Hydrometallurgy 86 (2007) 37 – 43

www.elsevier.com/locate/hydromet

An empirical rate equation for the partial removal of manganese from

solution using a gas mixture of sulfur dioxide and oxygen
J. Schulze-Messing a,⁎, D.C. Alexander a , K.C. Sole a , J.D.T. Steyl a ,
M.J. Nicol b , P. Gaylard c
a
Anglo Research, A Division of Anglo Operations Limited, Johannesburg, South Africa
b
Department of Mineral Science, Murdoch University, Perth, Australia
c
Department of Chemical Engineering, University of Cape Town, South Africa
Received 12 July 2006; received in revised form 7 November 2006; accepted 8 November 2006
Available online 15 December 2006

Abstract

The oxidation of soluble manganese by SO2–O2 gas mixtures is known to occur via complicated reaction pathways. An
empirical equation was derived for the rate of manganese precipitation from solution as a function of the gas composition, the
concentrations of dissolved sulfur and O2, and the solution temperature and pH. The relationships between the rate of manganese
precipitation and each of these parameters were obtained from batch tests.
The influence of SO2 was described by both the SO2 content of the gas mixture and the concentration of the dissolved sulfur
arising from the dissolution of the SO2 gas. The rate of manganese precipitation was found to be first order with respect to the
dissolved O2 concentration and inversely proportional to the pH of the solution. An Arrhenius relationship was used to relate the
solution temperature to the rate of precipitation, from which an activation energy of 23.5 kJ/mol was calculated. The manganese(II)
concentration had little influence on the rate at concentrations above 500 mg/L.
The rate equations for each of the operating parameters were combined into a single empirical rate equation for manganese
precipitation, which described all of the batch data and was also applicable to manganese precipitation in continuous mode.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Sulfur dioxide; Oxygen; Manganese oxide; Precipitation; Rate equation

1. Introduction of the lead anodes. However, there still needs to be some

Manganese is an unwanted cation in nickel leach
solutions, especially when processing laterites; the
soluble manganese (Mn2+) needs to be removed from
the solution prior to the electrowinning of cobalt or nickel.
When processing zinc ores, a certain level of manganese
is preferred in the zinc electrolyte for corrosion protection
⁎ Corresponding author. Tel.: +27 11 377 4824; fax: +27 11 377 4763.
E-mail address: jsmessing@angloresearch.com
(J. Schulze-Messing).
0304-386X/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2006.11.001
additional form of manganese removal to control its build-
up in the zinc electrolyte.
Oxidation of manganese with O2 is very slow in the
pH range from 3.5 to 6.0, even at high temperatures.
Other methods have consequently been developed to
remove manganese from leach solutions, including the
use of ozone (Sherritt Gordon Mines Limited, 1983),
ammonium persulfate (Newmont Exploration Limited,
1978) and Caro's acid (Hudson Bay Mining and
Smelting Company, 1957). The drawbacks of these
processes are the cost of the oxidising agents and their
38 J. Schulze-Messing et al. / Hydrometallurgy 86 (2007) 37–43

Fig. 1. The experimental set-up for the batch and continuous tests (1 SO2 flow control valve; 2 O2 flow control valve; 3 SO2 flow meter; 4 O2 flow
meter; 5 Gas dispersion chamber; 6 Glass sparge tube with frit; 7 Polypropylene reactor lid; 8 Water-jacketed glass reactor with glass baffles; 9,10
Water-jacket inlet, outlet; 11 Sample port; 12 Slurry over-flow port used during the continuous tests; 13 Type A315 impeller; 14 Polypropylene
inductor; 15 pH, temperature and dissolved O2 probes; 16 Graduated solution overflow container; 17 Thermometer; 18 Dissolved O2 meter; 19 Auto
titrator; 20 NaOH solution; 21 Peristaltic pump; 22 MnSO4 solution).

lack of selectivity for manganese over cobalt and nickel. overall rate equation derived from the batch tests was
Hydrogen sulfide can selectively precipitate nickel and then used to predict the residual manganese in a
cobalt while leaving manganese in solution, but this has continuous reactor to confirm its general applicability.
the disadvantage of having to re-leach the valuable
metals from the product sulfides. 2. Experimental
It is known that when SO2 is diluted with air or O2 and
sparged into a solution containing manganese or iron, a A schematic representation of the experimental set-
highly oxidising aqueous species is formed (Zhang et al., up appears in Fig. 1. The gas flow equipment consisted
2000; Berglund et al., 1994; Ferron et al., 1991).
Manganese precipitates as an oxide (MnO2, Mn2O3, or
Mn3O4 depending on the pH) when using SO2–O2 gas Table 1
mixtures. Competing with the oxidation of the soluble Ranges for the operating parameters investigated to derive the rate
manganese is the reduction of the formed precipitates by equation
aqueous forms of SO2 (Abbruzzese, 1990). The para- Parameter Range
meters identified as influencing the rate at which Gas composition⁎ (% SO2 in O2) 1 to 20
manganese precipitates from solution are: SO2–O2 gas Initial Mn(II) concentration (g/L) ⁎⁎ 0.25 to 4.0
composition; dissolved SO2 and O2; and the temperature Temperature (°C) 20 to 50
pH 3.5 to 6.0
and pH of the solution (Zhang et al., 2002).
Dissolved O2 concentration (mg/L) 4 to 30
Each of these operating parameters was indepen-
⁎The overall gas flow rate was kept constant at 500 mL/min but the
dently varied while keeping the other parameters
ratio of SO2 to O2 was varied.
constant, or in the case of SO2, an equal rate of transfer ⁎⁎ The effect of introducing Mn3+ on the rate of removal was not
to the solution for all of the batch tests. In this manner, a investigated although it is expected to dictate the induction period
rate equation was constructed one term at a time. The before precipitation commences.
 J. Schulze-Messing et al. / Hydrometallurgy 86 (2007) 37–43 39

of two Bronkhorst flow meters, a type F-201C for O2

and a type F-201D for SO2. The gases were mixed in a
dispersion chamber prior to the mixture entering the
reactor by means of a glass-fritted sparge tube. For all
tests, SO2–O2 gas mixtures were sparged into a 3-litre
glass reactor at a flow rate of 500 mL/min, which
equates to 0.17 mL/min of gas per mL of solution.
The glass reactor had a water jacket for temperature
control, and internal glass baffles to ensure that the flow
of solution inside the reactor was as turbulent as possible
to promote gas mass transfer. An impeller speed of
800 rpm was used. A glass valve situated halfway up the
side of the reactor was used to take samples. Solution Fig. 3. The influence of the gas composition on the rate of manganese
samples were analysed for manganese and for total removal (Overall gas flow rate of 500 mL/min; pH 4.0; 30 °C; [Mn] of
sulfur content. 1.5 g/L).
During the continuous tests, a solution of manganous
sulfate was pumped into the reactor using a peristaltic
pump. An overflow port allowed the solution to flow out 3.1. Deriving an empirical rate equation in terms of the
of the reactor at a rate equal to the feed rate. The pH, manganese concentration
dissolved O2 concentration and the solution temperature
were recorded during each test. The effect of the initial manganese concentration on the
rate of the manganese removal was investigated. It was
3. Results and discussion found that the rate of precipitation was almost identical over
the whole range of manganese concentrations tested except
Table 1 lists the range of conditions tested to derive below 500 mg/L (see Fig. 2). This would indicate that
the rate equation. The operating parameters identified as manganese acts as a catalyst for the formation of the
having an influence on the rate of manganese removal oxidising species and thus the manganese concentration
were each independently varied from the base-case was not included as a term in the overall rate equation.
conditions. For each operating parameter a rate equation
could therefore be written as: 3.2. Deriving an empirical rate equation in terms of SO2

d½Mn=dt ¼ constant  f ðoperating parameterÞ
An overall rate equation was then written by
combining the individual rate equations derived for
each operating parameter.
ð1Þ The influence of the gas composition on the rate of
manganese precipitation is shown in Fig. 3, while
Fig. 4 plots the average removal rate over the first
60 min of the batch tests. Also shown in Fig. 4 is the

Fig. 2. The influence of manganese concentration on the rate of Fig. 4. The influence of the gas composition on the average rate of
manganese removal (6% SO2 in O2; overall gas flow rate of 500 mL/ manganese removal over the first 60 min of the batch tests (conditions
min; pH 4.0 and 30 °C). as Fig. 3).
40 J. Schulze-Messing et al. / Hydrometallurgy 86 (2007) 37–43

[S from gas] which refers to the total aqueous sulfur

after 60 min attributed to the dissolution of the gas.
The rate of manganese removal increased linearly with
an increase in the SO2 content of the gas mixture up to
12%, whereafter the rate dropped with a further
increase in the SO2, probably due to the reduction of
the product manganese oxides by excess dissolved
SO2. This is consistent with the findings of Zhang
et al. (2002).
The rate of manganese removal decreased with time
as the dissolved SO2 increased. This effect was more
pronounced in tests which used a gas mixture rich in
SO2. In Fig. 5, it is shown that the rate at which SO2–O2 Fig. 6. Empirical relationship between the dissolved sulfur from the
gas mixtures precipitate manganese is dependent on the gas phase, the gas composition and the rate of manganese removal
dissolved sulfur attributed to the dissolution of SO2 from (conditions as Fig. 3).
the gas mixture. This drop in the rate of manganese
removal is closely described by an exponential decay 3.3. Deriving an empirical rate equation in terms of the
function — although this is not seen in Fig. 5 for gas dissolved O2 concentration
mixtures with a SO2 content of less than 9%.
The rate of manganese removal can therefore be To determine the influence of the dissolved O2
described by a combination of the gas composition and concentration, nitrogen was sparged into the manganous
the sulfur dissolved into the solution from the gas phase. sulfate solution while conducting batch tests, thereby
A rate equation can be written as: decreasing the partial pressure of O2 in the reactor gas
phase and subsequently the dissolved O2 concentration.
d½Mn=dt ¼ k1  ðPSO2 =PTotal Þ  eð−18½S from gasÞ
The results illustrated in Fig. 7 show that the rate of
|{z} |{z} ð2Þ manganese precipitation was first order with respect to
ðiÞ ðiiÞ the dissolved O2 concentration (Eq. (3)).
with part (i) describing the linear relationship between
the rate of manganese precipitation and the SO2 content d½Mn=dt ¼ k2  ½O2  ð3Þ
of the gas mixture up to 12% SO2 (Fig. 4); and part (ii)
describing the exponential decay in the manganese
3.4. Deriving an empirical rate equation in terms of the
removal rate with the build-up of the aqueous sulfur in
solution temperature
solution (Fig. 5). This relationship, plotted for the batch
data (Fig. 6), is seen to be an acceptable way to describe
An Arrhenius plot for the relationship between the
the influence of SO2 on the rate of manganese
manganese precipitation rate and the solution temperature
precipitation for gas mixtures up to 12% SO2.

Fig. 5. The effect of the aqueous sulfur obtained from the gas phase on Fig. 7. The influence of dissolved O2 on the rate of manganese removal
the rate of manganese removal using a range of different gas mixtures over the first 60 min of the batch tests (O2 flow rate 440 mL/min; SO2
(conditions as Fig. 3). flow rate 60 mL/min; Varied N2 flow rate; 30 °C; [Mn] of 1.5 g/L).
 J. Schulze-Messing et al. / Hydrometallurgy 86 (2007) 37–43
Fig. 8. Arrhenius plot (conditions as Fig. 3 with 6% SO2 in O2.)
is presented in Fig. 8. The activation energy of 23.5 kJ/
mol calculated from the slope of the line is higher than the
value of 15 kJ/mol measured by Zhang et al. (2002). The
rate equation for the manganese precipitation reaction in
terms of the temperature was then described by the
Arrhenius Eq. (4):
d½Mn=dt ¼ k3  eð−Ea =RTÞ ð4Þ
with Ea = 23.5 kJ/mol; R = 8.314 kJ/K/mol.
3.5. Deriving an empirical rate equation in terms of the
solution pH
It is known that the manganese precipitation rate
decreases with decreasing pH of the solution, with a
very slow rate of manganese removal below a pH of 3
(Zhang et al., 2002). The effect of pH was therefore
studied in the pH range from 3.5 to 6.0. Results in Fig. 9
indicate a linear relationship between the rate of the
Fig. 9. The influence of pH on the average rate of manganese removal
over the first 60 min of the batch experiments (conditions as Fig. 8
except for pH).
41
Fig. 10. Comparison of the manganese removal calculated by the
derived empirical rate equation (dotted lines) with the actual data
obtained from the batch tests where the gas composition was varied.
manganese removal and the inverse of the pH as
described by Eq. (5).
d½Mn=dt ¼ k4  ð1=pH−k5 Þ ð5Þ
with k5 = 0.3.
3.6. Combining the individual rate equations for the
operating parameters into one empirical rate equation
Combining rate Eqs. (2)–(5) into a single rate
equation for the removal of manganese with a gas
mixture of SO2 and O2 resulted in Eq. (6). The value for
the rate constant A, the only unknown, was then
determined by substituting the data of the base-case test
into the equation.
d½Mn=dt ¼ Ad½O2 dðPSO2 =Ptot ÞdeðBd½S from gasÞ
ð6Þ
dð1=pH þ CÞdeð−Ea =RT Þ
with d[Mn] / dt in mol/L/min; [O2] in mol/L; PSO2 in
atm; Ptot in atm; [S from gas] in mol/L; T in Kelvin;
A = − 6.8 × 105; B = − 18; C = − 0.3; Ea = 23.5 kJ/mol.
3.7. Comparing the derived rate equation to the
measured batch data
To test rate Eq. (6), the measured values for the
operating parameters ([O2]; PSO2; [S from gas]; pH and
temperature) for each batch test conducted were inserted
into the derived rate equation and the rate of manganese
precipitation calculated. This calculated rate was then
used to calculate the manganese concentration in
solution as a function of time.
42 J. Schulze-Messing et al. / Hydrometallurgy 86 (2007) 37–43
Table 2
Operating conditions for the continuous test work (Total gas
flow = 500 mL/min; residence time = 60 min; initial [Mn] = 1400 mg/L)
Test 1 Test 2 Test 3
Varying gas Varying Varying
mixture temperature pH
Gas mixture (% SO2) 6 and 12 12 12
Solution temperature (°C) 33 25 and 50 33
pH (controlled with NaOH) 4.0 4.0 4.0 and 5.0
Fig. 10 compares the assayed manganese concentra-
tions with those calculated using the derived rate
equation (dotted lines) for the batch tests where the
gas composition was varied. Ignoring the induction
period during the first few minutes of each experiment,
the calculated and measured rates of manganese
removal are in very good agreement in the range from
6 to 12% SO2. The rate is increasingly underestimated
below 6% SO2. The derived rate equation can only
describe the rate of manganese precipitation for gas
mixtures up to 12% SO2 in O2 due to the deviation from
the linear relationship between the rate of manganese
removal and the SO2 content of the gas mixture above
12% SO2 (Fig. 4). Good agreement of the model with
the experimental data was similarly found when
changing the dissolved O2, pH and solution temperature
in the ranges tested.
3.8. Testing the derived rate equation for manganese
precipitation on a continuous basis
In a continuous reactor, the sulfur in solution as a
result of the transfer and oxidation of SO2 stabilises
once steady-state conditions are achieved at a given
retention time. A solution of known manganese
Fig. 11. Accuracy of the derived rate equation under continuous
conditions in predicting the steady-state manganese concentrations on
changing the pH after 4 h (12% SO2 in O2; overall gas flow rate of
500 mL/min; 30 °C; [Mn] of 1.4 g/L).
Table 3
Results of the continuous test work (Total gas flow = 500 mL/min;
residence time = 60 min; initial [Mn] = 1400 mg/L)
Operating Value of Assayed steady- Calculated steady-
parameter operating state [Mn], mg/L state [Mn], mg/L
parameter
Gas mixture 6% SO2 1057 ± 20 1063
Gas mixture 12% SO2 923 ± 20 945
Solution 20 °C 1037 ± 20 951
temperature
Solution 50 °C 827 ± 20 761
temperature
Solution pH 4.0 964 ± 20 884
Solution pH 5.0 454 ± 20 445
concentration (1.4 g/L) was pumped at a constant flow
rate into the reactor, providing a one-hour retention
time. The manganese precipitated was calculated using
rate Eq. (6) with the steady-state temperature, pH, [O2],
[S from gas] and the partial pressure of the SO2 in the
gas as inputs. The manganese concentration of the
solution leaving the reactor was then calculated.
Table 2 lists the operating conditions for three
continuous tests, in which the operating parameter
investigated was changed once after four or five
residence times (SO2 from 6 to 12%, temperature from
20 to 50 °C and pH from 4 to 5, respectively). As seen in
Fig. 11, the model calculated a steady-state manganese
concentration of 884 mg/L compared to the assayed
value of 964 mg/L at pH 4.0 and 445 mg/L compared to
the assayed value of 454 mg/L at pH 5.0. Table 3 lists
the results of the continuous tests under different gas
compositions, solution temperature and pH. Good
agreement of the model predictions with actual data
was found, indicating the potential for using this
approach as a predictive tool. The slightly higher than
expected assays for manganese in the solution leaving
the reactor could be due to short-circuiting of the feed
solution to the overflow port of the reactor.
4. Conclusions
The relationships between the rate of manganese
precipitation and each of the influencing experimental
variables were determined using batch tests. The rate
of manganese precipitation was described by both the
SO2 content of the gas mixture, as well as by the
dissolved sulfur attributed to the dissolution of the gas
phase. The rate was first order with respect to
dissolved O2 concentration and inversely proportional
to the pH of the solution. An Arrhenius relationship
was used to relate the solution temperature to the rate
of precipitation, with an activation energy of 23.5 kJ/
 J. Schulze-Messing et al. / Hydrometallurgy 86 (2007) 37–43
mol. The rate of manganese removal was insensitive to
the manganese concentration except at concentrations
less than 500 mg/L Mn.
The rate equations stated for each of the operating
parameters were combined into a single equation
describing the precipitation of manganese by using a
SO2–O2 gas mixture:
d½Mn=dt ¼Ad½O2 dðPSO2 =Ptot ÞdeðBd½S from gasÞ
ð6Þ
dð1=pH þ CÞdeð−Ea =RT Þ
with A = − 6.8 × 105; B = − 18; C = − 0.3; Ea = 23.5 kJ/mol.
The equation is applicable at Mn concentrations
above 500 mg/L, temperatures below 50 °C and for
SO2–O2 gas mixtures containing up to 12% SO2.
An empirical rate equation has been derived that
describes the rate at which manganese precipitates from
solution by using a gas mixture of SO2–O2, under both
batch and continuous operation. To convert this into a
predictive tool, the rates of O2 and SO2 mass transfer into
the solution need to be combined with the rate equation
for manganese precipitation.
Acknowledgements
This work is based on the MSc. thesis of Jacobus
Schulze-Messing, awarded by the University of Cape
Town, South Africa, in 2005. Anglo Research is
43
acknowledged for the financial support and for
permission to publish this paper.
References
Abbruzzese, C., 1990. Percolation leaching of manganese ore by SO2.
Hydrometallurgy 25, 85–97.
Berglund, J., Elding, L.I., Buxton, G.V., McGowan, S., Salmon, G.A.,
1994. Reaction of peroxomonosulfate radical with manganese(II)
in acidic aqueous solution. J. Chem. Soc., Faraday Trans. 90 (21),
3309–3313.
Ferron, C.J., Kwateng, D.O., Duby, P.F., 1991. Kinetics of the precipitation
of goethite from ferrous sulfate solutions using O2–SO2 mixtures. In:
Gaskell, D.R. (Ed.), Extraction and Processing Division Congress. The
Minerals, Metals and Materials Society, Warrendale, PA, pp. 165–177.
Hudson Bay Mining and Smelting Co., 1957. Process for the
purification of aqueous solutions of zinc sulfate, Canadian patent
550,346, December 17.
Newmont Exploration Limited, 1978. Process for manganese removal
from zinc metal bearing solutions, United States patent 4,067,789.
Sherritt Gordon Mines Limited, 1983. Removal of manganese and
chloride ions from aqueous acidic zinc sulfate solutions, United
States patent 4,379,037.
Zhang, W., Singh, P., Muir, D., 2000. Iron(II) oxidation by SO2/O2 in
acidic media. Part I. Kinetics and mechanism. Hydrometallurgy 55
(3), 229–245.
Zhang, W., Singh, P., Muir, D., 2002. Oxidative precipitation of
manganese with SO2/O2 and separation from cobalt and nickel.
Hydrometallurgy 63, 127–135.