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Recovery of pure MnSO 4∙H 2O by reductive leaching of manganese from

pyrolusite ore by sulfuric acid and hydrogen peroxide

Article in International Journal of Mineral Processing · September 2011

DOI: 10.1016/j.minpro.2011.05.003

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International Journal of Mineral Processing 100 (2011) 116–123

Contents lists available at ScienceDirect

International Journal of Mineral Processing

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / i j m i n p r o

Recovery of pure MnSO4∙H2O by reductive leaching of manganese from pyrolusite ore

by sulfuric acid and hydrogen peroxide
A.A. Nayl a,⁎, I.M. Ismail b, H.F. Aly a
a
Hot Laboratory Center, Atomic Energy Authority. P.O. 13759, Inshas, Cairo, Egypt
b
Faculty of Engineering, Cairo University, Cairo, Egypt

a r t i c l e i n f o a b s t r a c t

Article history: Manganese leaching and recovery from pyrolusite ore, was investigated by using H2SO4 as a leachant and H2O2 as
Received 19 December 2010 a reducing agent. The effects of agitation, H2O2 concentration, H2SO4 concentration, liquid/solid mass ratio,
Received in revised form 20 February 2011 leaching time and reaction temperature on manganese recovery were studied. The optimal leaching conditions
Accepted 8 May 2011
were determined as 4.0 M H2SO4 and 0.8 M H2O2 using liquid–solid mass ratio of 5.0 for 90 min at 40 °C and ore
Available online 23 May 2011
particle size of 44–37 μm. Under these conditions, the leaching efficiency was 92.0% for Mn. It was found that the
Keywords:
use of H2O2 as a reducing agent for the reductive leaching of manganese increased the leaching rate. Analysis of
Manganese sulfate the experimental results indicted that the leaching process is fitted by a chemical reaction model in temperature
Reductive leaching range 20–40 °C, and at higher temperature, 45–70 °C, the diffusion reaction model prevails. Activation energies
Manganese ore for these models were calculated to be 49.5 kJ∙mol− 1 and 10.6 kJ∙mol− 1, respectively. Based on the experimental
Sulfuric acid results, a separation method and flow sheet were developed and tested to separate high purity MnSO4.H2O
Hydrogen peroxide (N 99.4%). Comparison between the present results and that reported in the literature are given.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction Several processes are reported to leach and recovery of manganese

from its ores. When manganese is present in its divalent soluble form
Manganese is a strategically important nonferrous element used (Mn+ 2), manganese salts are generally obtained directly by acid leaching
for production of steel, ferromanganese, non-ferrous alloys, dry cell and when it is present in the insoluble form (Mn+ 4), reducing agents
batteries, paints and other chemicals. Increasing demand for this are necessary to obtain the soluble Mn+ 2 compounds into solution
metal is leading to a fast depletion of their rich sources and has (De Michelis et al., 2009). Leaching of manganese from its ores with
therefore caused a great deal of attention to be devoted to improve sulfuric acid is one of the common known approaches (Belyi et al., 2006).
recovery from its ore and slags (Elsherief, 2000) Also, manganese salts Many studies were carried out by using various reducing agents
are important for the human health to maintain healthy nerves and such as natural gases, oxalic acid, methanol, carbohydrate, coal,
immune systems and to regulate blood sugar but excessive intake of graphite, sulfur dioxide, hydrogen, cornstalk, etc., and then the
manganese can damage the nervous system of the human body product was leached with sulfuric acid (Misra and Khangaonkar,
(Wang et al., 2010) . Subsequently, the leaching of manganese sources 1975; Guven and Hurman, 1995; Momade and Momade, 1999; Trifoni
is increasingly becoming important in the global metallurgical et al., 2000; Sahoo et al., 2001; Cheng et al., 2009). Leaching after
scenario owing to this sharp increasing demand (Frank Pettersson roasting manganese ore in presence of sulfatising agent such as SO2,
et al., 2009) and the recovery of manganese is important in order to FeS2 and Na2SO3 with hot water was also investigated (Masayasu et
protect our environment and health of humans and live stock from al., 1991; Jana et al., 1999). Jiang et al. (2003, 2004) studied the
serious health risk. leaching of manganese ore by sulfuric acid solution in the presence of
Manganese sulfate is important manganese compound produced hydrogen peroxide. They found that hydrogen peroxide is critical to
in largest amounts and is used as a raw material in the production of the simultaneous leaching of manganese at room temperature, and it
some manganese compounds in dyes, pharmaceuticals, textiles, and plays a main role as a reducing agent for manganese dioxide.
different industries. Therefore, the leaching of manganese ore for the In Egypt, manganese ore (pyrolusite) is present mainly in two
production of manganese sulfate is very important from the localities. The first location is West Central Sinai (Om Bogma area)
economical point view (Abali et al., 2007). with reserves of 4.1 million tons and the second located in the Eastern
Desert concentrated mainly in the southern east part of the Eastern
Desert with reverses of 2.4 million tons ( Rashad, 2006).
⁎ Corresponding author at: Hot Labs Centre, Atomic Energy Authority, P. Code 13759,
Ismail et al. (2004) studied the leaching of low grade Om-Bogma,
Cairo, Egypt. Tel.: + 20 2 3775 5410; fax: + 20 2 4462 0796. Sinai, Egypt, manganese ore by sulfuric acid using either sawdust or
E-mail address: [email protected] (A.A. Nayl). lactose as reducing agent. Both sawdust and lactose were used as

0301-7516/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.minpro.2011.05.003
 Author's personal copy

A.A. Nayl et al. / International Journal of Mineral Processing 100 (2011) 116–123 117

effective reducing agents during direct acid leaching of low grade Table 1
manganese ore. The optimum leaching conditions were; −100 mesh Chemical composition of the manganese ore.

particle size, 90 °C temperature, 90 min, 30% acid concentration, 1.5 Compound wt.% Compound wt.%
acid/MnO2 stoichiometric ratio. They, also, reported that, the
MgO 11.77 K2O 0.81
advantage of the direct reductive leaching (reduction–leaching in MnO (total Oxide) 51.32 Al2O3 1.97
solution) over the other reduction processes are the reduction and TiO2 0.40 S 0.35
leaching steps could be carried out in one step, and the produced CaO 3.5 SiO2 6.81
Fe2O3 23.05
manganese sulfate solution could be purified in the same system.
Leaching of manganese from a relatively low-grade ore located in
Um-Bogma, Sinai, was studied using molasses as reducing agent in
nitric acid solution (Lasheen et al., 2009). Leaching parameters for the unless otherwise stated the particle size fraction of 44–37 μm (main
system were optimized as 2.7 M HNO3 in the presence of molasses at fraction) is used. At first, the manganese ore was washed by mixed
95 °C with a solid–liquid ratio of 1:12 for 2 h. thoroughly with double distilled water in the beaker (liquid/solid
In the present work, a reductive leaching and recovery of mass ratio 4/1) to remove any soluble materials and then the mixture
manganese from pyrolusite manganese ore obtained from Morgan was dried in the muffle furnace to 100 °C. After drying at 100 °C for
Chemical Company, Egypt in sulfuric acid solution in the presence of 1.0 h, the leaching experiments were carried out in closed glass flasks
hydrogen peroxide as reducing agent was investigated. Based on the using 100 g ore sample and 500 g of 4.0 M H2SO4 and mechanically
experimental results, a process for recovery and preparation of high mixed at 350 rpm with 50 g of 0.8 M H2O2 at 40 °C for 90 min, unless
purity MnSO4 ∙ H2O was developed and tested. otherwise specified. At the end of each leaching experiment, the slurry
was filtered and the filtrate (leach liquor) was analyzed for leached
2. Experimental manganese and other associated metal values.
Manganese content in the leach solution was determined by
2.1. Materials and analysis inductively coupled plasma optical emission spectrometry (ICP-OES)
using the system ULTIMA-2 ICP, Jobin Yvon, France. All chemical
Upgraded manganese ore sample was supplied from Morgan reagents employed were of analytical grade and de-ionized water was
Company for Chemicals, Cairo, Egypt. The bulk chemical composition used through the experiments whenever needed.
of the manganese ore sample used in this study was determined using Manganese oxides are reduced from high-valance states to low-
Energy Dispersive X-ray Fluorescence (EDX) spectrometer Model valance states according to the following (Cheng et al., 2009):
(OXFORD) attached with SEM Model JEOL-JSM-5400. XRD analysis
was carried out using a Shimadzu (Japan) diffractometer (LA5X) at MnO2 ↔Mn2 O3 ↔Mn3 O4 ↔MnO ð1Þ
the Central Laboratories of the National Radiation Centre for Research
It is known that manganese can exist in acidic solution as Mn 2+. In
and Technology. The conditions of these measurements were
order to leach manganese, H2O2 was selected because it is thermo-
obtained using Cu-Kα radiation and Ni filter. Analysis of the
dynamically able to function as a reducing agent for MnO2. The
diffraction patterns was carried out by the whole-powder pattern-
chemistry of H2O2 in aqueous solution is summarized by the following
fitting computer program, intra-connected to the system.
reactions (Cotton and Wilkinson, 1988):
XRD pattern of the ore sample, Fig. (1), showed that the ore used is
mainly composed of pyrolusite (MnO2). Chemical analysis of the ore is þ −
given in Table 1, indicated that it contain mainly 51.32% manganese as H2 O2 þ 2H þ 2e ↔2H2 O ð2Þ
a total manganese oxides (MnO) , 23.05% iron as Fe2O3, 11.77% MgO
and 6.8% SiO2. The table showed also that there are small amounts of
the oxides of Ca, Al, Ti and K. þ −
O2 þ 2H þ 2e ↔H2 O2 ð3Þ
2.2. Procedure

Manganese ore sample was first crushed, ground and screened to  −

HO 2  þ H2 O þ 2e− ↔3OH ð4Þ
provide raw material sized to different particle size fractions and

2H2 O2 ↔2H2 O þ O2 ð5Þ

HO −2 is the hydrolysis product of H2O2 according to the following

reaction (Jiang et al., 2003);

þ −
H2 O2 ↔H þ HO2 ð6Þ

In acidic solution, the chemical leaching of MnO2 can be described

according to the following reactions:

þ − þ2
MnO2 þ 4H þ 2e ↔Mn þ 2H2 O ð7Þ

Combine Eqs. (3) and (7), the reaction for the reductive leaching of
MnO2 by H2O2 in acidic solution can be described as the following
reaction:

þ þ2
Fig. 1. XRD pattern of manganese ore. MnO2 þ H2 O2 þ 2H ↔Mn þ 2H2 O þ O2 ð8Þ
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118 A.A. Nayl et al. / International Journal of Mineral Processing 100 (2011) 116–123

The divalent manganese product is leached with sulfuric acid and Table 2
the major chemical reaction can be represented as following: Effect of particle size on the leaching percent of Mn and Fe.

Particle size

þ2 þ Element 20–10 μm 20–37 μm 44–37 μm 53–44 μm 62–53 μm 74–62 μm

Mn þ H2 SO4 ↔MnSO4 þ 2H ð9Þ
% Mn 92.1% 92% 92% 82.2% 78.4% 69%
% Fe 84.8% 84.6% 84% 83.7% 83.5% 83%

3. Results and discussion

tion, while the leaching of Fe is slightly increased with increase in
3.1. Leaching process H2O2 concentration.
These results can be explained on the fact that the pyrolusite ore is
3.1.1. Effect of agitation rate insoluble in H2SO4 solution in absence of a reducing agent (Ismail et
The effect of agitation rate on Mn recovery from the manganese al., 2004), but in the presence of H2O2, which used as reducing agent,
ore was carried out at agitation rate ranged from 100 to 600 rpm using Mn + 4 is converted to Mn + 2 which was easily leached in sulfuric acid
4 M H2SO4, a liquid/solid mass ratio of 5/1 at 40 °C for 90 min with solution according to Eqs. (7, 8).
particle size of 44–37 μm and 0.8 M H2O2. The results obtained given
in Fig. (2) show that the leaching of Mn and Fe increases with the
increase of the agitation rate, the leaching becomes almost indepen- 3.1.4. Effect of H2SO4 concentration
dent of the agitation rate at rpm higher than 350 rpm. Therefore, The effect of H2SO4 concentration, in the range 0.5–8.0 M, on
subsequent experiments were performed at agitation rate of 350 rpm leaching of Mn and Fe was studied using liquid/solid mass ratio of 5/1,
to ensure that the influence of external mass transfer is negligible. 40 °C, 90 min with particle size of 44–37 μm and 0.8 M H2O2 at
agitation rate of 350 rpm. Fig. (4), reveals that the leaching of Mn
increases from 8% to 92% as H2SO4 concentration increases from 0.5 M
3.1.2. Effect of particle size
to 4.0 M. This is followed by more or less constant leached fraction of
The effect of particle size was studied by taking different particle
Mn with further increase in H2SO4 concentration. In case of iron, the
size fractions: 20–10 μm, 37–20 μm, 44–37 μm, 53-44 μm, 62–53 μm
fraction leached was found to increase by increasing acid to reach
and 74–62 μm using 4 M H2SO4 with liquid/solid mass ratio of 5/1 at
about 95% at 8.0 M sulfuric acid. These results indicated that the
40 °C for 90 min at agitation rate of 350 rpm and 0.8 M H2O2, Table 2.
leaching percent increased with the increase of H2SO4 concentration
The data obtained shows that the leaching of Mn increases as the
which accelerate leaching rates resulted from the high H2SO4
particle size decreases. However, beyond 44–37 μm, the particle size
concentration (Song et al., 2010). Further, high acid concentration
had no effect on leaching of Mn. Thus, very fine grinding of sample is
will enhance the reduction of MnO2 to Mn + 2, Eqs. (7, 8), as a result of
not necessary for leaching of Mn. For Fe, the investigated particle size
the increase in hydrogen ion concentration and subsequently Mn + 2
range had slight effect on leaching of Fe.
will be easily released into the solution.
As shown from Eq. (7), manganese reduction leaching consumes
3.1.3. Effect of H2O2 acid and is self-catalyzed which referred to as the conversion of the
The effect of H2O2 on the leaching of Mn from manganese ore was element among its different valence states catalyzed by the element
carried out at different H2O2 concentrations (0.1–1.2 M) with 4 M itself. In this work, the reduction leaching of the tetravalent and
H2SO4, a liquid/solid mass ratio of 5/1, 40 °C for 90 min, agitation rate trivalent manganese to divalent manganese under acidic conditions is
of 350 rpm using particle size of 44–37 μm. Fig. (3), shows that the catalyzed by the presence of divalent manganese, as in Eq. (1),
concentration of H2O2 plays a critical role in the leaching process of resulting in a much faster conversion by a cascading action (Chi et al.,
both Mn and Fe. In the absence of H2O2, the leaching percent of Mn 2002) . Therefore, when H2SO4 is used as a leaching agent for
and Fe is only about 25% and 65%, respectively. The leaching of Mn is
rapidly increased with increase in H2O2 concentration to reach 92% at
0.8 M H2O2 then decrease with further increase in H2O2 concentra- 1.0
FRACTION OF Mn and Fe DISSOLVED
FRACTION OF Mn and Fe DISSOLVED

1.0
0.8

0.8
Mn
0.6
Fe
Mn
0.6 Fe
0.4

0.4

0.2
0.2

0.0
0.0 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
0 100 200 300 400 500 600 700 H2O2 (M)
AGITATION RATE (rpm)
Fig. 3. Effect of H2O2 concentration on the leaching of Mn and Fe in 4M H2SO4 solution
Fig. 2. Effect of agitation rate on the leaching of Mn and Fe in 4M H2SO4 solution at 40 °C. at 40 °C.

(liquid/solid) mass ratio = 5/1 time, min. = 90 min (liquid/solid) mass ratio = 5/1 time, min. = 90 min
particle size = 44-37 μm H2O2, M, = 0.8 M agitation rate, rpm = 350 rpm particle size = 44-37 μm
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A.A. Nayl et al. / International Journal of Mineral Processing 100 (2011) 116–123 119

1.0 1.0
FRACTION OF Mn and Fe DISSOLVED

FRACTION OF Mn and Fe DISSOLVED

0.8 0.8

Mn Mn
0.6 0.6
Fe Fe

0.4 0.4

0.2 0.2

0.0 0.0
0 1 2 3 4 5 6 7 8 9 0 2 4 6 8 10
[H2SO4], (M) (LIQUID/SOLID), mass ratio

Fig. 4. Effect of H2SO4 concentration on the leaching of Mn and Fe from manganese ore Fig. 6. Effect of liquid/solid mass ratio on the leaching of Mn and Fe in 4M H2SO4
at 40 °C. solution at 40 °C.

(liquid/solid) mass ratio = 5/1 time, min. = 90 min particle size = 44-37 μm [H2O2], M = 0.8 M
agitation rate, rpm = 350 rpm particle size = 44-37 μm agitation rate, rpm = 350 rpm time, min = 90 min
[H2O2], M = 0.8 M

3.1.5. Effect of leaching time

manganese ore (pyrolusite), the following chemical reactions for The effect of leaching time on the leaching of Mn and Fe was
manganese and iron need to be considered (Chi et al., 2002): carried out within the period range from 10 to 150 min with 4 M
H2SO4 , 0.8 M H2O2 at a liquid/solid mass ratio of 5/1, 40 °C, agitation
FeO þ H2 SO4 ↔FeSO4 þ H2 O ð10Þ rate of 350 rpm and particle size of 44–37 μm. The data obtained are
shown in Fig. (5), which show that at the first 20 min about 45% and
58% of the Mn and Fe are leached, respectively. After 90 min, about
92% of Mn and 84% of Fe were leached and after 100–120 min, a slight
MnO2 þ 2FeSO4 þ 2H2 SO4 ↔MnSO4 þ Fe2 ðSO4 Þ3 þ 2H2 O ð11Þ increase in the leaching fraction of Mn to reach about 93–94% was
observed. Accordingly, it can be recommended that the 90 min
leaching time would be adequate for the process.
The leaching of Mn from pyrolusite manganese oxide ore by some
2MnOðOHÞ þ 2FeSO4 þ 3H2 SO4 ↔2MnSO4 þ Fe2 ðSO4 Þ3 þ 4H2 O ð12Þ
reductants may involve at least four steps in series, hydrolysis,
diffusion of the reductant from the main bulk of the solution through
the boundary layer to active sites of the solid, i.e. to manganese ore
Fe2 O3 þ 3H2 SO4 ↔Fe2 ðSO4 Þ3 þ 3H2 O ð13Þ

1.0 1.0
o
FRACTION OF Mn and Fe DISSOLVED

20 C
FRACTION OF Mn DISSOLVED

o
0.8 25 C
0.8 o
30 C
o
35 C
Mn 0.6
0.6 o
Fe 40 C
o
45 C
0.4 o
0.4 50 C
o
60 C
o
0.2 0.2 70 C

0.0 0.0
0 20 40 60 80 100 120 140 0 20 40 60 80 100 120 140 160 180
TIME, (min) TIME, min

Fig. 5. Effect of leaching time on the leaching of Mn and Fe in 4M H2SO4 solution at 40 °C. Fig. 7. Effect of temperature on the leaching of Mn in 4M H2SO4 solution at different time.

(liquid/solid) mass ratio = 5/1 [H2O2], M = 0.8 M particle size = 44-37 μm (liquid/solid) mass ratio = 5/1
agitation rate, rpm = 350 rpm particle size = 44-37 μm [H2O2], M = 0.8 M agitation rate, rpm = 350 rpm
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120 A.A. Nayl et al. / International Journal of Mineral Processing 100 (2011) 116–123

0.25
1.0
o o
20 C 45 C
FRACTION OF Fe DISSOLVED

o o
25 C 0.20 50 C
0.8 o
o
30 C 60 C

1-2/3X-(1-X)2/3
o
o 70 C
35 C 0.15
0.6 o
40 C
o
45 C 0.10
o
0.4 50 C
o
60 C 0.05
o
0.2 70 C

0.00
0 20 40 60 80 100 120
0.0 TIME, hr
0.0 0.5 1.0 1.5 2.0 2.5 3.0
TIME, hr
Fig. 10. Plots of 1 − 2/3X − (1 − X)2/3 vs time for Mn leaching at different temperatures
(45–70 °C) in 4 M H2SO4 solution.
Fig. 8. Effect of temperature on the leaching of Fe in 4M H2SO4 solution at different time.
3.1.7. Effect of leaching temperature
particle size = 44-37 μm (liquid/solid) mass ratio = 5/1 In order to study the effect of temperature on the leaching process
[H2O2], M = 0.8 M agitation rate, rpm = 350 rpm of Mn and Fe from pyrolusite manganese ore, different experiments
were carried out at the temperature range 20–70 °C with different
grains, the nucleation of products at the active sites, and hydration of agitation time with 4 M H2SO4, liquid/solid mass ratio of 5/1, 0.8 M
the products and diffusion into the leaching solution. Therefore, the H2O2, agitation rate of 350 rpm and particle size of 44–37 μm. The
leaching process is a time dependent process (Ismail et al., 2004). results obtained are illustrated in Figs. (7, 8) for Mn and Fe,
respectively. It is observed that as the temperature increases the
3.1.6. Effect of liquid/solid mass ratio leaching percent of Mn increases from 44% at 20 °C to 92% at 40 °C,
Leaching of Mn and Fe from pyrolusite manganese ore by 4 M this may be due to the accelerating reaction rate of MnO with H2SO4.
H2SO4, 0.8 M H2O2 at 40 °C, agitation rate of 350 rpm, particle size of As leaching temperature increase from 40 °C to 70 °C, the leaching of
44–37 μm for 90 min was tested by varying the liquid/solid mass ratio Mn increased dramatically with time to reach maximum leaching
from 1/1 to 7/1. The data obtained are given in Fig. (6). It is observed after 1.0 h to reach more or less constant maximum leaching
that the leaching percent of Mn and Fe increased rapidly with the indicating the completion of leaching reaction. For Fe, with the rising
increase of the liquid/solid mass ratio from 1/1 to 5/1. At liquid/solid in the temperature, the chemical reactions (10, 13) were accelerated
mass ratio 1/1, Mn extraction is too low because sulfuric acid amount and the leaching recovery was also improved.
is insufficient to obtain significant manganese dissolution while as the In order to obtain the kinetic equation and apparent activation
liquid/solid mass ratio increase, the amount of sulfuric acid is energy for pyrolusite leaching by H2SO4 in the presence of H2O2, the
sufficient to leach manganese from the ore. When the liquid/solid experimental data in Fig. 7, were processed and correlated to various
mass ratio was higher than 5/1, the leaching of Mn slightly increased, kinetic models for solid–liquid reactions.
since most of manganese was leached into the solution to form MnSO4 The leaching rate of manganese was analyzed in terms of the
solution (Song et al., 2010), as in reaction (9), and leaching of Fe shrinking core model for reaction control under the assumption that
remained increase. the pyrolusite ore sample is homogenous spherical solid phase. The

0.7
-4.5

0.6 o
20 C
o
25 C -5.0
1/3
0.5 o 1- (1- X)
30 C
2/3
o 1-2/3X - (1- X)
35 C
1- (1-X)1/3

0.4 -5.5
o
40 C
ln k

0.3
-6.0
0.2

0.1 -6.5

0.0
0 20 40 60 80 100 -7.0
2.8 3.0 3.2 3.4 3.6
TIME, min
(T-1) x 10-3 (k-1)
Fig. 9. Plots of 1 − (1 − X)1/3 vs time for Mn leaching at different temperatures (15–40 °C)
in 4 M H2SO4 solution. Fig. 11. Arrhenius plot for manganese leaching in 4 M H2SO4.
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A.A. Nayl et al. / International Journal of Mineral Processing 100 (2011) 116–123 121

Table 3
Comparison between the conditions and products from recent studies.

Work Leaching agent Leaching time, min Agitation speed (rpm) L/S ratio Temperature (°C) Ea (kJ mol− 1) Product purity (%)

(Momade and Momade 1999) (0.3 M H2SO4 + methanol) 30 500 – 160 36.1 N 70.0
(Ismail et al., 2004) (30%H2SO4 + sawdust) 90 700 1.5/1 90 – 92.5
(Jiang et al., 2003) (0.9 M H2SO4 + 0.8 H2O2) 120 950 20/1 25–60 – 98
(El Hazek et al., 2006) (2.0 M HCl + 0.4 H2O2) 60 – 12/1 60–95 – N 97
(Lasheen et al., 2009) (2.7 M HNO3 + molass) 120 – 12/1 95 – 98
Present work (4.0 M M H2SO4 + 0.8 H2O2) 90 350 5/1 40 49.5 N 99.4

following chemical reaction controlled kinetic equation was examined, Table 3 compares the data between some recent works reported on
(Levenspiel, 1972) , and was found to fit the data best till 40 °C with a the reductive acid leaching of manganese ore and the results obtained in
correlation coefficient more than 0.96 (for temperature range 20–40 °C) this work. It is clear that the leaching of treated pyrolusite ore under our
as shown in Fig. 9. conditions has some advantages over other studies, particularly related
to the high purity of product produced (MnSO4.H2O in our study and
1=3 manganese in the other study) and the lower temperature and liquid/
1−ð1−XÞ = kc t ð14Þ
solid mass ratio of the leaching process.
where X is the fraction reacted, and kc is chemical reaction rate.
At temperature higher than 40 °C the experimental results do not
3.2. Recovery of manganese from leach solution
validate this chemical reaction controlled process. Subsequently,
these leaching results at temperature higher than 40 °C were
Based on the results obtained, a flow sheet for separation of
processed in terms of the diffusion-controlled kinetic equation given
manganese and iron form the ore was developed and tested as shown
by the following;
in Fig. (12). In this concern, ammonium hydroxide has been used for
2=3
1−2 = 3X–ð1−XÞ = kd t ð15Þ

where, kd is the apparent diffusion reaction rate constant (min − 1), t is

leaching time (min) and X is the fraction reacted. Pyrolusite Ore (100g)
The results obtained are presented in Fig. (10), as a relation 39.74g Mn, 16.14 g Fe
between 1 and 2/3X − (1 − X) 2/3 against time (t) gave straight lines at
different temperatures and pass through the origin which verify
Eq. (15) and suggests that under these conditions, the reaction is
controlled by diffusion. The correlation coefficients of these straight Leaching 4 M H2SO4, 40 oC
lines (for temperature range 45–70 °C) are 0.99.
1.5 hr, L/S: 5, 0.8M H2O2
These results suggest that the leaching rate of manganese from
pyrolusite ore by H2SO4 in the presence of H2O2 is firstly controlled by
the surface chemical reactions alone till 40 °C, then as the temperature Residue
Filtration
increase from 45 to 70 °C the leaching rate is controlled by the diffusion 28.5g Mn, 10.1g Fe
of reactants or products diffusion through the “product” layer. This may 4.2g Mg, 4.0g silica
be due to the fact that, for oxidizing acid like H2SO4 the validity of
diffusion controlled model may be influenced by formation of metal
oxides in the matrix (Ige et al., 2005). Precipitate 4.0 M NH4OH
Precipitation
For estimation of the activation energy, the reaction between the (Fe, Mg,..etc)
overall rate constant and temperature from Eqs. (14, 15) can be (pH=9)
expressed by Arrhenius equation, as the following;
Filtrate, boiling 100oC
Ea = RT
k = Ae ð16Þ
Precipitation
where k is the reaction rate constant, A is the frequency factor, Ea is
the apparent activation energy and R is the gas constant.
Rate constants for different temperatures at different time were
calculated from Figs. (9,10) for the both models. A plot of ln k versus 1/ 200 oC, 1 hr
Calcination
T for the two models is linear (Fig. 11) and the apparent activation
energy (Ea) was determined from the slope and it is found to equals
49.5 kJ/mol for chemically control mechanism, and equals 10.6 kJ/mol
for diffusion control mechanism.
The relatively high value of activation energy obtained, 49.5 kJ/
MnSO4.H2O
mol, for leaching of manganese by H2SO4 in the presence of H2O2 is (150.6g) (>99.4%)
clearly indicative of a chemical controlled reaction in the temperature (≤0.47g FeSO4)
range 20–40 °C. Further, at higher temperature, 45–70 °C, the
relatively low value of activation energy, 10.6 kJ/mol, for the leaching
process, indicates that the chemical controlled process is followed by Fig.12. Schematic flow diagram of the leaching and separation of manganese sulfate
diffusion controlled mechanism. from pyrolusite ore.
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122 A.A. Nayl et al. / International Journal of Mineral Processing 100 (2011) 116–123

separation of manganese from leach solution. After leaching 100 g

treated pyrolusite ore by 500 g 4 M H2SO4 at liquid/solid mass ratio of
5/1 with 0.8 M H2O2 at agitation rate of 350 rpm and particle size of
44–37 μm at 40 °C, the resulted leaching solution was found to
contain 28.5 g manganese, 10.1 g iron, 4.2 g magnesium, and 4.0 g
silica with 2.4 g of other impurities.
Different experiments were carried out in order to obtain suitable
conditions for removal of manganese from leaching solution by
precipitation of other metal species using 4.0 M ammonium hydrox-
ide at room temperature. The original pH of the solution is 1.8. As the
pH is raised from 1.8 to 8.0, Fig. (12), iron precipitates as the
hydroxide. As the pH increase higher than 9.0, manganese began to
precipitates along with the iron. From Fig. (13), it can be seen that
even at pH 2.5, only 6.4% of iron and 0.0% of manganese are removed
and with the increase of pH from 2.5 to 8.0, the removal percent of
iron (precipitation) increases to 98.2% with 0.7% of manganese. But at
pH 9.0, about 99.1% of iron and 4.6% of manganese are precipitated
from leaching solution. After filtration, the manganese value left
behind in the filtrate was precipitated by evaporation and boiling the
filtrate at 100 °C to1 /2 of it volume then the obtained precipitate was Fig. 14. X-ray diffraction pattern of the product MnSO4 ∙ H2O.
dried at 200 °C for 1 h.
The resulted powder obtained showed that the percentage precip-
itation of manganese sulfate was N99.4% (150.26 g MnSO4 ∙ H2O), 200 °C for 1 h. The obtained pure manganese sulfate precipitate was
containing less than 0.1% iron (≤0.47 g FeSO4) and b0.4%(≤0.8 g) of found to contains N99.4% (150.26 g MnSO4 ∙ H2O), with less than 0.1%
other impurities. The X-ray diffraction pattern of the product MnSO4 ∙H2O iron (≤0.47 g FeSO4) and b0.4% (≤0.8 g) of other impurities.
is shown in Fig. 14. Kinetic analysis of the experimental results indicated that the
leaching process is fitted by a chemical reaction model in temperature
range 20–40 °C, and at higher temperature range, 45–70 °C, the
4. Conclusions diffusion reaction model prevails. Activation energies for these
models were calculated to be 49.5 kJ∙mol −1 and 10.6 kJ∙mol −1.
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