y.-L., Zhang, X., Li, H.-R., Yang, Z.-C., 2014a. Pyrolusite leaching reactions in FeS2-
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Feng, Y., Zhang, X., Li, H., Cai, Z., 2014. Effect of H+ and Fe3+ on leaching MnO2 in
Declaration of Competing Interest MnO2-FeS2-H2SO4 leaching system. Zhongnan Daxue Xuebao (Ziran Kexue Ban)/J.
Central South Univ. (Sci. Technol.) 45, 12, 4123–4128.
Furlani, G., Pagnanelli, F., Toro, L., 2006. Reductive acid leaching of manganese dioxide
The authors declare that they have no known competing financial with glucose: Identification of oxidation derivatives of glucose. Hydrometallurgy 81
interests or personal relationships that could have appeared to influence (3–4), 234–240. https://doi.org/10.1016/j.hydromet.2005.12.008.
González, F.J., Somoza, L., León, R., Medialdea, T., de Torres, T., Ortiz, J.E., Lunar, R.,
the work reported in this paper. Martínez-Frías, J., Merinero, R., 2012. Ferromanganese nodules and micro-
hardgrounds associated with the Cadiz Contourite Channel (NE Atlantic):
Palaeoenvironmental records of fluid venting and bottom currents. Chem. Geol.
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