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Hydrometallurgy 89 (2007) 178 – 188

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Manganese metallurgy review. Part III: Manganese control in

zinc and copper electrolytes
Wensheng Zhang ⁎, Chu Yong Cheng
Parker Centre for Integrated Hydrometallurgy Solutions, CSIRO Minerals, PO Box 7229, Karawara, WA 6152, Australia
Received 6 July 2007; received in revised form 24 August 2007; accepted 25 August 2007
Available online 1 September 2007

Abstract

Manganese is often associated with zinc and copper minerals, and can build up in the processing circuits. Part III of the review
outlines the current practice and new developments to get a better understanding of manganese behaviour and control in
electrowinning of zinc and copper, and identifies suitable methods and processes to control manganese.
In zinc electrowinning, the presence of small amounts of manganese (1–5 g/L) can minimise the corrosion rate of the anodes
and reduce the contamination of the cathodic zinc with lead, but excess manganese results in significant decreases in the current
efficiency. The neutralized zinc feed solution that contains little acid is considered to be the best place to implement manganese
control. Various methods and processes for manganese control in zinc electrowinning have been developed. Oxidative precipitation
and solvent extraction are the most important methods. For the neutralized zinc solution at pH 5, oxidative precipitation using a
strong oxidant such as Caro's acid and SO2/O2 can selectively precipitate manganese as insoluble MnO2 or Mn(OOH), leaving
other impurities, e.g., Mg, Cl−, F−, etc. in the circuit. Solvent extraction of zinc using D2EHPA (di-2-ethylhexyl phosphoric acid)
can selectively recover zinc from the solution and leave other impurities including manganese in the raffinate.
In copper solvent and electrowinning circuits, the problem of manganese is mainly associated with the decrease in the current
efficiency and degradation of the solvent caused by the higher valent manganese species generated on the anode. The prevention or
minimisation of Mn(II) oxidation during the electrowinning is critical. This can be achieved by adding ferrous ions or sulfur
dioxide to control the cell potential.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Manganese control; Zinc electrowinning; Copper electrowinning

1. Introduction and Hanson, 1978). High extractions of zinc and

In the roasting–leaching–electrowinning process for
processing zinc sphalerite flotation concentrates, some
non-ferritic zinc and manganese are first dissolved in a
neutral leach liquor while most of the ferritic zinc and
manganese are then dissolved in a hot acid leach (Harris
⁎ Corresponding author.
E-mail address: wensheng.zhang@csiro.au (W. Zhang).
0304-386X/$ - see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2007.08.011
manganese are achieved in the oxidative pressure-
leach process (Bolton et al., 1981). In both processes,
most of the manganese reports to the leach liquor.
Secondary sources of manganese come from addition of
manganese, usually as MnO4−, to the leaching circuit to
serve as an oxidant (Filippou, 2004). Additional
manganese dioxide or potassium permanganate is
usually introduced to the zinc sulfate electrolyte from
the leaching process in order to oxidise iron impurities.
 W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 178–188
The amount of manganese added varies widely with the
amount of iron and other impurities in the solution. The
purified industrial zinc sulfate electrolyte usually
contains a substantial amount of manganese (MacK-
innon and Brannen, 1991).
In zinc electrowinning, the presence of manganese has
dual effects, positive and negative, depending on its
concentration in the electrolytes (Krupkowa et al., 1977;
Verbaan and Mullinder, 1981). Small amount of manga-
nese is needed to present in the electrolyte to reduce the
corrosion of anodes and minimise the contamination of
cathodic zinc by the dissolved lead. Higher concentrations
of manganese in the electrowinning can cause a
significant decrease in current efficiency and it has to be
removed or controlled when building up to a certain level.
In the copper solvent extraction and electrowinning
(SX–EW) process, manganese must be controlled to
obtain high current efficiency and to ensure the quality
of copper cathodes (Cheng et al., 2000). Higher valent
manganese ions which are generated on the anodes can
cause severe degradation of organic extractants in the
SX circuit. It is therefore essential to maintain a
manganese balance throughout the plant circuit. The
control of impurities involving manganese is still under
development for novel methods and processes.
This paper reviews current practice and new devel-
opments to get a better understanding of manganese
behaviour and control in the electrowinning of zinc and
copper, and identifies suitable methods and processes to
control manganese.
2. Effect of manganese on zinc electrowinning
Mn2+ ions in the electrolyte could be oxidised to
MnO4− (Vereecken and Winand, 1972) which was
proposed to react immediately with Mn2+ to form Mn3+
and finally MnO2 (Yu and O'Keefe, 2002). MnO2
formation initiated at about 1.6V, evidenced by formation
of a brown film on the electrode (Vereecken and Winand,
1972). Both MnO4− and Mn3+ ions decreased the current
efficiency of zinc deposition because they depolarised
discharge of the H+ ions. The positive and negative effects
on zinc electrowinning are summarised below.
2.1. Positive effects
2.1.1. Effect on anodes
Lead alloys containing silver are the primary insoluble
anodes used for zinc electrowinning. These anodes suffer
from corrosion and have a detrimental effect on cathode
purity from incorporation of lead corrosion products.
About 1–3 g/L Mn2+ ions are usually required in the
179
electrolyte to minimise the corrosion rate and to reduce the
contamination of the cathodic zinc with lead and thus to
promote the purity of cathodic zinc products (Krupkowa
et al., 1977; MacKinnon and Brannen, 1991). Schierle and
Hein (1993) identified that the MnO2 layer formed had a
depolarizing effect on the Pb–Ag–Ca anodes in a
synthetic zinc and manganese sulfate electrolyte. Newn-
ham (1992) investigated the corrosion rates of anodes
made from various lead/silver alloys under various
conditions. In the absence of manganese, the corrosion
rate was effectively independent of current density in the
range studied, whereas in the presence of manganese, the
corrosion rate decreased with decreasing current density.
Saba and Elsherief (2000) observed that the presence of
manganese up to 1.8 g/L in the electrolyte had little effect
on zinc polarization while Ivanov and Stefanov (2002)
found that up to 5 g/L of Mn(II) present in the zinc sulfate
electrolyte did not exert a large effect on zinc deposition.
2.1.2. Effect on higher electropositive metals
In addition to the inherent over-potential, impurities
such as Cu, Co, Ni and Sb in the electrolyte could have a
significant polarization impact (Ivanov, 2004). The
presence of manganese ions decreased the deleterious
influence of the above metals that are more electropos-
itive than zinc. It was proposed that the manganese
hydrates block the active hydrogen spots of the
impurities on the zinc cathodic surface. Thus, the
process of zinc re-dissolution was inhibited. This effect
was more pronounced at high temperatures. A small
amount of MnO4− (15–80 mg/L) had a beneficial effect
on zinc deposition when the electrolyte also contained
Sb3+ (Hosny et al., 1989; Ivanov and Stefanov, 2002).
2.1.3. Effect on anode chlorine gas evolution
A substantial amount of chloride ions may be present
in the zinc electrolyte when processing steel industrial
dust (Yoshida et al., 1997). Chloride anions in the
electrolyte attack the anodes which are commonly made
of Pb alloy and increase the corrosion rate (Newnham,
1992). It was proposed by Kelsall et al. (2000) that
deposition of manganese dioxide on anode surfaces
probably produced a diffusion barrier to anodic chlorine
evolution, and Mn(II) species scavenged any chlorine
that did form in the electrolyte. Hence, current efficiency
losses for zinc deposition were limited. In addition, the
inhibiting chlorine generation also has a major benefit
for the cell house hygiene.
2.1.4. Effect on positive interaction with other ions
MacKinnon (1994) studied the effects of foaming
agents, and their interactions with antimony, manganese
180 W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 178–188
and magnesium, on zinc deposition current efficiency,
morphology and orientation. Both Dowfroth and
Saponin decreased the zinc deposition current efficiency
and also changed the deposit morphology and orienta-
tion. The addition of MnSO4 to an electrolyte containing
10 mg/L Dowfroth increased the current efficiency for
zinc deposition and changed the deposit morphology
due to a positive interaction with manganese.
2.2. Negative effects
2.2.1. Effect on current efficiency
A concentration of Mn2+ ions higher than 3 g/L in the
electrolyte could result in a significant decrease in the
current efficiency (Cathro, 1991). The particles of
MnO2, produced on the anodes, were found to be
deposited on the cathode and formed galvanic pairs with
zinc, and the latter dissolved anodically. An increase of
10–15% in energy consumption at a high current
density (5000A/m2) was observed for industrial electro-
lytes containing manganese.
In a study on the effects of manganese, magnesium,
sodium and potassium sulfates on the current efficiency,
morphology and orientation (MacKinnon and Brannen,
1991), it was found that an increase in the concentration
of Mn(II) (sulfate) up to 5.5 g/L in the electrolyte
resulted in a decrease in the current efficiency and an
increase in the size of the zinc platelets.
2.2.2. Effect on oxygen over-potential
The reaction potential and over-potential required for
oxygen evolution is one of the important factors for
process economics. Rerolle and Wiart (1996) studied the
kinetics of oxygen evolution on Pb and Pb–Ag anodes
during zinc electrowinning in the absence and presence
of Mn2+ in a sulfate medium using impedance spec-
troscopy. It was found that the presence of silver in the
lead anode modified both the kinetic parameters of the
main reaction of oxygen evolution, and the potential
dependence of the condensed oxide layer. The reaction
of oxygen evolution was proposed to be inhibited by a
silver salt adsorbate. The electrode coverage by this
adsorbate appeared to be increased in the presence of
Mn2+ in the electrolyte, thus changing the inhibition into
a passivation process.
2.2.3. Effect on anode disposal and cleaning
Too much Mn2+ (N 4 g/L) was found to create an
anode disposal problem and increase the frequency of
anode cleaning (Pajunen et al., 2003). The manganese
dioxide layer formed on the anode could not be removed
without losing the active coating of the anode. The same
problem was also found for hybrid anodes in which a
mixed metal oxide coated titanium mesh was attached to
a lead base material.
2.2.4. Effect on organic reagents in zinc SX–EW circuit
In zinc SX–EW circuit, the presence of manganese
may result in decrease in organic reagent kinetics and
capacity due to reagent oxidation and degradation by
MnO2. It may also cause long phase disengagement time
and stable emulsion formation in SX settlers as a result
of surface-active degradation products and high organic
loss to the raffinate and high electrolyte loss to the
organic by entrainment.
3. Pre-treatment of anodes in zinc electrowinning
Anode composition and pre-treatment are two of the
important aspects in zinc electrowinning in terms of
MnO2 formation and tolerance of manganese levels in
the system. Some interesting methods are summarised in
this section, which may also be applied to copper
electrowinning.
3.1. Composite anode technology
Dattilo and Lutz (2001) reported the Merrlin
composite anode technology for metal electrowinning.
The Merrlin composite anode is a coating applied to a
conventional lead alloy anode that alters the electro-
chemical reactions during metal electrowinning. The
composite is a mixture of lead and manganese oxides,
which are bound to the surface with heat and pressure.
The use of this anode, relative to the normal lead alloy,
was evaluated both in zinc and copper electrowinning.
In zinc electrowinning, a significant reduction of anode
scale and cell sludge was observed. The reasons for this
alteration in cell operation were believed to be due to the
decreased oxidation of manganese.
A lead fluoride coating for passivation of 0.8% Ag-
alloyed lead anodes by a preconditioning process was
reported by Jaksic et al. (1987) and Rajkovic et al.
(1987, 1998). Anodic polarization from acidic sulfate
solution in the presence of F− ions produces a thin PbF2
layer, which catalytically affects the transformation of
the isolating PbSO4 layer into the protecting β-PbO2
layer and hinders crystallisation of α-PbO2 which has
much lower corrosion protecting capability. Further,
anodic polarization in the cells for zinc electrowinning
in the presence of Mn2+ ions created a glassy deposit of
mixed oxides, MnO2–β-PbO2, which exhibited ad-
vanced protecting properties, hindered further produc-
tion and precipitation of MnO2, and extended the life-
 W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 178–188
time of alloyed Pb electrodes from two to six or even
more than 10 years. An additional contribution was that
the detrimental MnO2 production was dramatically
reduced (Rajkovic et al., 1998).
An anode composite containing bismuth was applied
to zinc electrowinning by Harlamovs et al. (2003). The
electrowinning anodes were optionally manufactured
from Pb alloy containing 0.7–0.8% Ag and 1.7–1.9%
Bi, as an alternative to the Pb–(2%)Ag alloy. The zinc
could be recovered from the concentrated solution by
electrowinning in the absence or presence of manganese.
3.2. Treatment of anode by sulfite solution
Joslin (1985) reported that anodically deposited
manganese dioxide was removed by an aqueous sulfite
solution. The treatment of catalytic anodes with aqueous
sulfite solution caused the MnO2 deposit to flake off and
thereby restored its catalytic activity. The anodes were
treated every 3–4 weeks with the Na2SO3 solution and
the MnO2 was removed from the anodes without
dissolution.
4. Methods for manganese control in zinc
electrowinning
The concentration of manganese and other impurities
in the zinc electrolytes from the leach-EW circuit is
conventionally controlled by treating a bleed stream of
electrolyte with limestone at temperatures in the range of
50–90 °C at a pH between 6 and 8 to precipitate the zinc
as basic zinc sulfate and then at a final pH above 10 to
precipitate manganese hydroxide and other impurities.
The basic zinc sulfate can be used as a neutralizing agent
elsewhere in the circuit. For newer flowsheets include
SX–EW, the zinc electrolytes are usually manganese
deficient and some forms of manganese are added to
maintain manganese levels for its positive effects.
Various methods and processes for manganese
control in zinc electrowinning have been studied and
developed. Among these, oxidative precipitation, com-
bined precipitation and evaporation, solvent extraction,
electrolysis and electrowinning, are potentially useful
for manganese control in zinc electrowinning.
4.1. Manganese removal by oxidative precipitation
Oxidative precipitation of Mn(II) is based on forming
insoluble manganese dioxide (MnO2) by oxidation with
a strong oxidant. Mn3+ is proposed to be the initial
oxidised species which then disproportionates to form
MnO2 and Mn2+. The oxidative precipitation of Mn(II)
181
has found application in zinc electrowinning for con-
trolling the manganese concentration to an acceptable
level (b5 g/L). Various oxidants have been investigated
for the oxidation, including ozone, catalysed SO2/O2
mixtures, Caro's acid (H2SO5), persulfate salts (Zhang
and Cheng, in press). In addition to controlling the
amount of manganese in the electrowinning, oxidative
precipitation is also of importance for recovery of
manganese as manganese dioxide from solutions.
4.1.1. Oxidation by ozone
Ponelis (1995) investigated oxidative precipitation of
a high concentration of manganese (15 g/L in zinc
electrolyte) by ozonation. The experimental work was
carried out in a laboratory scale bubble reactor, which
was coupled with a small scale ozone generator. An
industrial electrolyte was used for the experiments in a
semi-batch mode for different reaction times in the
temperature range of 20–70 °C and the pressure range of
88–400kPa. An ozone demand of 0.94mol ozone per
mol manganese was determined. The reaction depended
on temperature with the apparent activation energy
being 56.6kJ/mol.
4.1.2. Oxidation by SO2/O2 mixture
Ferron (2000) patented a method for purification of
zinc ore leach solutions by oxidation of manganese
impurity by a SO2/O2 mixture. The manganese impurity
in the zinc ore leach solutions could be removed by the
treatment with an O2/(0.5–10%) SO2 gas mixture at 40–
80 °C and pH of 3–4, in which the Mn(II) was
oxidatively precipitated as manganese dioxides with a
minimised loss of zinc by co-precipitation. This process
was proposed for a removal of the manganese impurity
in a neutral zinc electrolyte.
A similar method for removal of manganese in zinc
ore leach solutions by SO2/O2 was patented by
Demopoulos et al. (2001). With this method, the Mn2+
ions in acidic sulfate leach solutions, especially from
roasted Zn-sulfide ores, could be precipitated without
the loss of zinc and other metal values. The weakly
acidic sulfate solution could be treated with an
oxidising SO2–O2 gas mixture at controlled pH N 2
and bath temperature of 60–90 °C to precipitate the
soluble Mn2+ ions as Mn3+ or Mn4+ hydroxides and/or
oxides for removal from the Zn-containing leach
solutions. The manganese precipitation as MnO2 from
an aqueous leach solution containing zinc at 30–170 g/
L is typically increased to 100% by neutralizing the
freshly formed acid with soda or ore calcine. By com-
parison, there was no manganese removal in the ab-
sence of SO2. The precipitated manganese compounds
182 W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 178–188
could be optionally used as oxidants in other parts of the
ore leach circuit.
4.1.3. Oxidation by Caro's acid and peroxydisufuric acid
Ammonium persulfate ((NH4)2S2O8) was used at a
pilot-plant scale for the control of excess manganese ions
in the zinc electrolyte in the processing of Gamsberg
deposit in South Africa (Deguire et al., 1978; Burkin and
Chouzajian, 1983). This chemical oxidation method was
comparatively tested with anodic oxidation method. The
chemical oxidation with ammonium persulfate was
performed at 90 °C for 2 h and the resulting pulp was
filtered to separate the precipitated manganese. The
anodic oxidation was carried out by electrolysing a
portion of the feed electrolyte (1000L/day) in a small
electrolytic cell with aluminium cathodes and lead anodes
at a current density of 600A/m2. The heavy accumulation
of manganese dioxide in the spent electrolyte needed
filtering and frequent cleaning of the anodes.
Compared with the anodic oxidation method, the
chemical oxidation was found to be viable with the
precipitated manganese dioxide being battery grade and
flexible in terms of varying concentrations of manganese
in the solution without affecting the process efficiency or
quality of the manganese dioxide produced. The main
disadvantage using the anodic oxidation was the
production of off-grade cathodic zinc and erratic cathode
current efficiency obtained during electrolysis.
The use of Caro's acid (H2SO5) to remove manganese
from a zinc electrolyte containing 150 g/L Zn and 6–7 g/L
Mn was reported (Burkin et al., 1981; Burkin and
Chouzajian, 1983). About 70–80% precipitation of
manganese could be achieved using Caro's acid at a pH
of about 2. It was concluded that removal of manganese
by ammonium persulfate was more convenient than the
use of Caro's acid, but the cost of peroxydisulfate was
expected to be higher than Caro's acid because Caro's
acid could be produced easily on site.
4.1.4. Oxidation by halide species from anode
compartment
Moyes and Houlis (2003) developed a halide-based
leaching for zinc recovery from complex ores with a
step for removal of manganese as MnO2 by the halide
species which were generated at the anodes. The process
was comprised of the following steps:
(1) The complex zinc ore feed was processed by
leaching the zinc with an aqueous solution contain-
ing halides with copper as catalyst.
(2) The resulting zinc leach solution was purified with
zinc dust, which was then processed by electro-
winning to deposit the zinc metal, and to generate
the halide species (preferably Halex, BrCl2−) for
recycling to the leaching stage.
(3) A portion of the spent electrolyte (up to 20%) was
optionally removed as a bleed stream from the
cathode compartment, and was treated with Halex
vapour and limestone to precipitate the manga-
nese as MnO2.
Among the above oxidants, SO2/O2 appears to be the
cheapest, particularly if the process involves roasting
zinc sulfide concentrates. However, it may need more
analytical and automatic control to enable the SO2/O2
mixture to function as an oxidant for Mn(II). There are
also significant problems associated with the scale-up of
reactors for SO2/O2 (or air) precipitation due to the
differing solubilities of the gases. In this regard, Caro's
acid offers better controls in real applications. Com-
pared with the conventional precipitation method,
oxidative precipitation has the following advantages:
(1) It is selective for oxidation of Mn(II) to insoluble
forms of manganese oxides, without first requiring
separation and recovery of zinc from the electrolyte.
(2) It can be used to treat the whole leach liquor or to
treat a bleed stream of the electrolyte.
(3) The oxidation is operative at relative lower pH
range (pH 3–6) and nearly a stoichiometric
amount of base reagent needed for neutralisation
under well-controlled conditions due to little
precipitation of other impurities.
(4) The manganese could be recovered as a relatively
pure marketable product with or without further
purification.
Its disadvantages are:
(1) Oxidative precipitation cannot remove other
impurities which accumulate in the electrolyte.
(2) More controls for the operation are expected, e.g.,
optimum SO2/O2 ratios and optimum solution pH.
(3) Significant difference in gas solubility between SO2
and O2 or air and subsequent problem of scale-up.
4.2. Manganese removal by hydroxide precipitation
The hydroxide precipitation method for recovery of
zinc and removal of manganese is one of the effective
methods for control of manganese in the zinc processing
circuit based on the significant difference between the pH
for precipitation of zinc hydroxide and that for manganese
hydroxide. Stolbova et al. (1989) investigated the removal
 W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 178–188
of manganese and magnesium from zinc-industry solu-
tions by an ammonia method. The purification of elec-
trolyte in zinc electrowinning was improved by treating
part of the electrolyte (Zn 130–140, Mg 5–7, Mn 2–8, K
1–3, Na 2–4, and Cl 0.2–0.4 g/L) with 25% NH4OH at pH
7–7.2 and 50 °C. The precipitation recovered 95–96% Zn
while the impurities (Mg 98–99 and Mn 85–95%, K, Na,
and Cl) were accumulated in the (NH4)2SO4 solution
which was evaporated and used as fertilizer. The zinc-
containing precipitate was dissolved in H2SO4 to prepare
pure ZnSO4. Compared with oxidative precipitation
methods, hydroxide precipitation does not need an
expensive oxidant but more base reagents for the two-
stage precipitation of both zinc and manganese together
with other impurities at higher pH. The precipitated base
zinc sulfate may be used as a neutralisation reagent in the
circuit. The hydroxide precipitation method has been
commercially adopted for manganese control in processes
for both zinc sulphide ores and zinc oxide ores. Two of the
processes are summarised below.
4.2.1. HydroZinc process for sulfide ores
The Canadian zinc producer, Teck Cominco, developed
a process, called HydroZinc, for recovery of zinc from
low-grade sulfide ores through heap bioleaching, solvent
extraction, and electrowinning (Lizama et al., 2003;
Filippou, 2004). In order to minimise the corrosion of
the Pb–Ag anodes and lead contamination of cathode zinc
product, manganese has to be added, usually as potassium
permanganate (KMnO4), into the zinc electrolyte. Either
the use of lead anodes with elevated silver content (2%) or
of lead anodes alloyed with bismuth (1.7–1.9%) and silver
(0.7–0.8%) are proposed to avoid a significant drop in the
current efficiency caused by the presence of MnO4−. The
major steps can be summarised as follows:
(1) The pregnant leach solution, which contained 10–
50 g/L zinc, was neutralized in stirred-tank
reactors to pH 4 with limestone slurry to
precipitate all the ferric iron.
(2) Zinc was extracted in two stages with 20% (v/v)
D2EHPA (di-2-ethylhexyl phosphoric acid) dilut-
ed in kerosene. Typically, only 30–50% of the
zinc was extracted.
(3) The zinc pregnant solution from the stripping of
the loaded organic phase reported to electrowin-
ning process.
(4) Part of the neutralized solution (about 5% v/v)
was further neutralized to pH 6.0 to recover all the
contained zinc as basic zinc sulfate.
(5) The bleed was treated with zinc powder to remove
cadmium and was then neutralized to pH 10 to
183
precipitate manganese and some other impurities
(Mg, Ca, etc.) as hydroxides.
(6) The rest of the neutralized pregnant leach solution
was fed to the solvent extraction circuit.
4.2.2. ZINCEX and Skorpion processes for zinc oxide
ores
The ZINCEX process was initially developed in the
early 1970s by TR (Técnicas Reunidas), Spain, and used
a solvent extraction process for the recovery of zinc
from chloride leach solutions (Martin San Lorenzo et al.,
2001). It included two separate sections using two
different extractants: an anionic extractant (a secondary
amine such as Amberlite LA-2) to extract pure zinc
chloride, and a cationic extractant (D2EHPA) to transfer
zinc into a sulfate electrolyte, from which zinc metal
was recovered by conventional electrolysis. This
process was then modified to recovery of zinc from
sulfuric leach solutions, the modified ZINCEX process
(Martin San Lorenzo et al., 2001, 2004, 2005).
The modified ZINCEX process has recently been
used by the Skorpion Zinc plant which is the first
commercial application of zinc SX–EW for processing
primary leach liquor (Cole and Sole, 2003; Sole et al.,
2005). The pregnant sulfuric acid leach solution is first
neutralized by lime to precipitate impurities including
iron, aluminium and silica. Zinc is then extracted using
D2EHPA reagent and electrowon onto aluminium
cathodes. The levels of soluble impurities including
manganese are controlled by bleeding about 8–15% of
the pregnant leach solution or the acid raffinate and
neutralizing the bleed with lime or limestone in two
steps at 70–90 °C. First, the solution is neutralized at a
pH between 6 and 8 to precipitate its zinc content in the
form of basic zinc sulfate, and then is further neutralized
to a final pH above 10 to precipitate the impurities
including manganese (Filippou, 2004). The basic zinc
sulfate is used as a neutralizing agent elsewhere in the
process while the impurity residue containing manga-
nese hydroxide is discarded. Manganese is actually
added back into the zinc electrolyte for maintaining a
certain manganese level for its positive effects.
4.3. Manganese removal by evaporation
Dyvik and Mioen (1987) patented a hydrometallur-
gical process for zinc production from its concentrate. In
electrowinning, a portion of the acidic solution was
withdrawn and vaporized to concentrate H2SO4 to
approximately 60% for precipitation of zinc, magnesium
and manganese impurities as sulfates to prevent
manganese accumulation. The residual H2SO4 solution
184 W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 178–188
containing 1–5 g/L Zn was recycled to the leaching
stage. The metal sulfate crystals could be dissolved in
water for further treatment. Zinc could be precipitated as
basic zinc sulfate or electrowon to produce zinc metal
whilst manganese was discarded after lime treatment of
the liquor.
4.4. Manganese removal by solvent extraction
In conventional treatment of a bleeding of the spent
electrolyte, the acid is lost by neutralization. Recovery
of acid by solvent extraction offers a useful step and
provides the conditioning of pH for subsequent
separation and recovery of zinc and/or manganese. An
iso-butyl alcohol was used for recovery of H2SO4
followed by recovery of zinc by D2EHPA or both zinc
and manganese by naphthenic acid in kerosene from
zinc spent electrolytes (Buttinelli and Giavarini, 1982).
In addition to alcohols, some stronger acid extractants
such as Tri(2-ethylhexyl)amine (TEHA) and Cyanex
923 were also investigated (Eyal and Baniel, 1991; Eyal
et al., 1991a,b; Alguacil and López, 1996).
So far not much work has been devoted to the use of
solvent extraction for the control of manganese in zinc
electrowinning; however, solvent extraction has shown
promise in several methods:
(1) For a neutralized zinc electrolyte containing a high
concentration of zinc, D2EHPA is selective for
zinc over manganese at pH 2.5. While the raffinate
containing manganese can be further treated or
discarded, the zinc stripped from the organic
solution can be recycled back to the circuit.
(2) Cyanex 272 can also be used for extraction of zinc
from a neutralized electrolyte at pH 2.5, leaving
manganese and other impurities in the raffinate.
However, Cyanex 272 is more expensive than
D2EHPA.
(3) For spent electrolyte containing a high concentra-
tion of sulfuric acid, Cyanex 923 could be used for
recovery of acid followed by extraction of zinc
with Cyanex 272 or D2EHPA.
The major advantage of using solvent extraction lies
in the separation and recovery of zinc in the electrolyte
from manganese and other impurities which remain in
the raffinate for further treatment or disposal. However,
there is a high cost of base for the extraction of high
concentrations of zinc in both (1) and (2) except where
associated with an RLE process. Up to 90% of the acid
could be recovered with method (3), but two SX circuits
are required.
4.5. Simultaneous electrolysis and electrowinning
Simultaneous electrolysis to deposit Mn as MnO2 on
the anode and Zn on the cathode for manganese removal
is used in the Glencore's Sulfacid plant in Argentinean.
Manganese is removed during the process typically 0.1 to
0.4 g/L per pass depending on the conditions (Harlamovs,
2007). The process is based on the following simplified
Eqs. (1) and (2).
At the anode,
Mn2þ þ 2H2 O→MnO2 þ 4Hþ þ 2e− ð1Þ
At the cathode,
Zn2þ þ 2e− →Zn ð2Þ
The overall cell reaction can then be expressed by:
ZnSO4 þ MnSO4 þ 2H2 O→Zn þ MnO2
þ 2H2 SO4 ð3Þ
This process could be applied to treatment of a bleed
stream of zinc electrolyte containing a sufficiently high
concentration of manganese.
Verbaan (1980) first patented a simultaneous electrol-
ysis and electrowinning method for removal of manga-
nese. In this method, the Zn- and Mn-containing solution
was electrolysed in the first electrolysis step to produce
MnO2 and zinc on the anode and cathode, respectively,
and the rest of the zinc was recovered in the final elec-
trolysis step. The preferred cathode material was alu-
minium, and the anode was carbon (graphite). The
produced MnO2 was reported to suit battery manufacture.
Simultaneous electrolysis was also used for removal of
manganese from some or all of the purified leach liquor
which contained up to 20 g/L Mn2+ (Verbaan and
Mullinder, 1981). H2SO4 in the range of 0–30 g/L was
found to maximise zinc current efficiency while that
below 50 g/L to maximalise manganese current efficien-
cy. A decrease in Mn concentration from 20 to 10 g/L
decreased Mn current efficiency from 74.7 to 61%.
A similar process for simultaneous electrowinning of
zinc and manganese dioxide was also developed by Toho
Zinc, Japan (1982). In this process, a solution containing
5–80 g/L Zn and 20–80 g/L Mn was electrolysed at a bath
temperature of 75–95 °C. The MnO2 product from the
simultaneous electrolysis was reported to be superior to
natural MnO2, but did not meet the specifications for
conventional EMD (Rodrigues and Dry, 1990).
In another patented process by Nattrass (1986) for the
control of manganese build-up in the electrolyte in zinc
plants, two-step electrolysis was used: (i) electrolysing a
zinc electrolyte containing manganese ions to produce
electrolytic zinc and a spent electrolyte, (ii) further
 W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 178–188
electrolysing the spent electrolyte under agitated condi-
tions to produce solid MnO2, which could be used in the
manufacture of dry battery cells.
The efficiency of the simultaneous electrolysis process
for removal of manganese was reported to be promoted by
using a cold electrolysis at 10–15 °C (Fussi et al., 1998). In
this process, the feed was acidified to 50–90 g/L H2SO4,
cooled to below 15 °C, and electrolysed at 200–400A/m2
using Pb anodes and Al cathodes with air injection for
stirring, followed by settling the slurry product with
addition of a flocculant. The manganese removal was
increased by tenfold compared with conventional chem-
ical pre-treatment, and the same anodes could be used for
30 days, resulting in low operating cost.
Simultaneous electrolysis and electrowinning are
attractive means to control the manganese level in a zinc
electrolyte by treating part or all of the electrolyte using
graphite as anodes for MnO2 deposition and aluminium
as cathodes for zinc deposition. Their advantages are:
(1) The same electrowinning equipment can be used
without many modifications.
(2) The treatment does not alter the acidity and other
conditions significantly.
(3) Recovery of manganese as a quality product close
to EMD is achievable under well-controlled
conditions.
However, their disadvantages are:
(1) Other impurities remain in the electrolyte.
(2) The optimum conditions for deposition of MnO2
and zinc are not identical and need separate
controls.
(3) Current efficiencies for zinc and MnO2 production
are low.
(4) High energy requirements are expected if the
concentrations of manganese are low in the
electrolyte.
5. Effect of manganese in copper SX–EW operations
Some problems caused by manganese during copper
SX–EW commissioning and operations were reported
by Miller (1995) and Miller et al. (1997). They include:
(1) Decrease in organic reagent kinetics and capacity
with high copper concentrations in raffinate due to
reagent oxidation and degradation by MnO2.
(2) Long phase disengagement time and stable
emulsion formation in SX settlers as a result of
surface-active degradation products.
185
(3) High organic loss to the raffinate and high
electrolyte loss to the organic by entrainment.
(4) MnO2 precipitating on electrode surfaces.
(5) Sticky cathodes and nodular growth on copper
cathodes.
It has been established that Mn2+ itself has no effect
on the operation of the SX plant. However, when the
manganese is transferred into the copper EW electrolyte,
the Mn2+ is oxidised to higher valent species (MnO4−
and MnO2) in the highly oxidising environment in the
EW cells. These, in turn, generate further symptoms
which can form positive feedback loops and very
quickly lead to a catastrophic reduction in plant
performance.
The mechanism of organic degradation caused by
manganese was identified by Cheng et al. (2000) with a
coupled SX–EW circuit using Acorga M5640 and LIX
984N as extractants. It was observed by visible spectra
that Mn2+ in the electrolyte was primarily oxidised to
Mn3+, which was further oxidised to MnO4− . The
formation of these high valent manganese species
were evidenced by the high redox potentials measured.
Solid MnO2 particles were also formed. It was further
determined that most of the observed organic oxidation
and consequent emulsion formation were associated
with the presence of Mn3+ rather than MnO4− species. A
number of degradation products of the hydroxyoxime
extractants were detected by a combination of gas
chromatography (GC), high performance liquid chro-
matography (HPLC) and pre-concentration techniques,
including an acidic oxidation product of 5-nonylsalicy-
laldehyde which was consistent with a 5-nonylsalicylic
acid. There was also evidence for oxidative cleavage of
the nonyl chain of the aldoximes or their degradation
products, the formation of a nonyl phenol dimer, and
possibly also polymerisation of the related hydroxyox-
imes or their degradation products.
Ipinza et al. (2003, 2004) studied the formation of
anodic slime in copper electrowinning. It was observed
that in the presence of manganese in the electrolyte, a
manganese dioxide double layer was formed at the
anode. This double layer was always composed of a
thick external layer of non-adhering and easily remov-
able scales, and a thin internal layer adhering relatively
well to the surface of the electrode. Manganese
deposited on the anode surface and reduced the presence
of lead compounds in the slime, which was interpreted
as a protective effect of this ion on the anodic corrosion.
The presence of iron in the electrolytes only inhibited
the formation of tetragonal manganese oxide, reducing
the volume of the slime formed.
186 W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 178–188
The presence of Mn2+ increased the density and
viscosity of copper electrolyte (Subbaiah and Das, 1994).
For example, the conductivity of copper electrolyte
dropped from 420 mΩ/cm to 370 mΩ/cm in the presence
of 19.9 g/L of Mn2+. The limiting current density and
copper mass transfer coefficient were found optimum at a
concentration of 5 g/L Mn2+. The manganese impurity
also significantly affected the surface morphology and
crystal orientation of the cathode copper, promoting a
growth of pyramidal and planar structures, while restrict-
ing the growth of ridge-type structures.
6. Methods for control of manganese in copper
electrowinning
6.1. Control of electrolyte Eh by addition of reductants
A number of solutions for the manganese problems in
copper SX–EW operations at Girilambone Copper
Company were reported (Miller, 1995; Miller et al.,
1997). As the main problems of manganese in copper
electrowinning were related to the high valent manganese
species generated in EW environment, a method for
maintaining the electrolyte Eh at an appropriate value
(around 400 mV) and thus keeping manganese in the Mn2+
state by addition of reductants was attempted. An initial
trial on the reduction of Eh by addition of ferrous sulfate to
the electrolyte was found kinetically slow. An addition of
SO2 successfully controlled the Eh in the range of 400–
450 mV. A concentration of 1 g/L Fe2+ was required to
maintain the Eh and the manganese in the Mn2+ state.
6.2. Oxidative precipitation
Shaw et al. (1999) reported a patented process for
control of manganese, iron, and chloride in copper
electrowinning tank houses which was tested in a pilot
plant. In the process, manganese was removed as
insoluble manganese dioxide by oxidative precipitation
with permanganate salts.
6.3. Solvent extraction of acid from bleed prior to
manganese hydroxide precipitation
For conventional impurity control in copper electro-
winning by bleeding, the acid can be recovered by solvent
extraction. A process using Cyanex 923 and a branched
long-chain aliphatic tertiary amine, tris(2-ethylhexyl)
amine (TEHA) for selective recovery of up to 90% of
the sulfuric acid from electrolyte bleed streams, was
developed by Gottliebsen et al. (2000). The process
involved extraction at ambient temperature and stripping
with water at elevated temperatures. Both extractants had
the ability to produce acid with a concentration of N120 g/
L sulfuric acid, which could be recycled back into the tank
house, reducing both neutralisation and acid make-up
costs. The weakly acidic raffinate could be further treated
by the conventional bleeding procedures to precipitate
manganese hydroxide. The reaction mechanisms between
TEHA and H2SO4 depended on acid concentrations. At
acid concentrations below 1M, it involved the formation
of the amine sulfate salt, combining two amines for every
sulfate, which can be expressed by Eq. (4).
P P
H2 SO4 þ 2R3 N ¼ ðR3 NHÞ2 SO4 ð4Þ
At higher concentrations of sulfuric acid, the formation of
amine bisulfate dominated as described by Eq. (5).
P P
H2 SO4 þ ðR3 NHÞ2 SO4 ¼ 2ðR3 NHÞHSO4 ð5Þ
7. Summary of manganese control in zinc and
copper electrowinning
The presence of higher valent species of manganese
resulting from the oxidation at the anodes has
detrimental effects on both copper and zinc solvent
extraction and on the electrowinning of zinc and copper.
Various methods have been investigated for manga-
nese control in zinc and copper electrowinning. These
include:
(1) Addition of a reductant, e.g. ferrous iron and
aqueous SO2 to the electrolyte to maintain a low
Eh value (400–450 mV) and to avoid occurrence
of any higher valent manganese species.
(2) Oxidative precipitation of manganese from neu-
tralized electrolyte as insoluble MnO2 using Caro's
acid or SO2/O2. A drawback of this strategy is that
other impurities, e.g. Mg, Cl−, F− etc., remain in the
circuit, which have to be treated when it exceed the
acceptable levels.
(3) Solvent extraction of zinc or copper using a
cation-exchange extractant, e.g. D2EHPA or
hydroxyloximes can selectively recover zinc or
copper from the solution and leave other impuri-
ties including manganese in the raffinate which
could be further treated for recovery of manganese
or discarded. The loaded organic phase can be
stripped using the spent electrolyte to produce a
metal-rich sulfate solution for electrowinning.
(4) The use of composite anodes to increase the
current efficiency with less anode scale and cell
sludge.
 W. Zhang, C.Y. Cheng / Hydrometallurgy 89 (2007) 178–188
For separation methods such as sulfide precipitation,
carbonate precipitation, and hydroxide precipitation, the
recovery of a large amount of zinc prior to removal of
manganese or copper makes these methods less
economically viable. Among various separation techni-
ques, oxidative precipitation and solvent extraction are
recommended for future work.
Acknowledgments
The authors would like to thank CSIRO Minerals
library staff for collecting some references, and Dr
David Muir for reviewing this paper and providing
valuable comments. We would also like to thank the
reviewer, Mr Juris Harlamovs (TeckCominco), and
another anonymous reviewer for some helpful com-
ments and useful information provided.
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