SME Annual Meeting

Feb. 19 - 22, 2012, Seattle, WA

Preprint 12-038
NEW DEVELOPMENTS IN THE RECOVERY OF COPPER, COBALT, ZINC AND MANGANESE IN THE BOLEO PROCESS
D. Dreisinger, Baja Mining Corp., Vancouver, BC, Canada
T. Glck, Baja Mining Corp., Vancouver, BC, Canada
J. Lu, Univ. of British Columbia, Vancouver, BC, Canada
F. Xie, Univ. of British Columbia, Vancouver, BC, Canada
K. Marte, Baja Mining Corp., Vancouver, BC, Canada
F. Parada, Univ. of British Columbia, Vancouver, BC, Canada

processing facilities on a bleed stream of copper SX raffinate to

produce cobalt metal and zinc sulfate monohydrate salt are brought on
line.

ABSTRACT
Baja Mining is currently constructing the Boleo metallurgical plant
in Santa Rosalia, Mexico to recover copper, cobalt, zinc and possibly
manganese products from the Boleo ore. The process involves an
acid seawater leach of the whole ore followed by solid-liquid separation
and washing of the leach residue. Solvent extraction is used to
separate copper, cobalt and zinc from solution. Copper and cobalt are
recovered as cathode metal products and zinc as a zinc sulphate
monohydrate. Manganese may be directly precipitated as manganese
carbonate which can be used as a feedstock for manganese metal
production. Laboratory testing has continued to refine various aspects
of the process including iron removal, cobalt and zinc solvent
extraction, cadmium cementation, cobalt electrowinning and
manganese metal electrowinning. The results of this testing are
reported in this paper.

The overall hydrometallurgical process for Boleo has been

reviewed in earlier publications [1-3]. Figure 1 illustrates the process
steps in block format. The process is a whole-ore leach in seawater
using a combination of acid oxidation and acid reduction leaching to
extract copper, cobalt, zinc and manganese from the ore. The leach
solution is separated from the barren solids by a high rate counter
current decantation circuit. Copper is recovered via solvent extraction
and electrowinning as LME grade A cathode.
ROM
Ore

Crush

Scrub and Grind

INTRODUCTION
Acid Plant and
SO2 Plant

The Boleo property is held by the Mexican company, Minera y

Metalrgicadel Boleo S.A. de C.V. (MMB). MMB is owned 70% by
Baja Mining Corp. and 30% by a consortium of Korean companies
consisting of KORES Korea Resources Corporation, LS Nikko
Copper, Hyundai Hysco, SK Networks and Iljin Copper. The project is
fully financed and is now under construction with an expected startup
in early 2013.

Leach

CCD

Cu SX and EW

Tailings Dam
Copper
Cathode

Neutralization

Fe Removal

Average annual production, for the first six years for each of the
metals is forecast as: 56,697 tonnes of copper cathode, 1,708 tonnes
of cobalt cathode and 25,364 tonnes of zinc sulphate monohydrate.
The project has an average life-of-mine cash cost (based on the three
year trailing average metal prices, as of December 31, 2009, in
accordance with SEC guidelines) of -$0.29/lb Cu, net of by-product
credits for cobalt and zinc and with no credit for manganese
production. There is the potential to produce up to 220,000 tonnes per
annum of manganese carbonate (~100,000 tpa contained Mn) via the
relatively simple addition of a small number of unit operations to the
proposed plant.

DSX

Manganese
Carbonate

ZnSX

Zinc
Sulphate

CoSX

Co IX and EW

Cobalt
Cathode

Figure 1. The Boleo Hydrometallurgical Process Flowsheet.

The project will consist of an underground and a surface mining

operation, providing run-of mine (ROM) ore to a fully integrated
hydrometallurgical facility. The mine plan developed for the Boleo
deposits provides for a combination of underground and open pit
mining of various mineralized layers within the orebody referred to as
mantos. Underground mining is by mechanized methods, employing
continuous mining machinery similar to that used in coal mining in
production and development modes. The underground mining
techniques proposed for the full scale operation were successfully
tested in a test mining exercise, conducted in late 2005 and early 2006,
that was followed up with a separate roof bolting optimization exercise
in November 2006.

The copper solvent extraction raffinate is split with a portion of the

raffinate returning to leaching and the balance advancing to cobalt,
zinc and manganese recovery. The raffinate for cobalt, zinc and
manganese recovery is first neutralized to remove iron and aluminum
from solution and then subjected to a novel direct solvent extraction
process (DSX) developed by CSIRO (Australia) [4-6]. The direct

solvent extraction process uses a mixture of Versatic 10 (Shell) and

LIX 63 (BASF) extractants to separate cobalt and zinc away from

manganese in the neutralized, iron-free raffinate. The raffinate from
the DSX extraction may be treated in the future to recover manganese
by precipitation as manganese carbonate.

The hydrometallurgical facility will be built and commissioned so

that the whole ore atmospheric leach, copper solvent extraction and
electrowinning facility will be operated for a quarter before the

The cobalt and zinc are stripped from the DSX loaded organic
solution and the strip solution advances to zinc recovery using a
phosphinic acid extraction circuit.
The zinc is stripped as a

Copyright 2012 by SME

SME Annual Meeting

Feb. 19 - 22, 2012, Seattle, WA
concentrated, high purity solution and will then be evaporated in spraydried granulator. o make the zinc sulfate monohydrate product for sale.
The raffinate from zinc solvent extraction advances to cobalt solvent
extraction (also with phosphinic acid extractant) and electrowinning to
produce high purity cobalt cathode.

ZnR2(org) + H2SO4 = ZnSO4 + 2HR(org)

DSX Cobalt Stripping (Bulk Stripping).
CoR2(org) + H2SO4 = CoSO4 + 2HR(org)

The copper, cobalt and zinc mineralogy in the Boleo ore is

complex. These metals exist as sulfides in the sulfidic zones of the
orebody and as a range of simple to complex oxides (including
apparently some association in ferrites and clays) in the oxidized zones
of the orebody.There is frequent association of copper, cobalt and zinc
with manganese. The acid leaching process uses simple acid attack of
the oxides and oxidation of the sulfides. The manganese dioxide in the
Boleo ores is a natural oxidant for the sulfides and is used as such in
the leaching process. The acid oxidation leach reactions for oxides
and simple sulfides are shown below. The reduction leaching process
reduces manganese dioxides with dissolved sulfur dioxide. The
reduction reactions are also shown below.

(1)

ZnO + H2SO4 = ZnSO4 + H2O

(2)

CoO + H2SO4 = CoSO4 + H2O

(3)

Cu2S + 2MnO2 + 4H2SO4 = 2CuSO4 + 2MnSO4 + S + 4H2O

(4)

ZnS + MnO2 + 2H2SO4 = ZnSO4 + MnSO4 + S + 2H2O

(5)

CoS + MnO2 + 2H2SO4 = CoSO4 + MnSO4 + S + 2H2O

(6)

Zinc Extraction.
ZnSO4 + 2HR(org) + Na2CO3 = ZnR2(org) + Na2SO4 + CO2(g)
+ H2O

ZnR2(org) + H2SO4 = ZnSO4 + 2HR(org)

(16)

Cobalt Extraction.
CoSO4 + 2HR(org) + Na2CO3 = CoR2(org) + Na2SO4 +
CO2(g) + H2O

(17)

Cobalt Stripping.
CoR2(org) + H2SO4 = CoSO4 + 2HR(org)

(7)
(8)

(18)

Cobalt Electrowinning.
CoSO4 + H2O = Co + H2SO4 + 0.5O2(g)

The cobalt, zinc and manganese in solution are not affected by

copper solvent extraction. Only small losses occur during CCD
washing and via co-precipitation with iron. The first step in cobalt and
zinc recovery from the iron-free neutralized raffinate is the DSX circuit
using a CSIRO designed extraction system. CSIRO has developed a
range of synergistic extractants tailored to specific metal separations
[4-6]. In the case of Boleo, the major challenge is the extraction of
cobalt and zinc without extraction of manganese. The particular

synergistic system selected for Boleo is a Versatic 10 LIX 63

mixture. With this system, cobalt is loaded in preference to zinc which
in turn is loaded in preference to manganese.

(19)

The Boleo process was piloted in 2004 and 2006. A number of

studies have been undertaken since the completion of the pilot plant in
order to provide additional definition to the design. These additional
studies include;

The DSX circuit was originally designed for bulk extraction and
selective stripping of zinc and cobalt. This was also the basis for pilot
plant testing of the circuit at SGS. Zinc and cobalt loading is performed
with pH control using sodium carbonate. Selective stripping was
abandoned in the Boleo design due to an inability to prevent cobalt
loss with the zinc sulphate strip solution. The current design has bulk
stripping followed by phosphinic acid separation of cobalt and zinc.

Iron removal
DSX solvent extraction optimization
Cadmium cementation
Cobalt electrowinning and;
Manganese metal production from manganese carbonate.

Each of these areas of further study is reported below.

IRON REMOVAL
The iron removal process is designed to remove iron and
aluminum to low levels prior to the DSX process, while minimizing the
precipitation and loss of cobalt, zinc and manganese.

DSX Cobalt and Zinc Solvent Extraction (with small amount of Mn

co-extraction).
CoSO4 + 2HR(org) + Na2CO3 = CoR2(org) + Na2SO4 +
CO2(g) + H2O
ZnSO4 + 2HR(org) + Na2CO3 = ZnR2(org) + Na2SO4 + CO2(g)
+ H2O
MnSO4 + 2HR(org) + Na2CO3 = MnR2(org) + Na2SO4 +
CO2(g) + H2O

(15)

Zinc Stripping.

Reduction leaching (addition of sulfur dioxide to the ore slurry).

MnO2 + SO2 = MnSO4
MFe2O4 + SO2 + 2H2SO4 = MSO4 + 2FeSO4 + 2H2O, M=Zn,
Co, etc.

(14)

The fully stripped organic is then recycled back to loading. The

DSX raffinate advances to manganese recovery. The bulk strip
solution from DSX contains zinc, cobalt and other minor impurities.
This solution will be treated sequentially by zinc solvent extraction and
stripping and then cobalt solvent extraction, stripping and
electrowinning. The zinc and cobalt solvent extraction circuits will both
use phosphinic acid extractants in identical reagent formulations, which
also eliminates any potential cross-contamination issues that might
result from organic carry-over. The zinc strip solution represents the
feed to zinc sulfate monohydrate granulation.

Acid oxidation leaching (acid leaching with manganese dioxide in

the ore).
CuO + H2SO4 = CuSO4 + H2O

(13)

During the 2006 demonstration pilot plant for the Boleo process,
iron removal was performed in a series of four stirred reactors with
oxygen addition for ferrous to ferric iron removal. Iron removal was
practiced at pH 4 (controlled by limestone slurry addition) and 50 C.
The iron removal reactors did not have sufficient gas-liquid mass
transfer rates for oxygen addition to the slurry so hydrogen peroxide
was added in the pilot plant as a trim to oxidize the last vestige of the
ferrous via oxidation to ferric and precipitation.

(9)
(10)
(11)

The key reactions in the iron removal process are shown below.
DSX Manganese Scrubbing.
MnR2(org) + CoSO4= ZnR2(org) + MnSO4

H2SO4 + CaCO3 + H2O = CaSO4.2H2O + CO2

Fe2(SO4)3+ 3CaCO3 + 9H2O = 2Fe(OH)3 + 3CaSO4.2H2O +
3CO2
Al2(SO4)3+ 3CaCO3 + 9H2O = 2Al(OH)3 + 3CaSO4.2H2O +
3CO2

(12)

DSX Zinc Stripping (now part of Bulk Stripping with Cobalt)

(20)
(21)
(22)

Copyright 2012 by SME

SME Annual Meeting

Feb. 19 - 22, 2012, Seattle, WA
FeSO4 + 0.25O2+ CaCO3 + 3.5H2O = Fe(OH)3 +
CaSO4.2H2O + CO2

quantify the rates of iron removal that may be achieved. The extent of
loss of cobalt and zinc as a function of pH will be confirmed as part of
this on-going testwork.

(23)

The average iron concentration in the thickener overflow for the

entire pilot plant campaign was 15.5 mg/L. The circuit was routinely
operated with residual dissolved iron levels below 5 mg/L with a few
short periods of high iron concentrations due to process upsets. The
losses of cobalt and zinc were calculated by the Fe tie method. For
example for cobalt, the loss was calculated as;
100*(Co in Ppte/(Fe in Ppte/(Fe Solution IN-Fe Solution
OUT)))/Co Solution IN
The losses of pay metals were generally low. Cobalt losses
averaged approximately 1.2% while losses of zinc were just above
4.5%. Much of the loss was due to spikes in precipitation due to pH
excursions in the iron precipitation tanks, leading to periods of higher
cobalt and zinc precipitation.
Experimental
In order to study the iron removal process further, a synthetic
solution of Boleo DSX raffinate was prepared from mixed salts. The
target concentrations were; 4150 mg/L Fe(II), 640 mg/L Fe(III), 2820
mg/L Al, 1.6 mg/L Cd, 248 mg/L Co, 31.1 mg/L Cu, 15200 mg/L Mn,
3970 mg/L Mg, 2.66 mg/L Ni and 1230 mg/L Zn. A KCl-NaCl-MgCl2
seawater matrix was used to reflect the use of seawater at the site.
The initial solution pH was 2.0. The iron removal experiments were
carried out with 500 mL of synthetic solution in a baffled reactor with a
Rushton turbine impeller. Oxygen gas was sparged at 100 mL/min
under the impeller. pH adjustment was automatic with addition of a
40% limestone slurry (particle size less than 50 um P80). The iron
removal experiments were started by initial adjustment of pH to the
target (3-5.5), followed by initiation of oxygen addition.
The
temperature was maintained at 40 C. Samples were taken for up to 6
hours in order to follow the rate of iron removal.

Figure 3. Photographs of the Precipitates Formed During the Iron

Removal Testing.
DSX SOLVENT EXTRACTION OPTIMIZATION
Pilot scale DSX tests have been conducted to support the Boleo
Definite Feasibility Study (DFS). The DSX circuit was fully stabilized
by 50 h of operation. Cobalt and zinc extraction ranged from +98 to
99.9%. This test work indicated the extraction of cobalt and zinc and
the rejection of manganese through the DSX circuit were excellent.
The bulk DSX strip solutions contained cobalt and zinc and minor
manganese and other impurities and this solution will be treated
sequentially by zinc solvent extraction and stripping and zinc sulphate
monohydrate granulation and then cobalt solvent extraction, stripping
and electrowinning. The DSX raffinate advances to the CCD thickener
or to manganese recovery via manganese carbonate precipitation.

Results
Figure 2 summarizes the results of the iron removal work. At pH
of 3 and 3.5, the rate of iron removal was very slow. Starting at pH of
4.0, the rate was much faster. The rate increased from pH 4.5 to 5.5.
At pH 5.5, the rate was so fast, all iron was oxidized and removed
when the first sample was taken after 15 minutes.

The DSX extractant formulation used in the 2006 pilot plant

contained 0.33 mol/L Versatic 10 and 0.3 mol/L LIX 63, corresponding
to a mixture of 6.25% and 13.2% by volume, respectively. However,
calculations of the loaded organic composition for the design for the
commercial facility has indicated that the total metal in the organic is
only about 0.034 mol/L. Comparing to the extractant concentration,
there is an opportunity to optimize the DSX system through potentially
increasing the metal loading on the organic by reducing the extractant
concentration in the solvent system. Note that this opportunity is
tempered by the fact that LIX 63 has syn and anti isomers. Only the
anti isomers are involved in the synergistic extraction of cobalt and
zinc. Nevertheless, there still appears to be a substantial excess of
reagent under the design condition. The optimization study was thus
conducted to examine the effect of modifying the DSX formulation on
separation of Co, Zn and Mn from Boleo solution.

FeConcentrationinSolution(mg/L)

6000

5000

4000
3
3.5

3000

4
4.5

2000

5
5.5

1000

Experimental
Industrial grade Versatic 10 was supplied by Shell Chemicals and
LIX 63 was supplied by BASF (formerly Cognis). The diluent, ORFOM
SX 80 CT was supplied by Chevron, USA. A synthetic mixture solution
of metals (Mn, Mg, K, Na, Ca, Co, and Zn) was prepared from reagent
grade salts.

0
0

Time(h)

Figure 2. Iron Removal Kinetics at pH Values of 3 to 5.5.

The solvent was prepared with different volumes of Versatic 10

and LIX 63, and diluted with ORFOM SX 80 CT. The temperature was
controlled through a water bath. For each test, the synthetic solution
and the solvent were put into the flask and mixed by shaking or
magnetic stirring. The pH was adjusted by addition of 10% H2SO4 or
25% sodium carbonate solution. Fresh organic and the synthetic leach
solutions were mixed at unit volume ratio of aqueous to organic and 40
C. Samples were collected at 0.5 pH intervals after mixing for 510
min and when the pH was stable at each target pH point. The aqueous
samples were filtered with Whatman No. 3 filter paper and the organic

Figure 3 shows the types of precipitates that were obtained. The

main precipitate is a mixture of aluminum hydroxide and gypsum. As
the pH increased, the amount of iron oxide co-precipitation increased,
resulting in an increase in the red colouration of the precipitate.
There was considerable difficulty in maintaining tight pH control
for the pH values at 4.5 and beyond as the slight over-addition of
limestone under these conditions can increase the pH to very high
values. Accordingly further work is underway to refine the lab
procedure with alternate neutralizing reagents in order to better

Copyright 2012 by SME

SME Annual Meeting

Feb. 19 - 22, 2012, Seattle, WA
100

100

80

80

60

Extraction, %

samples with 1PS filtered paper. The aqueous samples were sent for
direct ICP analysis. For the organic samples, 5 mL sample was
stripped with 25 mL of 2 mol/L H2SO4 solution and the strip solution
was collected for ICP analysis.

Co
Zn

Extraction, %

Results
In the first set of optimizing experiments the concentration of each
of Versatic 10 and LIX 63 was reduced progressively while maintaining
a constant molar ratio of Versatic 10 over LIX 63 as shown in Table 1.
Each of the five mixtures was then tested for metal loadings versus pH
and the results are shown in Figure 4. As expected, the extractants
exhibit a selectivity order for the three metals as follows: Co > Zn > Mn.
It appears that lowering the extractant concentrations of both Versatic
10 and LIX 63 in tandem has a negligible impact on the loading of
cobalt but does suppress the loading of zinc and manganese. The
separation factors for cobalt over manganese decrease from about
5000:1 to around 2000:1 as a result of lowering the extractant
concentrations from 6.25% v/v Versatic 10 and 13.20% v/v LIX 63 to
2.25% v/v Versatic 10 and 4.75% v/v LIX 63 (approximately three times
decrease). A separation factor of 2000:1 is still an excellent value upon
which to base a Co/Mn separation. At the same time, the separation
factor for zinc over manganese is reduced from about 350 to 150. The
lower zinc separation factor indicated the zinc loading would be
reduced slightly in order to maintain absolute selectivity over
manganese under lower extractant concentrations. In order to recover
greater amounts of zinc at lower extractant concentration, a higher pH
has to be used.

Mn

40

Zn
40

Mn
Co

20

20

0
3.75

60

4.25

4.5

4.75

5.25

5.5

0
3.75

5.75

4.25

4.5

(a)

5.25

5.5

5.75

(b)

100

100

80

80

Extraction, %

Extraction, %

4.75
pH

pH

60

Zn

40

60

40

Zn

Mn

Mn

Co

20

20
Co

0
3.75

4.25

4.5

4.75

5.25

5.5

5.75

0
3.75

4.25

4.5

4.75

5.25

5.5

5.75

pH

pH

(c)
(d)
Figure 4. The Extraction of Co, Zn and Mn. LIX 63 and Versatic 10
content (% v/v) of (a) 6.25 and 13.2, (b) 4.25 and 8.98, (c) 3.25 and
6.86 and (d) 2.25 and 4.75; 30 C. Orfom SX 80 CT diluent.
CADMIUM CEMENTATION
Cadmium is an undesirable impurity in both the final cobalt
product (cobalt metal cathode) and the final zinc product (zinc sulphate
monohydrate). Low levels of cadmium are leached from the Boleo ore
and deport to the feed to the DSX circuit. The DSX extraction system
loads and strips small amounts of cadmium into the DSX bulk strip
solution containing cobalt and zinc. Zinc dust cementation was tested
in the Boleo pilot plant for the purpose of removing cadmium from the
bulk strip solution before zinc and cobalt solvent extraction with
phosphinic acid.

It is believed that LIX 63 plays a synergistic role of increasing

selective extraction of cobalt and zinc away from manganese in the
DSX system [4-6]. A selectivityparameter of 2000-5000 for Co/Mn was
easily obtained according to the experimental results. That indicated
that it may be possible to reduce the LIX 63 concentration while
maintaining the V10 concentration in order to decrease the first fill
amounts for LIX 63 required for the commercial plant while maintaining
metal loading and selectivity. A second series of optimization
experiments were run by fixing the Versatic 10 content at 5.25% v/v
and varying the LIX 63 content of the organic. The results are
presented in Figure 5. Surprisingly, the cobalt extraction with all
formulations is very high. As LIX 63 content of the organic is reduced,
manganese extraction is suppressed and zinc extraction falls. These
extraction results have been used to estimate optimum formulations for
DSX and have resulted in specification of 4.5% v/v Versatic 10 and
6.7% v/v LIX 63 and pH 4.75. Under these conditions, it is expected
that Co and Zn extraction can be maintained close to 100% while
rejecting Mn in a multi-stage counter-current contact design. Further
increases in pH may provide higher metal loading but may also
promote higher overall soluble losses of Versatic 10 that are to be
avoided.

Small amounts of uranium and copper are also present in the bulk
strip solution and are also reduced by zinc dust cementation. The key
reactions are;
CdSO4 + Zn = Cd + ZnSO4

(24)

CuSO4 + Zn = Cu + ZnSO4

(25)

UO2SO4 + Zn = UO2 + ZnSO4

(26)

H2SO4 + Zn = H2 + ZnSO4

(27)

The levels of the key metals in solution are summarized in Table

2. The main element that will cement with zinc dust is copper, followed
by uranium. Cadmium is clearly a very minor species.

Table 1. The organic formulation of five solvent mixtures.

Versatic10
LIX 63
ORFOM SX 80 CT
Test No.
(%, v/v)
(%, v/v)
(%, v/v)
1
6.25
13.20
80.55
2
5.25
11.09
83.66
3
4.25
8.98
86.77
4
3.25
6.86
89.89
5
2.25
4.75
93.00

During the pilot plant, a number of cadmium cementation tests

were performed at room temperature and 60 C using powdered zinc
dust.
Table 3 summarizes the operating results for the hot
cementations. With these treatments, it was possible to reduce the
concentration of cadmium below 0.3 mg/L. Copper levels were also
reduced to 0.2 mg/L or lower. The other element that was found to
cement out was uranium. From initial levels over 90 mg/L (Table 2),
the concentration was reduced below 5 mg/L except in the first batch.

This work shows that it is possible to dramatically reduce the

extractant concentrations while maintaining cobalt loading. However, if
zinc loading is to be maintained at a high value, it is essential to
maintain a higher extractant concentration. For the conditions used in
this study, a Versatic concentration of 4.25% v/v and a LIX 63
concentration of 6.7% v/v should be sufficient to maintain high cobalt
and zinc recovery while essentially completely rejecting manganese.
Under the constant content of Versatic 10, manganese extraction is
suppressed and zinc extraction falls when the content of LIX 63 in the
organic is reduced.

A number of lab studies were performed under controlled

conditions to better define the design parameters for cadmium removal
from the bulk strip solution.

Copyright 2012 by SME

SME Annual Meeting

Feb. 19 - 22, 2012, Seattle, WA

80

60

Extraction, %

80

Extraction, %

Sulphuric acid was added to a concentration of 0.5 g/L to avoid

precipitation.

100

100

Zn
Mn

60

Mn

Co

Co

20

0
3.75

20

4.25

4.5

4.75

5.25

5.5

0
3.75

5.75

4.25

4.5

pH

4.75

5.25

5.5

5.75

pH

(a)

(b)

100

100

80

80

Extraction, %

Extraction, %

Cementation tests have been performed using 100, 150, 200, 250
and 300 % of the stoichiometric amount of zinc necessary to cement
o
(Fe + Cu + Ni + Cd) at pH 3.5, 40 C and 300 RPM agitation in a 200 ml
glass jacketed cell with baffles under a nitrogen atmosphere.200 ml of
o
solution were fed to the sealed cell, heated to 40 C using a circulating
water bath and kept under a nitrogen atmosphere for at least 30
minutes before beginning the test.

Zn

40

40

60
Zn
40

60

Zn

40

Mn

After the initial 30 minutes of purging nitrogen and reaching the

desired pH, metallic zinc powder (sample obtained from Teck Trail
Zinc Refinery) was added to the system and samples are drawn from
the cell at 2, 5, 10, 15, 20 and 30 minutes. Final filtrate and wash
solution are measured and kept in bottles. Solids are also kept.
Solution pH was controlled using a 25 % Na2CO3 to reach the desired
initial pH prior to starting the test. During the test a 1.0 % sulphuric acid
solution was fed to the reactor using a pH controller connected to a
peristaltic pump which added the sulphuric acid to the reactor. Acid
addition was required to counter the progressive rise in pH due to
hydrogen formation. Solution samples were analysed by ICP-MS. The
apparatus for cementation is shown in Figure 6. A closeup of the
reactor is shown in Figure 7.

Mn
Co
20

0
3.75

Co

20

4.25

4.5

4.75

5.25

5.5

5.75

0
3.75

pH

4.25

4.5

4.75

5.25

5.5

5.75

pH

(c)
(d)
Figure 5. The Extraction of Co, Zn and Mn with 5.25% (v/v) Versatic 10
and LIX 63 (%, v/v) of (a) 12.2, (b) 9.98, (c) 8.97 and (d) 6.65; 30 C.
Orfom SX 80 CT diluent.
Table 2. DSX Strip Solution Composition (2006 Pilot Plant).
Element
Assay (mg/L)
Cu
731
Cd
4.50
U
92
Zn
12500
Co
6300
Ni
215
Al
98
Fe
62
Na
45
Mg
25
Mn
15
Cl
11.7
Ca
5.8
Table 3. Hot Zinc Dust Cementation Results (60 C).
Batch
1
2
3
60C Treatment 1st 2nd 1st 2nd 3rd 1st 2nd
Zn Dosage, g/L 1
0.5
1
0.5 0.5
1
0.5
pH before
--- 5.86 --------- 5.36
adjust
pH before Zn
3.8 3.4 3.36 3.4 3.4 3.56 3.4
added
pH of final
5.7 5.35 5.29 5.55 --- 5.3 5.71
filtrate
Final Cd, mg/L 0.42 0.26 0.25 0.98 0.4 <0.3 0.18
Final Cu, mg/L 0.16 0.24 0.23 0.56 <0.1 <1 0.17
Final U, mg/L
7
7
7
10
3
38 0.8

4
1st
1

2nd
0.5

---

5.11

3.4

3.4

Figure 6. Cd cementation experimental setup.

Results
The results for cadmium and copper removal are shown in
Figures 8 and 9. Cadmium and copper were removed almost
completely after 30 minutes, especially with zinc additions above 200
% of the stoichiometric amount in fact, 200, 250 and 300 % of
stoichiometric zinc gives similar results and pH does not seem to
cause a considerable impact, except for iron and nickel in which case,
removal from solution increases slightly with pH, but does not go over
20 %. The final design of cadmium removal takes into account the
need for excess zinc dust addition and the residence times indicated in
the testing.

5.55 5.58
0.98 0.22
0.56 0.17
10
2

Experimental
Solutions for Cd cementation were prepared from reagent grade
salts and deionized water.
Metal

COBALT ELECTROWINNING
The DSX pilot plant circuit results for zinc and cobalt recovery
have been presented in an earlier paper [1]. Cobalt and zinc recovery
rates ranged from 98.3 to 99.9% throughout the stable period of pilot
plant operation (starting with an average of 232 mg/L Co, 10.28 g/L Mn
and 830 mg/L Zn).

[C] (g/L)

Zn

58.00

Co

10.50

Mn

0.200

Fe

0.200

Cu

0.110

Ni

0.048

Cd

0.050

The DSX circuit produced two strip liquors in the pilot plant
corresponding to the zinc strip and the bulk strip. The bulk strip
composition is shown in Table 4. This solution was fed to sequential
zinc and cobalt recovery using phosphinic acid based extractant.

Copyright 2012 by SME

SME Annual Meeting

Feb. 19 - 22, 2012, Seattle, WA
Cu Removal pH 4.0

100

80

80

Cu Removal (%)

Cu Removal (%)

Cu Removal pH 3.5

100

60

100 % Zn

40

150 % Zn

60

100 % Zn

40

150 % Zn
200 % Zn

200 % Zn
250 % Zn

20

250 % Zn

20

300 % Zn

300 % Zn

0
0

10

15

20

25

30

10

15

Tim e (m in)

20

25

30

Tim e (m in)

(a)

(b)
Cu Removal pH 4.5

100

Cu Removal (%)

80

60
100 % Zn
40

150 % Zn
200 % Zn
250 % Zn

20

300 % Zn
0
0

10

15

20

25

30

Tim e (m in)

(c)
Figure 9. Copper removal kinetics at pH of 3.5, 4.0 and 4.5 at 40 C.
v

Cobalt was recovered from the zinc raffinate using 30 /v Cyanex

272 in Orfom SX 80CT diluent. The solvent extraction circuit was
designed with 4 extract 2 scrub 3 strip and 1 conditioning stage.
Cobalt was stripped with spent electrolyte from cobalt electrowinning.
The cobalt strip liquor was fed through two ion exchange columns
operating in series prior to electrolysis. The first column was filled with
Purolite S-950 resin. This was used to capture any copper in the
cobalt advance electrolyte. The second column contained Dow XUS43758 resin. This resin is selective for nickel over cobalt and is
commonly applied in cobalt electrowinning circuits to reduce nickel to
acceptable levels. Cobalt was electrowon onto a 316 stainless steel
2
cathode blank at 250 A/m in a divided cell at 60-70 C. The typical
concentrations of batches of strip solution that were collected for
cobalt electrowinning are shown in Table 5.
Table 5. Co EW Electrolyte Feed Assays.

Figure 7.Cd cementation reactor.

Cd Removal pH 4.0
100

80

80

Cd Removal (%)

Cd Removal (%)

Cd Removal pH 3.5
100

60

40

100 % Zn

60

40
100 % Zn

150 % Zn

Co

Ni

Cd

Mg

Ca

Mn

68500

390

1.3

94

37

63

2.0

180

44

63

---

---

---

67150

67

67000

63

76750

47

2.2

210

40

79

66850

33

1.6

185

46

67

66600

39

2.2

230

60

65

68950

41

2.0

250

49

66

73940

39

2.1

300

61

69

150 % Zn

200 % Zn

20

Analysis (mg/L)

Period

200 % Zn

20

250 % Zn

250 % Zn

300 % Zn

300 % Zn

10

15

20

25

30

10

15

20

25

30

Tim e (m in)

Time (min)

(a)

(b)
Cd Removal pH 4.5

100
100 % Zn
150 % Zn
200 % Zn

80

Cd Removal (%)

250 % Zn
300 % Zn
60

40

20

The spent solution from cobalt electrowinning was collected and

analyzed (Table 6). The fate of the impurity elements that did make it
into the EW cell can be seen from comparing the data in Table 5 and
Table 6. Cadmium was plated with the cobalt. In the feed electrolyte
concentrations were consistently around 2 mg/L, with levels below 1
mg/L in the spent electrolyte. Magnesium concentrations in the feed to
EW were of the same order as those found in the spent electrolyte.
Calcium levels in the spent electrolyte were also similar to
concentrations in the feed to the cell. Manganese was the impurity
element that showed a significant decrease in concentration from feed
electrolyte to spent electrolyte. Manganese dioxide formed at the
anodes.

0
0

10

15

20

25

30

Tim e (m in)

(c)
Figure 8. Cadmium removal kinetics at pH of 3.5, 4.0 and 4.5 at 40 C.
Table 4.Bulk Strip Liquor Assay Ranges
Concentration (g/L for Co and Zn, mg/L for others)
Co
Zn
Mn
Cd
Mg
Al
U
Ni
Min
4.3
6.3
3.0
2.1
13
39
45
163
Max 13.7 26.7
43
7.2
63
180
255
420
All of the bulk strip solution was treated for cadmium, copper and
uranium removal by zinc dust cementation and ion exchange prior to
v
the zinc solvent extraction process. Zinc is loaded selectively (30 /v
Cyanex 272 in Orfom SX 80CT diluent) and stripped from the bulk
strip liquor to form a solution of +150 g/L Zn with a Zn:Co ratio of >
4000:1. The cobalt losses to the zinc strip (in the zinc circuit) are
negligible (much less than 0.1% of the leached Co).

Two cobalt cathode samples were submitted for analysis. The

results are given in Table 7. Cadmium was analysed by two
techniques and both results are given, to show the degree of
agreement. The cobalt cathodes were of excellent quality and cobalt
purity was estimated at over 99.98% calculated by difference.

Copyright 2012 by SME

SME Annual Meeting

Feb. 19 - 22, 2012, Seattle, WA
Table 6.Co EW Spent Electrolyte Pail Assays
Assays, mg/L
Period
Co
Ni
Cd
Mg
0.6

Ca

Mn

27

13

---

---

---

180

51

190

46

10

175

45

46

43750

46

82

49200

58

---

47500

47

0.5

46100

36

0.7

42000

31

<1

42800

35

0.5

200

The cobalt electrowinning carried out for the feasibility study

demonstrated that cobalt metal could be produced from the Boleo
leach solutions. As the project has moved through design and now
into construction, there has been a need to continue working on
refinement of the cobalt electrowinning process for successful
commercial implementation.
Experimental
Cobalt electrowinning has been conducted in a divided cell which
was placed in a water bath for the temperature control (Figure 11).
With the use of a peristaltic pump, the catholyte was circulated from
the cell top to a mixing reservoir, then to a heating reservoir (in the
water bath), and finally back to the cell from the bottom. The feed
solution was pumped to the mixing reservoir with the use of another
peristaltic pump. The cathode and anode were separated by a
polyester diaphragm. The cathode-anode distance was about 100 mm.
The catholyte flowed through the diaphragm to the anode compartment
due to the hydraulic head. The anolyte level was controlled through a
Teflon tube connected to a peristaltic pump.

There was a tendency for the cobalt cathodes to self-strip during

pilot plant operation.
Higher temperature and better pH control
seemed to provide a solution to this problem. The overall current
efficiency in the pilot plant run was typically over 90%. Figure 10
shows a picture of one of the best cobalt cathodes produced.
Table 7.Co Cathode Assays (g/t)
Sample
Co by difference
Cd
Ni
Pb
S
Zn
Se
Fe
Cu

1
99.98%
69/66
55
40
< 50
< 10
<5
<4
<2

2
99.99%
46/43
56
41
--< 10
<5
<4
<2

Figure 11. Cobalt electrowinning setup.

Baja Mining has tested cobalt round deposition as an alternative
to plating of full cathode sheets. The cathode blanks for cobalt round
deposition were 304 stainless steel mandrel with a coating of dielectric
ink supplied by Ionic Technology Limited. The anode was made of Pb0.75% Ag alloy. To start a test, the starting catholyte was heated to a
target temperature and used to fill the cell and the solution reservoirs.
The catholyte composition was: 45 g/L Co as CoSO4, 120 g/L Na2SO4 ,
0.07 g/L Mn as MnSO4. All the chemicals were reagent grade. A
number of different cobalt salts were used to make up the solutions.
Results
There were numerous pits on the cobalt rounds produced at 65 C
and pH 3.5 from the solution prepared using reagent grade cobalt
sulfate from Alfa Aesar (Figure 12). As certain organic compounds are
known to significantly enhance pitting, the solution was treated with
activated carbon in an attempt to remove any organic species present.
However, pitting was still significant (Figures 13 to 14). The source of
cobalt used to make the plating solutions influenced the formation of
pits. The cobalt rounds produced from the solution prepared using
cobalt hydroxide were bright and had very few of pits (Figure 15) as it
contained a significant amount of organic which was not completely
removed by activated carbon treatment. It is suspected that the type of
organic contained in the hydroxide suppressed pitting.
Figure 10. Cobalt Cathode.
Pitting is a common problem in the electrodeposition of base
metals such as cobalt, nickel, zinc and iron from aqueous solution, but
it rarely occurs in the electrodeposition of more noble metals such as
copper and silver. The adhesion of hydrogen bubbles on the deposit is
the cause of pitting because hydrogen evolution is unavoidable for
base metal deposition. To reduce pitting, surfactants such as sodium
lauryl sulfate can be used to reduce the surface tension and facilitate
the detachment of hydrogen bubbles. However, in the Boleo flowsheet,
as solvent extraction is used to separate cobalt from other metals the
use of surfactants have the potential for interfering with solvent
extraction phase separation. The test program therefore aimed to
avoid the use of surfactants to control pitting.

Figure 12. Cobalt deposits produced from the solution prepared using
2
cobalt sulfate from Alfa Aesar. Conditions: 65 C, pH 3.5, 530 A/m and
4 hours
Temperature affected the cobalt deposit morphology and the
number of pits found on the deposit. With decreasing temperature
from 65 to 55 C, the number of pits was significantly decreased
(Figures 16 and 17). However, the deposit dendrites grew laterally.

Copyright 2012 by SME

SME Annual Meeting

Feb. 19 - 22, 2012, Seattle, WA
lower pH, affects the nucleation and crystal growth, and modifies the
morphology and shape of a cobalt round. It was found that at a pH of 3
and 50 C, the lateral growth of the cobalt rounds was suppressed.
Practically no pits formed on the cobalt rounds (Figure 18) and the
cobalt current efficiency was 98%. The darkish grey colour of the
cobalt rounds was determined by their morphology.

Figure 13. Cobalt buttons produced at 435 A/m from the solution
prepared using cobalt sulfate from Alfa Aesar and treated with
2
activated carbon. Conditions: 65 C, pH 3.5, 435 A/m and 5 days.

Figure 18. Cobalt rounds produced from the solution prepared using
purified cobalt carbonate from Shepherd Chemical Company.
2
Conditions: 50 C, pH 3.5, 435 A/m and 5 days.

Figure 14. Cobalt buttons produced from the solution prepared using
cobalt carbonate from Shepherd Chemical Company and treated with
2
activated carbon. Conditions: 65 C, pH 3.5, 435 A/m and 5 days

MANGANESE ELECTROWINNING
The recovery of manganese from the DSX raffinate is made
possible by precipitation using soda ash.
MnSO4 + Na2CO3 = MnCO3 + Na2SO4
(28)
The Boleo process was piloted in 2006 with manganese
precipitation. The DSX raffinate was treated with sodium carbonate
solution to selectively precipitate manganese carbonate as a potential
by-product. The equipment used consisted of two successive reactors
followed by a thickener and then batch filtration. A solution containing
150 g/L sodium carbonate prepared in synthetic seawater was dosed
into both reactors for pH modification. The target for manganese
precipitation was varied from 75 to 90% so as to maintain product
purity. Nitrogen gas was sparged into both reactors to maintain an
inert atmosphere.

Figure 15. Cobalt buttons produced from the solution prepared using
cobalt hydroxide from Alfa Aesar and treated with activated carbon.
2
Conditions: 65 C, pH 3.5, 435 A/m and 7 days.

The analysis of the feed solution to precipitation is shown in Table

8. The key impurities to reject in precipitation are calcium and
magnesium.
Table 8. Average Composition of Mn Precipitation Feed and Product
Solution.
Concentration, mg/L
Co Zn
Mn
Ca
Mg
Al
Ni
Si
Feed
1.2 8.7
9910
596
6620
63
16
24
Prod.
2.2 4.9
2800
396
5930
5.9
10.3
13.6

Figure 16. Cobalt buttons produced from the solution prepared using
cobalt sulfate from Alfa Asear and treated with activated carbon.
2
Conditions: 55 C, pH 3.5, 435 A/m and 1 day.

The manganese carbonate formed as a fine pinkish precipitate

that settled, filtered and washed very well. The typical composition of
the manganese carbonate is shown below. Nearly 200 kg of wet
MnCO3 was recovered.

Figure 17. Cobalt buttons produced at 435 A/m from the solution
prepared using purified cobalt carbonate from Shepherd Chemical
Company and treated with activated carbon (Test S6). Conditions: 55
2
C, pH 3.5, 435 A/m and 1 day.

Table 9. Typical analyses of MnCO3 precipitate.

Analysis (%)
Species
Mn
Ca
Mg
Na
Al
Precipitate
47
1
0.3
0.6 0.5
Analysis (g/t)
Species
Ni
Zn
Fe
Cu
Co
Precipitate
350
300
200
<5
50

At a pH of above 3.5, the cobalt current efficiency can reach

99.9%. At such a high current efficiency, the rate of hydrogen evolution
is low and slow bubble growth resulting in large pits is expected. At
lower pH, more hydrogen is expected to evolve which enhances the
agitation of the catholyte at the surface and facilitates the detachment
of hydrogen bubbles.

Different forms of manganese carbonate are used as raw material

for the manufacture of a variety of commercial products including
manganese chemicals, electrolytic manganese dioxide (EMD) or
manganese metal [9]. Electrolytic manganese metal (EMM) production
has been evaluated.

CO3
45

SO4
2

Cd
<5

Cl
100

Commercial production facilities of electrolytic manganese metal

can be found in China and South Africa. The Chinese manganese
metal industry predominantly uses locally mined manganese carbonate
ore (10-18%Mn) as feed stock while the South African operation uses
manganese oxide ore sourced from mines located in the Kalahari
manganese fields of the Northern Cape Province.

At a pH of above roughly 3, cobalt is deposited through a pH

dependent mechanism by the formation of cobalt hydroxide complex
+
(Co(OH)2 or CoOH ) [7, 8]. At a constant potential, the cobalt
deposition current decreases with decreasing pH, indicating an
increase in the inhibition of cobalt deposit. Therefore, dendrites should
be suppressed at a lower pH. At a pH of below roughly 3, cobalt
2+
electrodeposition occurs through the direct reduction of Co . At a
constant potential, cobalt deposition is practically independent of pH
[8]. Decreasing pH mainly increases the hydrogen evolution. More
atomic hydrogen is also adsorbed on the cobalt deposit surface at a

South African manganese ores contain higher manganese oxides

(Mn IV and III) MnO2, Mn2O3, Mn3O4 and Mn7SiO12 braunite
manganese (II,III) that need to be reduced to the soluble form of
manganese Mn (II) or MnO. This is achieved by drying, milling and

Copyright 2012 by SME

SME Annual Meeting

Feb. 19 - 22, 2012, Seattle, WA
reducing the higher manganese oxides at elevated temperature (700o
950 C) with methane, hydrogen and carbon monoxide derived through
the partial combustion of coal, bunker or fuel oils [10].
The manganese (II) form found in manganese carbonate MnCO3
does not require reduction of the higher manganese oxides and
manganese carbonate ores can be added directly to the leaching
tanks.
Experimental and Results
The process of manganese metal production involves acid
leaching, leach residue separation, purification and manganese
electrowinning in a divided cell. The main chemical reactions for each
of these steps are summarized in reactions (29) to (35) below.

MnCO3 Ore with 16% Mn

Boleo MnCO3
Figure 19. Comparison of the composition of MnCO3 ore and Boleo
Manganese Carbonate.

Manganese leaching in anolyte.

MnO + H2SO4 = MnSO4 + H2O
MnCO3 + H2SO4 = MnSO4 + H2O + CO2(g)

The deleterious elements are removed by sulphide precipitation

using ammonium sulphide solution.

(29)
(30)

Solution purification using sulphide precipitation.

The leaching of manganese carbonate was tested by contacting
manganese carbonate made in the Boleo pilot plant at 50 C for 4
hours with a synthetic anolyte solution comprising 130 g/L (NH4)2SO4,
12 g/L Mn as MnSO4 and 36 g/L H2SO4. Table 10 summarizes a typical
leach extraction achieved during leaching. The manganese extractions
are generally high reaching more than 99% extraction of the
manganese in the manganese carbonate.

MSO4 + (NH4)2S = MS + (NH4)2SO4,

where M=Cu, Ni, Co, Zn, Cd

(31)

The ammonium sulphide addition was set at 2% based on

stoichiometric manganese requirements and the test was performed at
50 C for 1 hour under a nitrogen atmosphere. Table 11 summarizes
the typical results of a purification test. This shows that the purification
was very successful in removing Al, Cd, Co, Cu, Ni and Zn and was
confirmed by successful plating of manganese metal. A small amount
of manganese is lost as manganese sulphide which acts a seed for
initiating the precipitation reactions.

Table 10. Leach Extraction for Acid Leaching of Boleo Pilot Plant
Manganese Carbonate Sample.
Feed
Leach
MnCO3
Residue
Extn*
Species
Solution Solution
(g/t)
(g/t)
(%)
(mg/L)
(mg/L)
Mass/Volume
1.5 L
1.5 L
71.1 g
1.05 g
CO3
447,000
48,700
99.8
Mn
12600
31400
410,000
82,600
99.7
Cl
1.2
11.8
168
100.0
Al
182
4500
165,000
45.9
Cd
0.0584
0.82
0.17
99.7
Ca
2.16
518
11700
1400
99.8
Cr
3.45
7.65
19
319
75.2
Co
1.2
0.69
17.2
63.2
Cu
0.0747
2.6
32.8
81.4
Fe
1.11
0
2400
Pb
0.0365
2.1
91.3
35.8
Mg
2.67
117
2400
500
99.7
Ni
9.78
131
93.4
98.9
Na
353
6800
1000
99.8
Zn
1.24
12
185
131
99.0
*Extraction is calculated based on feed and residue solid assay

Table 11. Purification Results for Manganese Electrolyte. Addition of

Ammonium Sulphide at 2% of Stoichiometric Manganese
Concentration.
Feed Leachate Purified Leachate Precipitate Precipitation
Species
(mg/L)
(mg/L)
(g/t)
(%)
Mass/Volume
1.35L
1.35 L
2.01 g
Mn
33,000
32,300
253,000
1.2
Al
155
15.8
106,000
90.9
Cd
0.057
0
53
99.6
Ca
431
489
2500
0.8
Cr
5.1
7.1
321
6.3
Co
1.08
0.12
736
90.1
Cu
0.059
0
63
100.0
Fe
0
0.81
0
Pb
0
0
71
Mg
115
121
0
0.0
Ni
11.3
0.021
6120
99.8
Na
328
352
0
0.0
Zn
13.9
0.94
8090
92.7

The environmental aspects of producing electrolytic manganese

metal include the disposal of wastes [11]. For operations that process
mined ores, the majority of waste is due to leach residues. Figure 19
illustrates the waste generating potential of Boleo manganese
carbonate compared to a hypothetical manganese carbonate ore
containing 16% Mn grade.

Commercial manganese electrowinning is conducted in divided

cells with permeable diaphragms that separate the cathode and anode
compartments and allow the following reactions to occur.
Manganese electrowinning (Cathode (Mn and H2), Anode (O2) and
Overall).

A significant reduction in waste generation is expected with

processing manganese carbonate produced by chemical precipitation
at Boleo.

2-

MnSO4 + 2e = Mn + SO4
2H2O +2e = H2 + 2OH
+
H2O = 0.5O2 + 2H + 2e
MnSO4 + H2O = Mn + 0.5O2 + H2SO4

The leach solution contains minor amounts of deleterious

elements including Cd, Co, Ni, Cu and Zn. As manganese is the most
active metal deposited from aqueous solution, co-deposition of
impurities and hydrogen evolution always result in reduced manganese
current inefficiency.Selenium can be added to tank house feed
solutions to reduce the effect of impurities and increase the current
efficiency. In these tests selenium was not added as it results in a
lower quality product that has associated toxicity aspects during
manufacture and application.

(32)
(33)
(34)
(35)

Titanium or stainless steel cathodes and lead anodes are used.

Manganese electrolysis was tested on purified electrolyte solutions
using a bench top cell and a full height cell. Selected results from the
bench top test program are reported here. Results from the full height
cell will be reported in the future.

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SME Annual Meeting

Feb. 19 - 22, 2012, Seattle, WA
trap solution which decreases the quality of the product. The sections
in Figure 22 show that the morphology of the deposit can change
during a plating cycle.

Mn current efficiency / %

66

65

64

Figure 20. Bench top experimental cell for manganese electrolysis.

63

The general conditions used for plating were; Temperature: 42

2
C; Current Density: 550 A/m ; Catholyte: pH 8.2 to 9.0, 12 g/L Mn, 150
g/L eq(NH4)2SO4; Anolyte: 12 g/L Mn, 130 g/L (NH4)2SO4 and 36 to 46
g/L H2SO4. The catholyte was circulated at a constant rate to improve
cathode mass transfer and to minimize the concentration variation
during plating.

16

17

18

19

20

Mn bite / g L

21

22

-1

Figure 21. The effect of manganese bite on manganese current

efficiency at constant catholyte Mn (12g/L).

The manganese electrolysis test program included investigations

into the parameters that influence the plating performance of the
manganese cell. Parameters that are reported in this paper include
catholyte manganese concentration, manganese bite and plating time.
Increasing the manganese catholyte concentrations is expected
to improve manganese current efficiency. The maximum manganese
concentration is limited by the precipitation of manganese hydroxides
that can occur at the elevated pH of the catholyte solution. Table 12
shows results obtained from comparative 6 hour plating tests done at
different catholyte concentrations and constant Mn bite. The Mn bite is
the difference in manganese concentration between the feed and
catholyte solutions. Constant Mn bite was achieved by making up
different feed compositions, viz 30.8, 31.7 and 33.1g/L Mn respectively
and controlling the flow to the cell to achieve the required catholyte Mn
concentration.
Table 12. Test work at varying
Mn bite.
Catholyte
Average
Mn
Mn bite
(g/L)
(g/L)
11
19.8
12
19.7
13
20.1

(a)

(b)
Figure 22. Cross sections of manganese metal deposits. (a) Section
of deposit with low addition rate of smoothing agent and (b) Section of
deposit with high addition rate of smoothing agent.

catholyte Mn concentration and fixed

Figure 23 shows the results of test work done at different plating

times and the same addition rates of smoothing agent.

C.E.
(Mn)
(%)
63.6
64.0
62.9

The test program included measurements to characterize the

physical and mechanical properties of the electrodeposited
manganese. Figure 24 shows a typical profilometer measurements
made of the electrodeposit. The negative effects of rough deposits can
be reduced by adding surface active smoothing agents as shown in the
deposit sections.

Average
C.V.
(V)
4.66
4.63
4.65

Energy
Consumption
(kWh/kg Mn)
7.15
7.05
7.20

Figure 25 shows photographs taken of cathodes produced during the

test program. Sample (b) shows deposit with pinholes and stress
cracks. Sample (b) is free of pinholes and cracking.
This was
achieved by controlling solution quality, smoothing agent addition and
other plating parameters.

Table 12 shows that under the selected experimental conditions

the current efficiency and power consumption are optimized at 12.0g/l
Mn in the catholyte.
The effect of Mn bite can be anticipated from the overall cell
reaction (35). This shows that as the bite increases, an equivalent
increase in acid concentration can be expected in the anode
compartment. The increased acidity results in increased transport of
hydrogen ions through the diaphragm to the catholyte which in turn
reduces the manganese current efficiency. Results of short plating
cycle runs conducted to investigate the effect of the manganese bite
shown in Figure 21 confirmed expected trends in cell behavior.

CONCLUSIONS
The Boleo process allows for recovery of copper, cobalt, zinc and
manganese products from a complex oxide-sulfide orebody. The key
steps involve (a) acid oxidation and acid reduction leaching in
seawater, (b) counter current decantation washing of the leach residue
to recover a mixed metal solution, (c) conventional copper SX-EW
recovery as copper metal cathode, (d) treatment of a portion of the
copper SX raffinate for iron oxidation and removal, (e) DSX recovery
of cobalt and zinc using the CSIRO DSX solvent system comprising a
mixture of LIX 63 and Versatic 10, (f) zinc recovery from the DSX bulk
strip solution using SX and crystallization to form a zinc sulphate
monohydrate product, (g) cobalt recovery from the zinc SX raffinate by
SX-EW as cobalt cathode rounds and (h) the possible precipitation of a
manganese carbonate product from the DSX raffinate. The manganese
carbonate product can be further refined to produce electrolytic
manganese metal.

Pure manganese metal is brittle and electrowon product can be

stripped from the cathode and recovered in the form of flakes of metal.
The plating of manganese metal includes complex structural effects
[10, 12] that influence deposit morphology and mechanical properties
such as internal stress and adherence to the cathode. One of the
parameters that influence metal structure and manganese current
efficiency is plating time. Increased plating times during manganese
electrolysis is expected to result in increased roughness of deposit.
This creates local surface conditions that favor hydrogen evolution and
dissolution of metal. Nodular metal is not desired as the surface can

10

Copyright 2012 by SME

SME Annual Meeting

Feb. 19 - 22, 2012, Seattle, WA
REFERENCES

Mn current efficiency / %

70
1.

D. Dreisinger, E. Norton, R. Molnar, K. Baxter, M. Holmes, J.

Riordan, The Recovery Of Zinc From Baja Mining Corps El
Boleo Orebody, Proceedings of Zn-Pb 2008, CIM (Montreal), 16
pages.

2.

D. Dreisinger, W. Murray, K. Baxter, M. Holmes, H. Jacobs and R.

Molnar. The metallurgical development of the El Boleo coppercobalt-zinc project. ALTA Copper 2005, Perth, ALTA Metallurgical
Services, Melbourne, Australia.

3.

D. Dreisinger, K. Baxter and R. Molnar. New development in the

Boleo copper-cobalt-zinc-manganese project. ALTA Copper 2006,
Perth, ALTA Metallurgical Services, Melbourne, Australia.

4.

C. Y. Cheng and M. D.,Urbani. Solvent extraction process for

separation cobalt and/or manganese from impurities in leach
solutions. Patent Publication No. WO 2005/073415 A1.

5.

C. Y. Cheng and M. D. Urbani. Solvent extraction process for

separation cobalt and/or nickel from impurities in leach solutions.
Patent Publication No. WO 2005/073416 A1.

6.

C. Y. Cheng. Solvent extraction of nickel and cobalt with

synergistic systems consisting of carboxylic acid and aliphatic
hydroxyoxime. Hydrometallurgy, Vol 84, pp 109-117, 2006.

7.

O. E. Kongstein, G. M. Haarberg and J. Thonstad, Current

efficiency and kinetics of cobalt electrodeposition in acid chloride
solutions. Part I: The influence of current density, pH and
temperature, Journal of Applied Electrochemistry, Vol. 37, pp.
669-674, 2007.

8.

J. T. Matsushima, F. Trivinho-Strixino and E. C. Pereira,

Investigation of cobalt deposition using the electrochemical quartz
crystal microbalance, ElectrochimicaActa, Vol. 51, pp. 1960-1966,
2006.

9.

W. Zhang, and C.Y. Cheng Manganese metallurgy review. Part I:

Leaching of ores/secondary materials and recovery of
electrolytic/chemical manganese dioxide. Hydrometallurgy, Vol
89, pp 160177, 2007.

68
66

64
62
60
5

10

15
Time / hour

20

25

Figure 23. The effect of plating time on manganese current efficiency

at contact smoothing agent addition rates.

10. M.Harris, D.M. Meyer and K. Auerswald. The production of

electrolytic manganese in South Africa. Journal of South African
Institute of Mining and Metallurgy, Vol 77 No 7, pp 137-142, 1977.

Figure 24. Surface roughness profiles of manganese electrodeposits.

11. D. Ning, F. Wang, C. Zhou, C. Zhu and H Yu. Analysis of pollution

materials generated from electrolytic manganese industries in
China. Resources, Conservation and Recycling, Vol.54 pp 506
511, 2010.
12. J. Gong J., G; Zangari. Electrodeposition and characterisation of
manganese coatings. Journal of Electrochemical Society , 149,
Vol 4, pp C209-C217, 2002.
(a)
(b)
Figure 25. Manganese Cathodes Produced from Boleo Manganese
Carbonate.
The Boleo project has been moving through engineering design
and construction toward an expected startup in early 2013. Further
investigations of various aspects of the process have continued. The
main results of this work have been to;
1.
2.
3.
4.
5.

Define the kinetics of iron oxidation and precipitation from

the copper SX raffinate bleed.
Optimize the formulation of Versatic 10 and LIX 63 in the
DSX solvent system.
Confirm the conditions required to obtain rapid and complete
cadmium cementation from the DSX bulk strip solution.
Develop conditions for plating of cobalt rounds as the final
form of the cobalt product.
Demonstrate that Boleo manganese carbonate precipitate
can be refined to high quality electrolytic manganese metal.

11

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