Hydrometallurgy 101 (2010) 5863

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Hydrometallurgy
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 / h yd r o m e t

Investigation of methods for removal and recovery of manganese in

hydrometallurgical processes
Wensheng Zhang , Chu Yong Cheng, Yoko Pranolo
The Parker Centre/CSIRO Process Science and Engineering, 7 Conlon Street, Waterford, WA 6152, Australia

a r t i c l e

i n f o

Article history:
Received 23 July 2009
Received in revised form 26 November 2009
Accepted 27 November 2009
Available online 3 December 2009
Keywords:
Manganese removal and recovery
Oxidative precipitation
Sulphur dioxide

a b s t r a c t
Manganese is a major impurity which needs to be removed in many hydrometallurgical processes while
some waste solutions are also important secondary manganese sources. Precipitation methods were
investigated for the removal and recovery of manganese from a typical nickel laterite waste solution.
Hydroxide precipitation alone was not an attractive option for the recovery and removal of manganese to
very low levels due to its poor selectivity. Carbonate precipitation could be used for partial recovery of
manganese from the waste solutions, but not desirable for removal of manganese to very low levels due to
substantial co-precipitation of calcium and magnesium. Aeration at appropriate pH or using pure oxygen did
enhance manganese removal, but this approach remains either kinetically slow or expensive due to the cost
of oxygen. The oxidative precipitation with SO2/air is very promising for both removal and recovery of
manganese from laterite waste solutions and was investigated in detail to identify optimum conditions. It
was found that solution pH was the most critical factor for maximising the rate of the oxidative precipitation
with little co-precipitation of magnesium and calcium impurities. The SO2/air (O2) system worked efciently
in a nearly neutral pH range of 67, indicating that the system was favourable for treatment of metallurgical
waste solutions. SO2/air (O2) ratio is another important factor for maximising the oxidising capacity of the
SO2/air (O2) system and the utilisation of SO2 and O2 reagents with minimum consumption of base reagents
for neutralisation. In this paper, potential commercial applications of these methods and their constraints are
discussed.
2009 Elsevier B.V. All rights reserved.

1. Introduction
Manganese is an impurity in many hydrometallurgical processes
and needs to be removed to an acceptable level (normally b10 mg/L)
in the waste stream to comply with environmental guidelines for
discharge. These waste efuents containing manganese could also be
secondary sources of manganese. Manganese demand has been
increased in recent years driven by soaring growth of the world
steelmaking industry. This makes the recovery of manganese from
secondary sources such as industrial waste solutions economically
viable. Waste streams in nickel laterite processing containing 25 g/L
manganese with magnesium and calcium as major impurities are such
a potential source. In recent years, an increasing world demand for
nickel and cobalt has motivated the development of processes for the
treatment of nickel laterite ores. Worldwide, more than ten nickel
projects are in different stages of development (Manchanda, 2008;
Wills, 2008), including Cawse (Australia), Murrin Murrin (Australia),
Coral Bay (Philippines), Moa Bay (Cuba), Ravensthorpe (Australia)
and Goro (New Caledonia). The recoverable manganese from

Corresponding author.
E-mail address: wensheng.zhang@csiro.au (W. Zhang).
0304-386X/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2009.11.018

downstream processes of laterite ores is estimated to be more than

120,000 tonnes/year. However, a cost effective method and process is
not available to remove and recover manganese of relatively low
concentrations from a large volume of solution containing a large
amount of magnesium (N10 g/L).
In recent years, research work on separation and recovery of
manganese from leach liquors by solvent extraction has been carried
out at the Parker Centre (Cheng, 2000; Cheng et al., 2004; Ward et al.,
2004). Solvent extraction systems can be applied to both recovery and
separation of manganese from other metals. Di-2-ethylhexyl phosphoric acid (D2EHPA) has been identied and is one of cheapest
reagents for selective extraction of manganese over other metals such
as nickel, cobalt and magnesium. However, D2EHPA cannot separate
manganese from calcium. Synergistic SX systems offer better
selectivity for purication of manganese solutions, but the organic
systems are generally more costly due to the use of expensive
synergists such as hydroxyoxime and pyridinecarboxylate esters.
Thus capital and reagent costs may limit its application for the
recovery of manganese from waste solutions containing a low
concentration of manganese. More recently, the methods for the
separation and recovery of manganese from leach and waste solutions
have been reviewed (Zhang and Cheng, 2007a,b,c). The major
methods for recovery of manganese from solutions containing one

W. Zhang et al. / Hydrometallurgy 101 (2010) 5863

or more of the metals such as iron, zinc, copper, nickel and cobalt
include solvent extraction, hydroxide precipitation, carbonate precipitation, and oxidative precipitation. The challenge to remove and
recover manganese by a precipitation method remains the relatively
low manganese concentrations compared to a large amount of
impurities such as magnesium. The co-precipitation of magnesium
and other impurities with manganese would result in substantial
increase in consumption of neutralisation reagents and therefore,
increased operating cost. Selectivity and kinetics for removal and
recovery of manganese by precipitation are two key factors of concern
in terms of capital and operating costs. Oxidative precipitation of
manganese to MnO2/Mn2O3 is highly selective, especially when the
solutions are free from iron. The main concern for the use of oxidative
precipitation method is the cost of oxidants such as ozone, Caro's acid,
and peroxy-disulfuric acid compared to the cheap SO2/air oxidising
mixture (Zhang et al., 2002; Mouton et al., 2007; Van Rooyen et al.,
2007; Menard and Demopoulos, 2007).
Although the solubility constants of the metals at 25 C are
available in the literature and used in modelling programs such as OLI
System and MINEQL Chemical Equilibrium Modelling System (Lide
and Frederikse, 2007; Monhemius, 1977; OLI Analyser 2.0, 2009;
Schecher and McAvoy, 2001), there are substantial differences in the
available solubility constants from different sources and predictions
by different modelling programs. The predictions is often difcult due
to the complex nature of a real solution in hydrometallurgical
processing for which ion interactions, kinetic factors and condition
controls have to be considered. In the present study, preliminary tests
were performed to compare different precipitation methods for the
removal and recovery of manganese from a typical synthetic nickel
laterite waste solution. The precipitation methods tested included
hydroxide precipitation, carbonate precipitation, and oxidative precipitations with air, O2 and SO2/air (O2). This paper presents the test
results, discusses the features of precipitation methods in terms of
selectivity and kinetics, and suggests suitable methods for further
development and potential applications.
2. Experimental
All the tests were carried out in a two-litre acrylic reactor with a
water jacket. A Eurostar Digital overhead stirrer and 40 mm diameter
Ruston turbine impeller was used for mixing. The air and SO2 gases
were supplied from a laboratory air hose and a SO2 cylinder,
respectively. The gas mixtures were pre-mixed in a ask before
entering the reactor and their ow rates were manually controlled
through gas regulators and calibrated ow meters. The temperature of
the solution was maintained by water circulation from a temperature
controlled water bath through the water jacket. Solution pH was
monitored by a thermo pH probe and automatically controlled by a
Walchem pH controller using an appropriately diluted base solution
for neutralisation. The solution Eh was monitored by a platinum
electrode with an Ag/AgCl reference electrode.
An investigation of precipitation behaviour of elements from a
synthetic upstream laterite solution after direct solvent extraction
(DSX) demonstrated that Fe(III), Al(III) and Cr(III) in the solution were
precipitated to below 0.2 mg/L (detection limits) when pH above 5.5
while the complete precipitation of Cu(II) and Zn(II) occurred at pH
above 6.5 (Zhu et al., 2009). Nickel and cobalt remaining in the rafnate
from the DSX fully continuous circuit were decreased to below 0.2 mg/L
(detection limit) under optimum conditions (Cheng et al., 2009).
Therefore, in this study, a typical nickel laterite waste efuent containing the main elements: 2 g/L Mn, 15 g/L Mg, 0.5 g/L Ca and 2 g/L Na was
synthesised by dissolving the required amounts of respective technical
grade MnSO4H2O, MgSO46H2O, CaCl2 (for easy dissolution), and
Na2SO4 in de-ionised water. For each test, the synthetic solution was
charged into the reactor and preheated to a desired temperature. The
solution was constantly stirred with addition of a base and/or oxidant.

59

Samples were taken regularly and ltered through a 0.45 membrane

lter. The liquor samples were sent for analysis of metals by Inductively
Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) at Analytical
Laboratory of CSIRO Minerals.
3. Results and discussion
3.1. Hydroxide precipitation with NaOH
Hydroxide precipitation was performed at 60 C with NaOH
solutions which were added slowly and the system pH was allowed
to approach equilibrium before taking samples. No attempt was made
to prevent air from entering the system and thus a small amount of
possible oxidative precipitation of Mn(II) by O2 in the air might occur.
The results are given in Table 1 and shown in Fig. 1.
Signicant precipitation of manganese occurred at pH 8.2 with 71%
Mn being precipitated together with about 5% Mg co-precipitation. Less
than 10 mg/L Mn in the solution was obtained at pHN 9 at which
magnesium concentration decreased to below 2.5 g/L and calcium to
0.5 g/L, corresponding to 90% Mg and 10% Ca co-precipitation,
respectively. These results suggest that hydroxide precipitation is not
efcient for the separation and recovery of manganese in the waste
efuents containing relatively low manganese concentration but high
magnesium concentration (N10 g/L) due to substantial co-precipitation
of magnesium and thus consumption of base for neutralisation.
The selectivity of manganese from magnesium and calcium can be
expressed by reactions (1) and (2), respectively (Lide and Frederikse,
2007):
2

MgOH2 Mn

CaOH2 Mn

MnOH2 Mg

MnOH2 Ca

LogK1 1:44

LogK2 7:36

where the selectivity constant K = [Me]/[Mn] was derived from the

solubility constants. The value of logK(Ca/Mn) is much larger than that of
logK(Mg/Mn), indicating that the precipitation of manganese hydroxide is
thermodynamically more favourable with respect to calcium than
magnesium. However, the log{[Mg]/[Mn]} and log{[Ca]/[Mn]} values
measured signicantly deviated from the K values, and varied with pH
(Table 1). These deviations suggest that the thermodynamic conditions
in the systems might be quite different due to the factors such as
temperature, kinetics and interactions among the ions.
3.2. Carbonate precipitation with Na2CO3
Carbonate precipitation was conducted at 60 C by adding Na2CO3
solution. The solution pH at each point was allowed to approach
Table 1
Hydroxide precipitation with NaOH at 60 C.
Equilibrium Concentration (mg/L) Precipitation (%)
pH
Mn
Mg
Ca
Mn
Mg
Ca

[Mg]/[Mn] [Ca]/[Mn]

3.5
6.0
6.5
7.1
7.6
8.2
8.5a
9.0a
9.1
9.6
10.1
10.5
11.0

1.8
2.1
2.8
2.9
2.2
1.3
1.3
1.5

1791
1813
1864
1870
1683
534
100
10
4
2
25
14
1

14546
14878
15070
14905
15593
14830
6000
2500
1474
145
237
124
11

534
527
544
546
576
568
500
500
478
128
95
52
39

Results estimated by interpolation.

0.0
0.0
0.0
0.0
9.98
71.4
95.0
99.5
99.8
99.9
98.7
99.3
99.96

0.0
0.0
0.0
0.0
0.0
4.9
60.0
83.3
90.6
99.1
98.5
99.2
99.9

0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
10.6
76.1
82.3
90.3
92.6

Log

2.2
1.9
0.7
0.7
1.9

60

W. Zhang et al. / Hydrometallurgy 101 (2010) 5863

Fig. 1. Metal concentrations in solutions after precipitation with NaOH at equilibrium

pH and 60 C.

constant before taking samples. Similar to the hydroxide tests, the

system was open to the atmosphere and agitated slowly to minimise
the possible oxidative precipitation by air. The results for the
carbonate precipitation are shown in Table 2 and Fig. 2.
Manganese precipitation occurred at pH N 7.5 and reached 90% at
pH 8 with about 13% Mg and 43% Ca co-precipitated. Compared to the
hydroxide precipitation, the carbonate precipitation was more
selective for manganese over magnesium than calcium. This generally
agrees to the equilibrium selectivity as indicated by reactions (3) and
(4) (Lide and Frederikse, 2007). The much larger value of logK(Mg/Mn)
than that of logK(Ca/Mn) suggests that the precipitation of manganese
carbonate is more thermodynamically favourable with respect to
magnesium carbonate than calcium carbonate. This is important for
obtaining better quality manganese precipitation product from the
waste efuent containing higher concentration of magnesium and
lower concentration of calcium.
2

MgCO3 Mn

CaCO3 Mn

MnCO3 Mg

MnCO3 Ca

LogK3 5:48

LogK4 2:35

However, the measured log{[Mg]/[Mn]} and log{[Ca]/[Mn]} values

(Table 2) were much lower than the K values. This suggests that more
magnesium may be dynamically precipitated under locally more
caustic conditions and need longer time to obtain equilibrium which is
normally impossible in a practical operation. Therefore, the kinetics

Table 2
Results for carbonate precipitation with Na2CO3 at 60 C.
pH

5.9
6.0
6.4
7.0
7.5
8.0
8.2a
8.5
9.0
9.5
a

Concentration (mg/L)

Precipitation (%)

Mn

Mg

Ca

Mn

Mg

Ca

[Mg]/[Mn]

[Ca]/[Mn]

1764
1739
1701
1725
1729
164
100
9
2
1

13800
13653
13418
13573
13603
11993
8000
3966
1907
1111

507
503
501
500
502
288
200
13
7
5

0.00
1.42
3.57
2.23
2.00
90.7
95.0
99.5
99.9
99.9

0.00
1.07
2.77
1.65
1.43
13.1
46.7
71.3
86.2
91.9

0.00
0.79
1.20
1.44
0.99
43.1
60.0
97.5
98.6
99.0

2.2
2.3
3.0
3.3
3.3

0.4
0.4
0.3
0.6
0.8

Results estimated by interpolation.

Log

Fig. 2. Metal concentrations in solution after precipitation with Na2CO3 at equilibrium

pH and 60 C.

of the precipitation is another issue for minimising co-precipitation of

magnesium and calcium in the industrial waste solutions.
The results suggest that carbonate precipitation could be used for
partial recovery of manganese from the waste efuent to obtain the
manganese carbonate product with fairly good quality, depending on
the concentration of manganese relative to magnesium in the solution
and balance between the yield and the product quality. Carbonate
precipitation was used in the development for the Boleo Copper
CobaltZincManganese Project to produce marketable manganese
carbonate product from the downstream solution containing about
23 g/L Mn, 7 g/L Mg and 0.62 g/L Ca (Dreisinger et al., 2005, 2006). This
is an example of favourable conditions for using carbonate precipitation
in terms of concentrations of metals concerned. In addition, manganese
carbonate is a favourable form which can, after drying, be sold directly to
the manganese industry or further processed for production of chemical
manganese dioxide (CMD), electrolytic manganese (EM) and electrolytic manganese dioxides (EMD).
For removal of manganese to below 10 mg/L by carbonate
precipitation, the solution pH needs be increased to above 8.5 at
which only about 4 g/L Mg and about 20 mg/L Ca remained in the
solution, corresponding to about 71% Mg and 97% Ca precipitations
(Table 2).
3.3. Oxidative precipitation with air and O2
The stability diagram for the MnH2O system shows that
manganese oxides of higher oxidation states such as MnO2, MnO
(OH) and Mn2O3 can be precipitated at lower pH range than
manganese hydroxide and carbonate in the presence of an appropriate oxidant (Zhang et al., 2002; Menard and Demopoulos, 2007).
However, kinetics of the oxidative precipitation is a critical factor for
practical application. Therefore, the rates of manganese oxidative
precipitation at different pHs were investigated using both air and
oxygen for comparison. As shown in Fig. 3, there was little manganese
precipitation with air at pH b 6. At pH 7, about 10% Mn precipitated in
30 min, but the precipitation eventually stopped afterwards. Equilibrium could be reached at this pH between the MnO(OH)/Mn2+ or
MnO2/Mn2+ redox couples and the O2/H2O redox couples. The rate of
precipitation increased with further pH increase, which was apparently caused by the hydroxide precipitation of manganese (Fig. 1),
and also evidenced by the lower Eh values measured, e.g. Eh b 280 mV
at 60 C and pH 8, corresponding to a stable region of Mn(OH)2 and
Mn3O4 in the EhpH diagram (Zhang et al., 2002; Menard and
Demopoulos, 2007). The enhanced precipitation of manganese with

W. Zhang et al. / Hydrometallurgy 101 (2010) 5863

61

almost linearly with reaction time at pH N 5 and below 70% Mn

precipitation, indicating that the oxidation did not strongly depend on
the Mn(II) concentrations remaining in the solution in the pH range.
This is a favourable kinetic feature of the SO2/air system for the
removal of manganese to low levels with high efciency. It is noted
that the oxidative precipitation rate signicantly decreased after
10 minutes at pH 7 (Fig. 4). It appeared that the side reactions (7)(9)
might became signicant and reached equilibrium with the oxidation
reactions (5) and (6) after the Mn(II) concentration in the solution
decreased to a certain value. This is supported by the steady linear
increase in the Mn(II) oxidation after 20 minutes at pH 7 (Fig. 4). The
precipitation rate increased again as pH further increased to
8 apparently due to joint hydroxide precipitation (Fig. 1).
Oxidation
2

2Mn

SO2 O2 3H2 O2MnOOH SO4 6H

Fig. 3. Comparison of Mn precipitation with air and oxygen.

2

Mn
air could possibly be accomplished in the pH range of 8.59 although
the oxidation rate was slow. In practical application, the oxidation rate
and the amount of co-precipitation of magnesium may need to be
balanced for economical considerations.
Compared to air, the use of O2 signicantly enhanced the rate of
manganese precipitation. The oxidation rate by O2 at 60 min is more
than double that by air at pH b 7 (Fig. 3). Less than 10 mg/L of residual
Mn (N99.5% precipitation) could be obtained in the relatively lower
pH range of 88.5 and thus less co-precipitation of magnesium, but
this is at the expense of use of expensive oxygen (Fig. 3).

3.4. Oxidative precipitation with SO2/air (O2)

3.4.1. Effect of pH
The effect of pH on the rate of manganese precipitation from the
synthetic solution was investigated in the range of 48. Compressed
air was sparged into 0.5 L of solution at a ow rate of 0.5 L/min and a
stirring speed of 1000 rpm at 60 C. Typical manganese precipitation
curves with 1.9% SO2 are shown in Fig. 4.
At pH below 5, the oxidation of Mn(II) was relatively slow and
eventually stopped. The oxidation rate became fast at pH N 5 and reach
maximum at pH 6.5 with 99.5% Mn(II) precipitation (b10 mg/L Mn)
within 60 minutes. The co-precipitation of magnesium and calcium
was less than 5%. The amount of the oxidative precipitation increased

Fig. 4. Oxidative precipitation of Mn(II) with 1.9% SO2 in air (0.5 L/min/L) and 60 C.

SO2 O2 2H2 OMnO2 SO4 4H

Reduction

2MnOOH SO2 4H 2Mn

2

MnO2 SO2 Mn

SO4 2H2 O

SO4

7
8

Catalysed side reaction

1

SO2 =2 O2 H2 OSO4 2H

An increase of SO2 content in the gas mixture from 1.9% to 3.8% SO2
signicantly increased the oxidation rate in pH 45 and almost
doubled at pH 6 where the rate reached maximum (Fig. 5). At pH N 6.5,
the trend of the oxidation rate with 3.8% SO2 was similar to that with
1.9% SO2 as discussed above.
Compared with air (O2) oxidant, the SO2/air (O2) oxidising system
was much more effective and efcient for removal and recovery of
manganese in a lower pH range of 67 with minimum co-precipitation
of magnesium and calcium impurities. In this pH range, it is likely that
the co-precipitated magnesium and calcium were caused by adsorption
and ion exchange mechanisms.
3.4.2. Effect of SO2/air (O2) ratio
Manganese oxidative precipitation with different SO2/air and SO2/
O2 ratios are investigated at pH 6 and 60 C by varying SO2 content in the

Fig. 5. Initial rate of Mn precipitation at different pH and 60 C.

62

W. Zhang et al. / Hydrometallurgy 101 (2010) 5863

Fig. 7. Initial rates of Mn precipitation vs. SO2 input at pH 6 and 60 C.

Fig. 6. Mn precipitation with different %SO2 in air at pH 6 and 60 C.

gas mixture at a xed air or oxygen ow rate (1 L/min/L solution). As

shown in Fig. 6, the initial rates of the precipitation signicantly
increased with SO2/air and SO2/O2 ratios. With 3.8% SO2, the two curves
with air gas mixture and pure oxygen gas mixture are almost identical,
suggesting that the rate was dominantly controlled by SO2 input rates in
the range of 03.8% SO2. A further increase to 7.6% SO2 in oxygen
resulted in a further increase in the precipitation rate. Similar to the
results shown in the effect of pH above, the manganese precipitation
features initially nearly linear increase with reaction time and then
decrease as the Mn(II) concentration left in solution decreased to below
0.5 g/L, corresponding to about 70% precipitation (Fig. 6). This could be
attributed to the competition of the Mn(II) oxidative reactions with
other catalysed side reactions (7), (8) and (9).
From the basic reactions involved, the utilisation of SO2 reagent is
determined by the rate ratio of reactions (5)(6) to reactions (7)(9).
Excess SO2 dissolved in the solution would react according to the
catalysed side reaction (9) to produce extra free acid and need more
base reagent for neutralisation. Therefore, the conditions for the
maximum rate of Mn(II) oxidation is consistent to the minimum
consumption of SO2.
In order to assess the efciency of Mn(II) oxidation as a function of
SO2 addition rates, initial rates of the Mn(II) oxidation, taking from the
slope values of linear part of the precipitation curves, were plotted
against the SO2 addition rate (Fig. 7). The SO2 addition rate was
calculated based on the specic molar volume of SO2 that was
determined by solving van der Waals Equation for SO2 (Petrucci,
1982). Under standard state, the specic molar volume was estimated
to be 23.92 L/mole. Hydrogen ion (H+) generated by the reactions
was estimated by the usage of base reagent (NH3 solution) for the
neutralisation to keep the pH constant during the oxidative
precipitation.
With SO2 in air, the ratio of the Mn(II) oxidation rate to the SO2
input rate (RMn/RSO2) decreased from 1 with 1.9% SO2 to 0.8 with 3.8%
SO2 (Table 3). This generally indicates that the utilisation of SO2 for
the oxidation reactions (5) and (6) becomes poorer with higher SO2

input rate, or higher SO2/air ratios, due to more involvement of side

reaction (9). The RMn/RSO2 ratios were far less than the stoichiometric
ratio of reaction (5), but close to that of reaction (6), supported by the
ratio of the rate of hydrogen ions produced to that of SO2 input rate
(RH+/RSO2).
With SO2 in pure oxygen, the RMn/RSO2 ratio increased from 1 to
1.3 when SO2 increased from 1.9% to 3.8% (Table 3). This may suggest
the involvement of reaction (5) with the stoichiometric RMn/RSO2 ratio
of 2. A further increase in the SO2 input rate (7.6% SO2) resulted in a
decrease in the RMn/RSO2 ratio similar to the observation for the SO2/
air system with a higher SO2/air ratio. This corresponded to a decrease
in the RH+/RSO2 ratio, suggesting that the side reaction (9) became
signicant at a higher SO2/O2 ratio.
Compared to the system of SO2/air, the Mn(II) oxidation rate at a
SO2 input rate was marginally higher in the range of 03.8% SO2,
indicating that the Mn(II) oxidation rate was dominantly controlled
by the SO2 input rate in the range of 03.8% SO2, but it is expected that
the rate would be eventually controlled by the mass transfer of
oxygen with a sufciently high SO2 input rate and the efciency of gas
dispersion equipment would become critical.
3.4.3. Discussion of issues using SO2/air system
Compared to carbonate and hydroxide precipitation, the recovery
of manganese as MnO2 and 2MnO(OH)/Mn2O3 oxides is favourable.
These manganese oxides with high purity are exible for subsequent
processing to produce chemical manganese dioxide (CMD), electrolytic manganese (EM) and electrolytic manganese dioxide (EMD).
However, the oxidative precipitation with SO2/air is a three phase
system, involving mass transfer and diffusion of the gas reactants into
the solution to react with Mn(II) at an optimum ratio of the dissolved
S(IV) species to the dissolved O2. In addition to the parameters of SO2/
air (O2) ratio and pH, gas dispersion parameters and gas ow rate are
also critical in a large commercial operation. It is well known that O2 is
much less soluble than SO2 and needs a large interfacial area for mass
transfer to keep oxidising conditions in the solution. This would
require a high gas ux with vigorous dispersion by efcient dispersion

Table 3
Comparison of the rates of Mn(II) oxidation, SO2 input and acid produced.
%SO2

RSO2 (mMmin)

1.9
3.8
7.6

0.79
1.59
3.18

SO2 in air

SO2 in O2

RMn (mM/min)

RH+ (mM/min)

RMn/RSO2

RH+/RSO2

RMn (mM/min)

RH+ (mM/min)

RMn/RSO2

RH+/RSO2

0.8
1.2

5.80

1.0
0.8

3.7

0.8
2.0
2.7

3.4
4.0
10.6

1.0
1.3
0.9

4.3

3.3

W. Zhang et al. / Hydrometallurgy 101 (2010) 5863

agitator because the rate of Mn(II) oxidation may be potentially

limited by gas dispersion equipment in an industrial application
(Mouton et al., 2007; Van Rooyen et al., 2007). For the removal of
manganese, the results in this study suggest the feasibility for using
joint precipitation methods, i.e., removal of a substantial proportion of
the manganese by either hydroxide or carbonate precipitation at an
appropriate pH for minimum co-precipitation of magnesium followed
by enhanced oxidation to remove the remaining manganese of low
levels by the oxidative precipitation with SO2/air. In this way, both
efciency of SO2 utilisation and feasibility to scale-up to an industrial
operation are expected to be increased. For recovery of manganese,
the SO2/air (O2) ratio and gas ow rate could be optimised against the
concentration of Mn(II) left in the solution. Partial recovery of Mn(II)
at the expense of some yield may lead to better recovery efciency
and better utilisation of SO2 reagents with minimum generation of
excess acid. The use of pure O2 in the gas mixture can increase the
maximum allowable SO2 content for maintaining the oxidising
conditions, but this benet has to be balanced by the expensive O2
reagent.
4. Conclusions
Precipitation methods including hydroxide, carbonate and oxidative precipitations with air, O2 and SO2/air (O2) mixtures have been
investigated and compared for removal and recovery of manganese
from a typical synthetic laterite waste solution containing 2 g/L Mn,
15 g/L Mg and 0.5 g/L Ca at 60 C. The general selectivity for
manganese over magnesium and calcium by hydroxide and carbonate
precipitation agreed to the thermodynamic predictions based on
single metal solubility constants, but there were signicant deviations
in the equilibrium concentrations of metals between the measured
and the derived, suggesting the importance of the factors such as
kinetics, ion interactions and condition controls in a real precipitation
process.
Hydroxide precipitation alone cannot be efciently used for
recovery and removal of manganese to very low levels due to its
poor selectivity for manganese over magnesium and need for higher
pH above 8.5 to obtain b100 mg/L Mn and pH above 9 for b10 mg/L
Mn with substantial co-precipitation of magnesium. The carbonate
precipitation offers better selectivity for manganese over magnesium
for partial recovery of manganese, but is not desirable for removal of
manganese to very low levels due to substantial co-precipitation of
magnesium impurity at pH above 8.
Oxidative precipitation with air is kinetically slow at lower pH
(b8) and requires a higher pH at the expense of substantial coprecipitation of magnesium or using expensive pure O2 for improved
kinetics. The oxidative precipitation with SO2/air (O2) has shown
much faster kinetics in a neutral pH range of 67 with 99.5%
manganese recovery (b10 mg/L Mn(II)) and is very promising for
both removal and recovery of manganese from laterite and other
waste solutions. SO2/air (O2) ratios could be optimised to obtain
maximum rate of Mn(II) oxidation and minimum consumption of SO2
and base reagents for neutralisation. A combination of the hydroxide
or carbonate method for the removal or recovery of a large proportion
of Mn(II) with oxidative precipitation for the reduction of manganese

63

concentration to very low level may be the best option in terms of

efciency and economics.
Acknowledgement
The authors would like to acknowledge Parker CRC for Integrated
Hydrometallurgical Solutions and CSIRO Minerals for the permission
to publish this paper and thank Dr Dave Robinson for reviewing this
paper and providing valuable comments.
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