Hydrometallurgy 84 (2006) 187 191

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Reductive leaching of manganese from low grade Sinai ore

in HCl using H2O2 as reductant
M.N. El Hazek, T.A. Lasheen, A.S. Helal
Nuclear Materials Authority, P.O. Box 530 El Maadi, Cairo, Egypt
Received 17 March 2006; received in revised form 17 May 2006; accepted 25 May 2006
Available online 7 July 2006

Abstract
Manganese leaching from a low-grade ore (8.52% Mn) from Sinai was investigated by using hydrochloric acid in the presence and
absence of hydrogen peroxide as a reducing agent. Sample characterization by XRD showed the presence of a variety of manganese
minerals mainly cryptomelane, chalcophanite, pyrolusite, and crednerite. The presence of iron minerals like goethite, hematite, and
minor quantities of pyrite were also observed, as well as gibbsite and dolomite. Although pyrite can act as a reductant for the tetravalent
manganese minerals, it was necessary to use H2O2 as an additional reductant to realize over 97% Mn leaching. Both Zn and Cu that are
present in the manganese minerals chalcophanite and crednerite respectively, were simultaneously leached.
The relevant leaching factors were optimized as 2 M HCl and 0.4M H2O2 for 1 h when using a solidliquid ratio of 1/12 at 6095 C.
Under these conditions, the leaching efficiencies were >97% Mn, 98% Zn together with about 81% Al and complete leaching of Cu;
whilst iron dissolution did not exceed 14%.
2006 Elsevier B.V. All rights reserved.
Keywords: Manganese ores; Hydrochloric acid leaching; Reductive leaching; Hydrogen peroxide

1. Introduction
Manganese is a strategic element that has several industrial applications such as steel production, carbonzinc
batteries production, fertilizers, as well as colorants for
bricks, dyes and medicines (Sahoo et al., 2001). The world
annual consumption of manganese is above 1,300,000
annual tons and it is destined to increase. Low grade ores
are gaining increasing attention due to developments in
exploitation technologies.
Various hydrometallurgical methods have been suggested in the literature for treatment of low grade manga-

Corresponding author. Tel.: +20 23304172.

E-mail address: ahmed_samihelal@yahoo.com (A.S. Helal).
0304-386X/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2006.05.006

nese ores. Such ores can be treated either by reduction

roasting followed by acid leaching (Sahoo and Srinivasa,
1989) or directly by reductive acid leaching using different reducing agents. To realize the latter, several procedures have been suggested; namely mixed methanol
sulphuric solution (Momade and Momade, 1999), coke
(Panda and Gupta, 1988), non aqueous dimethyl sulfoxide (Raisoni and Dixit, 1988), sulphuric and oxalic acid
mixtures (Sahoo and Srinivasa, 1989), iron() sulphate
(Das et al., 1982), aqueous sulphur dioxide (Abbruzzese,
1990; Abbruzzese et al., 1990; Naik et al., 2000; Vegli
and Toro, 1994), sulphuric acid and hydrogen peroxide
(Tao Jiang et al., 2003, 2004), hydrochloric acid and nickel
matte (Chen et al., 1992), hydrochloric acid and pyrite
(Kanungo, 1999a,b). Recently, Jana et al. (1995) have
reported the dissolution of MnO2 in an aqueous alcoholic-

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M.N. El Hazek et al. / Hydrometallurgy 84 (2006) 187191

Table 1
Chemical composition of Abu Zeneima ore material

Table 2
Mineralogical composition of Abu Zeneima ore material

Component

Wt.%

Mineral/oxide

Wt.%

SiO2
TiO2
Al2O3
Fe2O3
MnO
MgO
CaO
Na2O
K2O
P2O5
LOI*
ZnO
CuO
Total

16.00
0.33
8.80
20.08
11.00
5.94
8.32
0.67
0.34
0.55
26.80
2.00
0.25
101.08

Quartz
Dolomite
Gibbsite
Iron oxide minerals*
Manganese minerals
ZnO**
Total

16.00
27.00
13.46
29.15
11.00 (equivalent MnO)
2.00
98.94

*LOI includes 13.07% CO2 present in dolomite and 13.73% water

present in gibbsite (4.66%) and in the iron mineral goethite (9.07%).

HCl acid mixture. These authors have pointed out that the
chloride ion at high concentrations was responsible for
the reduction of higher valence state oxides. On the other
hand leaching processes in basic media involve the use
of ammonium sulphite as reductant (Das et al., 1986), in
addition to several patented leaching processes (Cardwell
and Kane, 1976; Kane and Card well, 1974; Van Peteghem,
1977).
The high grade Paleozoic manganese deposit of south
west Sinai has essentially been exploited. Nevertheless,
extensive tonnages of low grade ore material still exist
and require developed technologies for their economic
processing. A proper mineralogical sample of this low
grade ore was therefore collected from Abu Zeneima
locality (11.00% MnO) and was subjected to processing
via reduction leaching. For this study, a mixture of hydrochloric acid and hydrogen peroxide was used for the
first time. The redox chemistry of the latter in aqueous
solution shows that it is a strong oxidizing agent in either
acid or basic solution as shown from the following
equations (Cotton and Wilkinson, 1988).

*Calculated as goethite.
**Involved in the Mn mineral chalcophanite.

MnO2 in acidic solution can be described by the following

equation
MnO2 4H 2Mn2 2H2 O
This study examines the different relevant factors affecting the leaching of manganese and other impurities
from the ore. These factors involved the concentration of
both acid and H2O2, the leaching temperature and time, as
well as the pulp density and the grain size of the ore.
2. Experimental
2.1. Ore material
To define the mineralogical composition of the working ore material, the bulk and sieved samples were subjected to X-ray diffraction analysis. For this purpose, a
Philips X-ray diffractometer, model PW 223/20 was used
where the copper tube was operated at 40 kV and 20 mA.
The obtained diffractogram was properly interpreted using
standard diffraction mineral patterns. The obtained results
revealed the presence of several manganese minerals such

H2 O2 2H 22H2 OE 0 1:77V
O2 2H 2H2 O2 E 0 0:68V
HO2 H2 O 23OH E 0 0:87V
However, H2O2 behaves as a reducing agent only
towards very strong oxidizing agents such as MnO4
and MnO2 and chloride ion is not a reductant in dilute
acid solutions. Accordingly, the chemical dissolution of

Fig. 1. Effect of HCl concentration upon the leaching efficiencies of

Abu Zeneima ore (0.4 M H2O2, 95 C, 1/12 pulp density, 2 h, 74 m).

M.N. El Hazek et al. / Hydrometallurgy 84 (2006) 187191

Fig. 2. Effect of H2O2 concentration upon the leaching efficiencies

(2 M HCl, 95 C, 1/12 pulp density, 2 h, 74 m).

as cryptomelane, chalcophanite, pyrolusite and crednerite

associated with some iron minerals as well as the
aluminium mineral gibbsite and the carbonate mineral
dolomite. The ore material was also chemically analyzed
for its major and minor elements (Table 1).
From the obtained analytical and mineralogical results,
the following potential mineralogical composition of
the working Abu Zeneima low grade Mn ore material is
indicated (Table 2).
2.2. Leaching procedure
The ore sample was first crushed to 60 mesh size
( 250 m) and was then ground to the required particle
size of 200 mesh ( 74 m). The leaching experiments
were carried out using 10 g sample fractions to which
the proper acid and H2O2 contents were added. The
obtained ore slurry was then agitated at the required
temperature using a hot magnetic plate. Except where
otherwise cited, 2 h leaching time was allowed while a
solid/liquid ratio of 1:12 was used. At the end of each
leaching experiment, the slurry was filtered, and the
leach liquor was analyzed for manganese and associated
metal values.
The leaching efficiency was calculated by referring the
leached metal amount in the leach liquor to its original
input value.

189

material, the dissolved components were dissolved in HCl

and made up to volume. Proper aliquots of the latter were
then used for elemental analysis as follows: Trace element
analyses for Cu, Zn and Al were performed using Unicam-969 atomic absorption spectrophotometer at the
following wavelengths: 222.60 nm Cu, 307.60 nm Zn,
309.30 nm Al. Manganese was aspirated through a nebulizer in the presence of La+ 3 as a releasing agent at
wavelength 403.10 nm. The measurements were carried
out in air/acetylene flame. Repeated analysis in-house and
international standards gave a good reproducibility of
standard deviation equal to 0.57. Other major elements
were analyzed using standard analytical methods for rock
analysis, (Marczenko, 1986).
3. Leaching results and discussion
3.1. Effect of HCl concentration
A series of leaching experiments was carried out at
different HCl concentration (1.25 to 3.25 M). The other
leaching conditions were fixed at 0.4 M H2O2, a solid/
liquid ratio of 1:12 at 95 C for 2 h and an ore grain size
of 200 mesh ( 74 m). From the obtained leaching
efficiencies as shown in Fig. 1, it is clear that as the HCl
concentration increases, the dissolution efficiencies of
all the studied metal values increase. Thus, at 2 M acid
concentration, the economic metal values of Mn, Cu and
Zn are almost completely dissolved while the leaching
efficiency of Al attains 84.8%. At this acidity level, the
dissolved iron content amounts to only 16%. Increasing
the HCl concentration to just 2.25 M slightly improved
the leaching efficiency of Al to 86.3%; however, iron
dissolution amounted to about 40%. A further increase in
the acid molarity to 2.75 M resulted in almost complete
iron leaching with little change in aluminium. It is

2.3. Analytical procedures

2.3.1. Analysis of the ore material
The ore material was completely analyzed for its
major and minor constituents after its complete dissolution in HNO3HClO4 acid mixture and using HF acid for
silica removal. After complete dryness of the opened ore

Fig. 3. Effect of time upon the leaching efficiencies. (2 M HCl, 0.4 M

H2O2, 95 C, 1/12 pulp density, 74 m).

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M.N. El Hazek et al. / Hydrometallurgy 84 (2006) 187191

concluded that gibbsite is dissolved whilst the unleached

Al (< 10%) corresponds to some clay minerals in the ore
material. Therefore an acidity of 2 M HCl is sufficient for
almost complete recovery of the four metals studied, yet
keeping iron dissolution to minimum.
3.2. Effect of H2O2 concentration
In order to evaluate the effect of H2O2, a second series
of leaching experiments was carried out using 2 M HCl.
These experiments were performed in the absence and
presence of different concentrations of H2O2 varying from
0.2 to 1.0 M.
The other leaching conditions were fixed at a solid/
liquid ratio of 1/12 at 95 C for 2 h and using 74 m
ore grain size. From the obtained data shown in Fig. 2, it
is evident that about 67% Mn dissolved in the absence of
H2O2 together with about 80% Al, 65% Cu and 76% Zn.
Apart from Al, these results are indeed lower than the
corresponding yield in presence of 0.4 M H2O2. On the
other hand, increasing the H2O2 molarity beyond 0.4 M
has an adverse effect upon iron dissolution which increased to about 29% and 35% at 0.6 and 1.0 M H2O2
respectively.
It can be concluded that reduction of manganese(IV)
minerals to the bivalent state is necessary before their
dissolution, but manganese(II) minerals are readily
leached. However, in the ore minerals, manganese is
present in both the bivalent and tetravalent states.

Table 3
Effect of pulp density upon the leaching efficiencies (2 M HCl, 0.4 M
H2O2, 2 h, 95 C, 74 m)
Pulp
density

Leaching efficiency, %
MnO

Fe2O3

Al2O3

CuO

ZnO

79.99
85.17
98.00
98.00

61.00
76.00
99.90
99.90

70.16
79.51
84.80
85.00

1.00
9.00
16.00
22.54

83.54
90.71
98.60
99.80

01:08
01:10
01:12
01:14

Fig. 3, it is evident that only half an hour leaching time is

needed for leaching Mn, Cu and Zn, but the leaching
efficiency of Al decreased to 71.0% and Fe decreased to
11%. Therefore, 1 h leaching time could be considered
as optimum as this decreased both iron and aluminium
contamination in the liquor.
4. Effect of temperature
In order to reduce the heat energy and in turn the
leaching costs, three further leaching experiments were
carried out at room temperature, 60 C and 85 C under
the same leaching conditions previously used at 95 C.
Fig. 4 indicates that temperature plays an important role,
especially in case of Al and Cu leaching. Accordingly,
the extraction of aluminium decreased to only 16.9%
while that of copper decreased to about 55% at room
temperature. This compared to about 84% Mn and 91%
Zn extraction.

3.3. Effect of time

4.1. Effect of pulp density
In a trial to improve the leaching conditions, another
experimental leaching series was performed using <2 h
leaching time. In these experiments, the other leaching
conditions were kept fixed. From the results shown in

Working with the fixed concentration of 2 M HCl and

0.4 M H2O2 solution, another 3 leaching experiments
were performed at pulp densities of 1:8, 1:10 and 1:14
(i.e. the excess acid quantities varied by changing the
wt./vol. ratio). The results in Table 3 show that at 1:8
and 1:10 pulp ratios, the leaching efficiencies of all the
studied metal values decreased. Increasing the acid
amount by applying a pulp ratio of 1:14, did not affect
the leaching efficiencies of Mn, Al, Cu and Zn; but the
leaching of Fe was increased to about 22.5%. This result
supports the conclusion that some clay minerals, equivalent to about 13% of Al, are present in the working ore
material.
5. Conclusions

Fig. 4. Effect of temperature upon the leaching efficiencies. (2 M HCl,

0.4 M H2O2, 2 h, 1/12 pulp density, 74 m).

A reductive leaching process for Sinai low grade

manganese ore material has been successfully demonstrated for the first time using an optimum mixture of

M.N. El Hazek et al. / Hydrometallurgy 84 (2006) 187191

hydrochloric acid and hydrogen peroxide as reductant.

In the proposed leach system, relatively little iron was
leached from the goethite matrix but other associated
metal values were leached; namely Al present in gibbsite
as well as the Cu and Zn values replacing some Mn in its
minerals. The studied leaching factors were optimized as
2 M HCl and 0.4 M H2O2 at 6095 C for only 1 h
leaching time using ore ground to 200 mesh size. Almost
complete leaching efficiencies were realized under these
conditions for Mn, Cu and Zn together with about 81% Al
and only 14% Fe contamination. At ambient temperatures,
aluminium and iron dissolution decreased to about 17%
and 10% respectively, whilst manganese extraction decreased to 84%.
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