Direct production of high-purity

cobalt sulfate heptahydrate from

a NICO deposit concentrate

Direct production of cobalt sulfate heptahydrate from a cobalt concentrate Alex Mezei, Michael Johnson and
Cornelia Lupu. SGS Mineral
originating from Fortune Minerals’ nico deposit was investigated at a pilot
Services, Canada
scale. The process flowsheet tested involved pressure oxidation at 180°C, 60
Ron Molnar. METNETH2O Inc.,
minutes residence time, arsenic removal, purification, cobalt solvent extrac-
Canada
tion, manganese removal, evaporation and crystallization. The final heptahy-
Keith Lee and Robin Goad. Fortune
drate product averaged 20.75% mass fraction Co, and in g/t, 2.5 Ni, < 10 Fe, < 13
Minerals Limited, Canada
Mn, < 2 Zn and 35 Mg. Crystallization discharge predicted the maximum
vacuum filtration throughput at 0.9 bar and 18 mm cake thickness of 1197 kg/
m2· h as well as a discharge cake residual moisture mass fraction of 18.2%.
Cobalt was recovered from the mother liquor bleed stream by a scavenging
carbonate precipitation. This produced a pure cobalt carbonate by-product
assaying 48.5% Co, and in 126 g/t Ni, 124 g/t Fe, 61 g/t Mn, 7 g/t Zn and 59 g/t
Mg. The final discharge stream was subjected to scavenging precipitation
aiming to remove any residual metals. Based on the dynamic settling response
of the discharge scavenging precipitate stream at ~100 g/t anionic flocculant
dosage and 1.2 hours solids residence time, the predicted specific underflow
and hydraulic thickener unit areas were 1.6 and 0.7 m2/t · day, respectively. The
thickened underflow displayed a light Bingham plastic rheological behavior
with a critical solids density mass fraction of ~5.9%, showing an unsheared
yield stress of 5.5 Pa. A comprehensive process model was established and
validated by the test data. The model output provided the complete process
and equipment design package for the commercial plant.

59
INTRODUCTION
The NICO cobalt-gold-bismuth-copper deposit is located in the Mazenod Lake district near the
Snare hydroelectric complex, approximately 160 km northwest of Yellowknife in Canada’s
Northwest Territories. The mine development is planned based on a reserve of 33.1 million tonnes
of ore averaging 0.11% Co, 0.14% Bi, 0.04% Cu and 1.03 g/t Au that will be mined using a
combination of open pit and underground methods within a lower grade overall resource. These
reserves support a minimum 20-year mine life at a production rate of 4,000 tonnes per day. The
economic metals occur throughout the deposit in concordant and discordant sulphide-rich fractures
and disseminations. Cobalt is contained predominantly within a solid solution series between
arsenopyrite and cobaltite, with minor cobaltian loellingite. Bismuth occurs as native bismuth,
bismuthinite, and tellurides, while copper is hosted in chalcopyrite. Gold occurs as microscopic
grains of native gold and as various gold-bismuth-antimony-tellurium alloys.
Cobalt and bismuth are concentrated by bulk flotation followed by selective flotation. Most of the
gold reports to the resulting cobalt and bismuth selective concentrates. Bismuth is recovered from
its concentrate by oxidative hydrochloric acid leaching followed by purification and
electrowinning. The cobalt concentrate is subjected to pressure oxidation which extracts the cobalt
while rejecting most of the arsenic and iron. Residual iron and arsenic are further removed by
normal pressure oxidation. According to the original flowsheet, the iron-arsenic-free stream is
further purified by selective copper precipitation and ion-exchange and directed to electrowinning,
as described in previous papers (Mezei et. al., 2000, 2008). This paper reports the results of the
development work aimed towards establishing the process for the direct production of high purity
cobalt sulphate heptahydrate (CoSO4•7H2O) along with a cobalt carbonate (CoCO3) by-product.
Direct production means that the process does not use cobalt cathode as feed. Instead, the preferred
purification route was solvent extraction (SX) of cobalt in conjunction with advanced manganese
removal. The process development consisted of conceptual bench-scale testwork validated by an
integrated pilot exercise proving its technical feasibility and generating engineering design criteria
for the NICO processing plant which will be built in Saskatoon, Saskatchewan, Canada. Samples of
the cobalt sulphate heptahydrate produced were sent to potential off-take partners for evaluation.

METHODOLOGY
The testwork was structured around extensive bench-scale SX along with base-line manganese
removal and evaporation-crystallisation testwork. The results were used to establish a “real data
process model” linking the SX circuit producing the cobalt strip solution to the downstream
manganese removal (MnRe), evaporation (Ev) and crystallisation (Cry) circuits. An integrated pilot
plant was designed using the process model, then built and operated continuously for 120 hours.
After reviewing the results (while updating the process model), the MnRe circuit was operated for
an additional 24 hours, this time being fed with SX feed (not strip) as the goal was to prove that
manganese could also be removed prior to the SX. SGS proprietary standard safety and operating
procedures were applied throughout the bench and pilot scale metallurgical testwork. This paper
describes the results of the pilot testwork.

60
Solvent extraction
The solvent extraction (SX) reagent consisted of Cyanex® 272 (Cytec Industries) in Orfom® SX80
diluent (Chevron Phillips). Cyanex® 272 is bis (2,2,4-trimethylpentyl) phosphinic acid. Orfom®
SX80 is a high flash petroleum distillate containing about 80% paraffinic hydrocarbons with the
balance being alkyl aromatics. Organic mixtures from 10 to 15% by volume extractant were tested
in bench-scale experiments and 10% was selected for the piloting.
The solvent extraction pilot circuit was comprised four extraction stages (E1 to E4), two scrub stages
(B1, B2), three cobalt strip stages (CS1 to CS3) and two final acid strip stages (ZS1 and ZS2),
nominally to strip any co-extracted zinc as well as any other elements that were loaded but not
stripped with cobalt. The organic flow was from E1→E4→B1→B2→CS1→CS3→ZS1→ZS2 and back
to E1. All the mixer-settler units were of a conventional design with square mixer boxes and
rectangular settlers. Each mixer unit was equipped with a variable speed mixer driving a pump-mix
impeller. The impellers were of a design having a flat disc top shroud over swept-back blades. This
reduced the shear minimizing the formation of micro-droplets and emulsion. All interstage
pumping was by the pump-mix impellers. The circuit was fed continuously at about ~310 mL/min
aqueous feed. Extraction operating temperature 55ºC and pH was controlled using 150 g/L Na2CO3
solution. Loaded organic was scrubbed at ~54ºC with a bleed of cobalt strip liquor diluted with
water at a pH of ~4.0-4.5, attained without pH modifying reagents. Cobalt strip operated at
pH ~2.6-2.8, 40ºC and zinc strip at pH below 1.0 and ambient temperature as there was after the
scrub stages. Sulphuric acid solutions were used to control pH in both strips. Advance volumetric
phase ratios (organic/aqueous) averaged 0.7, 40 and 17 in extraction, scrub and Co strip. No
aqueous was advanced in Zn strip because of the low Zn tenor and relatively short campaign.
Minor phases recycles were pumped in scrub and strip to achieve phase ratios of ~1 in the mixers.

Manganese removal, evaporation and crystallisation

The manganese removal (MnRe) pilot circuit consisted of two baffled agitated tanks equipped with
pH and temperature control and ORP (redox potential) Total residence time across the circuit was
12 h at the 16 mL/min target feed rate. A dual gas sparging system delivered the oxidizing mixture
of 2.5 % by volume SO2 in O2. The pH was maintained at the 3.6 target using 300 g/L NaOH
solution fed through a solenoid valve actuated control loop. The circuit discharge was flocculated
using ~330 g/t equivalent dry anionic flocculant. The settled slurry was filtered and sampled. The
filtrate was analysed and then advanced to the evaporation circuit. The precipitate containing the
rejected manganese was washed, dried and analysed. The wash water was collected and recycled to
the SX circuit to be used for the fresh strip solution make-up.
The manganese removal, evaporation and crystallisation pilot circuits operated simultaneously. The
evaporation circuit consisted of two tanks with a 2.26 h total residence time across the circuit at the
14 mL/min target feedrate. The evaporators were maintained at the target temperature of ~101ºC
using thermocouple-controlled heating mantles. They operated under 0.474 bar vacuum. The
flowrates were controlled using calibrated metering pumps. Condensate was trapped and
withdrawn at the prescribed rate with any excess recirculated. The evaporation circuit discharge
was pumped directly into the crystallisation circuit consisting of three tanks. Total residence time
was 3 h at the 8.5 mL/min target feedrate. Each crystalliser stage was kept at a relatively constant
equilibrium temperature by indirect cooling using an open-loop thermocouple-controlled water-

61
cooling system. The discharge slurry from the third crystallisation stage was vacuum filtered.
Filtrate and crystals were collected, weighed, sampled and analysed.

Measurement, sampling and analysis

All operating parameter data were collected manually based on pre-set sampling and measurement
timetables. In addition, parameters such as pH, ORP, temperature and flowrates were read by the
in-house data acquisition system. Samples were taken on a regularly scheduled basis to provide
control and full profiles suites. Aqueous and organic samples were prepared and analysed for
cation content by the SGS analytical laboratories either by Atomic Absorption Spectroscopy (AAS)
or by Inductively Coupled Plasma Optical Emission Spectrophotometry (ICP-OES), as appropriate.
Organic samples were also analysed by ICP-OES after dilution with an organic solvent.

Targets definition and real model updates

The pre-pilot update of the ‘real data model’ was based on bench-test results. It included the
process and equipment design criteria needed for the pilot plant design, ranging from feed
characterization through operating targets definition for all unit operations. The final update
reflected the validation through the pilot results and included rheometallurgical data needed for
scale-up as well as equipment design criteria for the physical separation and materials handling
unit operations. The final output included all the necessary data required for the full feasibility and
engineering design studies.

RESULTS AND DISCUSSION

Feed preparation
The pilot plant feed sample consisted of about 2200 L bulk POX (pressure oxidation at 180ºC, 60
minutes residence time,) discharge PLS (pregnant leach solution) and wash solution mixture
produced during a prior pilot campaign. Iron and arsenic were removed from the PLS according to
the process parameters previously established, namely 50ºC, 6.2 h residence time, aeration and a pH
of 3.6, after which copper was taken out at pH 6.9, 50ºC, 1 h residence time. Lime slurry was the
reagent used throughout the entire purification sequence. The resulting copper-free solution
became the SX extraction feed for the pilot testwork. In TABLE 1, important analytical results on
this stream are summarized as averages of the results for samples taken during pilot plant.

Table 1 Cobalt solvent extraction feed for pilot plant

Co Mg Mn Ni Na Ca K Cu Cl Zn
2275 976 66.7 55.1 675 495 29 <0.1 245 <1

Solvent extraction results

Bench SX data (Figure 1A) predicted good cobalt extraction at and above pH 4.5, with some
possible some Ca and Mg co-extractions, to be minimized by loading the organic well with cobalt,
and by scrubbing the loaded organic at pH 4 to 4.4. Manganese was loaded at a pH just below that
for cobalt, thus precluding its displacement. The isotherm shown in Figure 1B reflects the true

62
capacity of the organic phase in terms of all the extractable elements. The McCabe Thiele diagram
predicted that four stages would yield good extraction and that organic loading capacity would
approach 3.5. g/L Co.

100 4000

90
3500
Co+Zn+Mn
80

Co Equivalent in Organic, mg/L

3000
70
Percent Extracted

2500
60
Co Mg Ca
50 2000
Mn
40
1500

30 A/O = 1
1000
20
Ni 500
10

0 0
2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 0 500 1000 1500 2000 2500 3000
[A] Equilibrium pH [B] Co Equivalent in Aqueous, mg/L

Figure 1 [A] Extraction vs. pH; [B] Cobalt-(equivalent) extraction isotherm, pH 4.25

The pilot plant solvent extraction circuit operated continuously for 106 h, a relatively short pilot
campaign, with stable performance (Figures 2 and 3). Organic degradation, stable emulsions and
crud formation were not observed. Excellent (i.e. rapid and clean) phase separation occurred in all
stages. The results demonstrated that cobalt could be recovered with high efficiency with overall
cobalt recovery exceeding 99.9% in four extraction and three stripping stages. The major impurities
in the strip liquor were manganese and magnesium with lesser amounts of calcium and nickel.
Data suggested that the magnesium could be further reduced by maximizing cobalt loading,
adding a third scrub stage and lowering the pH profile in the scrub stages. Nickel and calcium
could also be lowered by more efficient scrubbing.

76 6
5
5 E1 4 CS1
3
6|4 2
5 E2 5|1
4 4 CS2
3
6|3 2
5 E3 1
Mixer pH

5|0
Mixer pH

4 4
3 CS3
6|3
2
5 E4 1
4 5/0
6|3 4
3
5 2 ZS1
4
B1 1
5/0
6|3 4
5 3
B2 2 ZS2
4 1
3 0
0 10 20 30 40 50 60 70 80 90 100 110 0 10 20 30 40 50 60 70 80 90 100 110
[A] Elapsed Time, h [B] Elapsed Time, h

Figure 2 Relevant pH profiles: [A] extraction (E), scrub (B); [B] strip (CS-Co, ZS-Zn)

63
Downstream circuit results
The performance of the manganese removal circuit downstream of SX was robust throughout the
entire 126 continuous operating hours under the bench-work defined targets. Relevant cobalt and
manganese tenor profiles are shown in Figure 3A. Steady state manganese removal efficiency from
the cobalt strip solution during the 12-hours residence time was 96.6% with the cobalt loss at 6.3%.
The manganese removal rate averaged 195, 33 and 227 mg/L·h in tanks 1, 2 and overall,
respectively. Most of the manganese (82.7%) was removed in tank 1, with 13.9% removed in tank 2.
The manganese removal discharge dry cake assayed on average 13% wt. Mn, 45% wt. Co, less than
500 g/t Na, and less than 100 g/t of other elements.
The evaporation and crystallisation circuits ran well in tandem throughout the entire operation.
The crystallisation mass balance indicated that about 37% of the cobalt was recovered in the
heptahydrate form, 53% reported to the mother liquor and ~10% to the wash solution. These two
liquid streams were recycled to solvent extraction upstream so that their cobalt content was
recovered. The heptahydrate product entrapped about 20% of the manganese, 7% of the
magnesium and 1% of the sodium. The cobalt tenor of the stage-3 crystallisation discharge mirrored
quite closely that of the circuit feed suggesting a consistent cobalt ‘delta’ or ‘bite’ of 24 g/L. This
enabled the production of crystalline heptahydrate by cooling (Figure 4B). The Co and Na content
profiles (Figure 5) of the crystallizer feed indicated that the sodium brought into the system
increased continuously, building up to levels that could not be controlled by crystallisation despite
its high selectivity, i.e. 99% rejection on average throughout the campaign. The cobalt sulphate
heptahydrate product averaged 20.75% wt. Co and had less than 2.5 g/t Ni, less than 10 g/t Fe, less
than 13 g/t Mn, less than 2 g/t Zn, 35 g/t Mg, 99 g/t Ca and 1500 g/t Na. The results confirmed that
the flowsheet tested allowed for the direct-production of a high-purity cobalt sulphate
heptahydrate product with the caveat that the sodium build-up in the system could lead to product
purity issues. Therefore, the flowsheet was changed by relocating the manganese removal circuit
ahead of the solvent extraction.

`
10000 800 6
1
4 4 4
Feed 4 3 3 1
3 700
4
4 4
1000 3
4 2 600 CS1O 5
Co in Strip Organics, mg/L

2 2 1
3
Co in Loaded Org, g/L
3 3 1
4 E4R 500
100 4
2
1
Co, mg/L

3 3 E3R 1
3 1
2 2 E2R 1 2 400 4
1 1 E1R (Raffinate) 2 2 2 Loaded
10 4 4 E4O (Loaded) Organic
300
3 3 E3O 1 1
2 2 E2O 2 1 1
1 1 200 3
1 1 E1O 1 1
1 1 1 1
1 2 CS2O 2
1 1 100 2
1
1
CS3O
0 0 3 3 3 33 2
0 10 20 30 40 50 60 70 80 90 100 110 0 10 20 30 40 50 60 70 80 90 100 110
[A] Operating Time, h [B] Operating Time, h

Figure 3 Cobalt concentration profiles in: [A] extraction; [B] strip

64
 120 1500 180
Co in Feed
1350 170
Co in Discharge
110
Mn in Feed 1200 160
Crystallisation
Mn in Discharge
1050 150 Feed
100
900
Cobalt, g/L

Mn, mg/L
140

Cobalt, g/L
90 750
130
600
120
80
450 Crystallisation
110
300 Stage 3 Discharge
70
100
150
90
60 0
80
3

3
-2

-2

-2

-2

-2

-2

-2

-3

-0

-0

-0
pr

pr

pr

pr

pr

pr

pr

pr

ay

ay

ay
0 10 20 30 40 50 60 70 80 90 100
A

M
Date [A] [B] Elapsed Operating Time, h

Figure 4 Feed and discharge profiles: [A] Mn Removal circuit; [B] Crystallisation circuit

180 50 280 35

170 45
240 30
160 40

150 35 200 25
Manganese, mg/L

140 30
Sodium, g/L

Sodium, g/L
Cobalt, g/L

160 20
130 25
120 15
120 20

110 15 80 10

100 10
40 5
90 5

80 0 0 0
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100
[A] Elapsed Operating Time, h Elapsed Operating Time, h [B]

Figure 5 Crystallisation feed profiles: [A] Co and Na; [B] Mn and Na

Final flowsheet
The final flowsheet (Figure 6) was established based on the performance of the pre-SX manganese
removal circuit that defined the optimized conditions for both reactors as follows: pH ~4.2
maintained with lime, ORP ~500 mV (measured vs. Ag|AgCl, sat’d KCl standard electrode)
realized with 2.3% (volume fraction) SO2 in O2, 50 ºC and ambient pressure. Under these operating
conditions, the manganese removal rates were 53 mg/L·h in tank 1, 27 mg/L·h in tank 2 and
40 mg/L·h across the circuit. The corresponding manganese removal efficiencies per hour of
residence time were ~65% in tank 1 and ~33% in tank 2, i.e. 49% across the circuit equivalent to 98%
with 2 h residence time. The corresponding overall cobalt loss was 12%. Overall pure reagent
consumptions in kg of reagent per kg manganese removed were 39.4 Ca(OH)2, 2.9 SO2 and 63.8 O2.
The results allowed prediction of an achievable sodium target of less than 5 g/t for the commercially
produced NICO heptahydrate cobalt sulphate product. Furthermore, the results of this work

65
considered with the proposed flowsheet allowed prediction of the key assays of the commercially
produced NICO cobalt carbonate by-product produced by the precipitation from the crystallisation
mother liquor bleed stream with a purity of 48.5% Co, with in g/t: 126 Ni, <124 Fe, 61 Mn, 7 Zn and
59 Mg. All of these targets were attained in the pilot plant product.

Cobalt Concentrate Co SX Feed Co Extraction Raffinate Na2CO3

150 g/L pH 5.3-4.8, 55ºC
POX S Na2(CO)3 4 stages
O2 CIL Ni Ppt'n
180ºC 1 h L
pH 7
10% solids pH 1.8 Loaded Scrub
O2 Ca(OH)2 Pond Organic Liquor
Gold L
(acid or LO Scrub Water S
Fe-As Ppt'n
base) pH 4.6-4.4, 55ºC
50ºC, 2 h, pH 4.6
2 stages Scrub Pond Storage
Scrubbed Feed
®
S Cu Releach Organic 10% v/v Cyanex 272
in Orfom® SX80
Recycle to Fe-As Removal

L from Fe-As Ppte Co Strip

H2SO4
pH 3.0-3.3, 30-40ºC
S 3 stages
L Co-stripped Organic
Fe Tailings Zn-stripped
Zn Strip organic recycle
H2SO4
pH 0.9-1, 25-30ºC to extraction
Cu Cementation
2 stages
ZnSO4 Strip Liquor
S
Na2CO3 L Zn Ppt'n Co Strip Liquor
Na2CO3
Smelter pH 10 to evaporator

Cu Removal
L
pH 6.45-7.45
S
Zn Sludge
S to Storage
L
Cu Removal Discharge
SO2/O2 @
2.5% (v/v) Ca(OH)2
Evaporation
Crystalliser Feed Condensate Na2CO3
Mn Ox/Ppt'n
Ag|AgCl
50ºC, 500 mV pH 4.2
Mother
Crystallisation Co Scavenging
Liquor
Precipitation
DI water
Flocculant
to wash DI Water
S L
L Wash Crystal Washing S
Tailings Water (Centrifuge)
Purified
Co SX Feed CoSO4•7H2O CoCO3

Figure 6 Final flowsheet

Based on the dynamic settling response of the discharge scavenging precipitate stream at ~100 g/t
anionic flocculant dosage and 1.2 hours solids residence time, the predicted specific underflow and
hydraulic thickener unit areas were 1.6 and 0.7 m2/t·day, respectively. The thickened underflow
displayed a light Bingham plastic rheological behaviour with a Critical Solids Density mass fraction
of ~5.9%, showing an unsheared yield stress of 5.5 Pa. Crystallisation discharge predicted the
maximum vacuum filtration throughput at 0.9 bar and 18 mm cake thickness of 1197 kg/m2·h as

66
well as a discharge cake residual moisture mass fraction of 18.2%. Therefore, centrifugation could
be considered for the commercial operation. Predicted maximum vacuum filtration throughput for
the cobalt carbonate product under similar vacuum conditions with a 5 mm cake thickness was 127
kg/m2·h and a discharge cake residual moisture mass fraction of 47.7%.

CONCLUSION
A process flowsheet for the direct production of high purity cobalt sulphate heptahydrate and
cobalt carbonate by-product was established and validated.

REFERENCES
Mezei, A., Ferron, C.J., Krstic, S., & Goad, R.E. (2000) ‘Recovery of Cobalt, Gold and Bismuth from the NICO
Deposit, NWT, Canada - Part II: Recovery of Bismuth’, Proceedings of SME Congress, Minor Elements
2000, Salt Lake City, Utah.

Mezei, A., Fleming, C.A., Canizares, M., Ashbury, M., Brown, J., Todd, I., Imeson, D., Jackman, I., Goad, R.E.,
Samuels, M., Ferron, C.J., Hayden, A., Molnar, R., Konigsmann, K., King, D., Marshall, D., & Ngai, E.
(2008) ‘Recovery of Cobalt, Gold and Bismuth from the Polymetallic Concentrates - NICO Deposit,
NWT, Canada – Pilot Plant Results’, Proceedings of ALTA 2008 Congress, Nickel and Cobalt, Perth, WA,
May.

67