CHAPTER 6

COBALT PRECIPITATION

6.1 INTRODUCTION

The ‘Base Case’ flowsheet for the Kolwezi Tailings project employed Co solvent
extraction for the transfer of Co into the electrowinning (EW) circuit, and partial
purification of Co by rejecting the majority of the Ni and Mg. For the current flowsheet
under consideration by FQM, Co precipitation and redissolution are used to transfer Co
into the EW circuit. Initially it was proposed to use NaOH as precipitant, which would
have caused a diluted sodium sulphate waste stream that would have had to be taken care
of environmentally. Hence, it was decided to use MgO as primary precipitant with
NaOH only for final pH control. The advantages of using MgO as precipitant instead of
lime are:

 The final mass of solids after redissolution is smaller, hence there should be less
of a water balance problem due to the addition of wash waters to recover the Co
entrained in the filter cake (at 55-60 g/L Co), and
 Ca scaling in the EW circuit would be eliminated or significantly reduced, as the
majority of the Ca would be rejected in the barren stream from the CP operation.

The disadvantages of the use of MgO as precipitant are:

 It is expensive,
 And it would increase the deportment of Mg to the EW circuit which would have
to be taken care of through the Co EW bleed stream.

Limited laboratory test work was performed to determine optimum conditions for the
precipitation of cobalt, using MgO, for First Quantum’s Kolwezi Tailings project.
Following the laboratory test program, a continuous mini plant campaign was run during
October/November 2006, at Mintek on the entire Co refining circuit, which included Co
precipitation. Synthetic solutions, representing the bleed from an upstream copper circuit,

1
were prepared for both the laboratory test work and the continuous mini plant campaign.
This chapter discusses the laboratory and pilot plant results in detail for the Co
precipitation (CP) unit operation.

6.2 PROCESS

6.2.1 Description

A schematic representation of the cobalt precipitation circuit employed during the mini
plant campaign is shown in Figure 6-1.

Recycled
slurry Dry powdered MgO
CPREP

Mg leach
Combined CP1 40 g/L NaOH
Filtrate CP2
CP3
CPSTOR CP4 Flocculant
CP5
CP6
Reactor train

66% of slurry recycled

after thickening
34% of slurry to
Mg Leach

Wash water
S
L
Co precipitate to Mg leach
Barren liquor
to waste

Figure 6-1 Schematic representation of Co precipitation circuit for the mini plant campaign

The feed to the cobalt precipitation circuit consisted of filtrate from the magnesium leach
step. This solution was stored in a separate tank, called CPSTOR, from where it was
continuously pumped into the next tank, CPREP. A portion of the overflow from the last

2
precipitation reactor, CP6, was recycled internally. The slurry leaving the reactor train via
CP6, was handled on a 2-hour cycle basis, as follows:

 Slurry collected during the first 80 minutes was flocculated and thickened.
 Thickener underflow was returned to the Co precipitation circuit via CPREP.
 Thickener overflow was filtered. This solution will be a waste stream on the full-scale
plant. During the mini plant campaign, filtrate and wash waters from the cobalt
precipitation circuit were collected in 24-hour batches and frozen, for possible use
later.
 Slurry collected during the next 40 minutes was flocculated and filtered.
 The 40-minute filtrate was collected and stored frozen.
 The filter cake (average wet mass ~0.65 kg) was washed three times, on the filter pan,
with roughly 1 liter of fresh water per wash.
 The washed filter cake continued to the Mg Leach unit operation.
 The three wash waters were collected and frozen.

Filtrate from the Mg Leach and the 80-minute underflow slurry were mixed in CPREP,
from where it was pumped at a fixed rate to the first reactor in the train of six, i.e. CP1.
The 6 precipitation reactors were fitted with overflow pipes, to allow for continuous flow
of slurry to the next reactor by gravity.

A slurry profile was taken across the circuit, i.e. CPREP, CP1 to CP6, roughly once per
eight-hour shift. The slurry sample was filtered to produce a solution sample. The solid
portion was washed three times with fresh water, to remove entrained feed solution,
before being dried in an oven at ~100 oC. Solutions and washed solids were analysed by
Inductively Coupled Plasma-Optical Emmission Spectroscopy (ICP-OES).

The temperature, pH and redox potential in reactors CP1 to CP6, as well as the flowrates
of Mg Leach filtrate to CPREP and combined slurry (Mg Leach filtrate and 80-minute
slurry recycle) to CP1, were measured hourly.

3
Dry magnesium oxide (MgO) powder was manually screened into the first reactor, CP1.
Provision was made for MgO addition into the first three reactors, but this was changed
during the mini campaign run to addition to the first reactor only. MgO was supplied as
EMAG45 by Queensland Magnesia. The MgO powder was not slurried with water, but
rather added as a dry powder, to conserve its reactivity. MgO loses its reactivity shortly
after being hydrated (<1 hour), due to the absorption of CO2 from the surrounding air. It
was added through a screen (220 µm aperture), to ensure even dispersion of the material
in the reactor. Larger, agglomerated particles are likely to get coated with cobalt
solution. Such particles are difficult to break up during normal agitation, rendering the
trapped reagent unavailable for reaction, and thus resulting in a high Mg deportment to
the solids.

Automatic pH control was done by the addition of sodium hydroxide solution (40 g/L
NaOH) to the last three reactors, CP4 to CP6, to maintain the desired pH values in these
reactors.

Reactors CP1 to CP6 were fitted with equipment to allow for nitrogen purging, but this
was not employed during the mini plant campaign.

6.2.2 Equipment

Six 5-L polypropylene reactors were used. Each reactor (CP1 to CP6) had an active
volume of 5 liters and was fitted with the following:
 Steam coil and thermocouple for automatic temperature control
 Overhead stirrer
 pH probe
 reactors CP4, CP5 and CP6 were linked to a pH controller with NaOH reservoir and
pump, to enable automatic pH control

6.2.3 Changes to cobalt precipitation circuit

4
During the course of the mini plant campaign, the following changes were made to the
CP circuit:

 The slurry leaving CP6 was initially filtered and the filter cake split for recycling
(~66% of the wet cake) to CP and processing in the Mg Leach (~34% of the cake). It
was found that the filtration step was limiting the rate of transfer of process streams,
so the processing of the CP6 overflow slurry was changed, to the process described in
Section 6.2.1.
 MgO was initially added to the first three reactors, CP1 to CP3. To allow more
residence time for complete utilisation of the MgO, this was changed to addition of
the required amount of MgO into CP1 only.
 The agitator speed in CP1 to CP6 was increased, to allow for more efficient mixing.

6.2.4 Process targets

The targets of the CP unit operation were the following:

 Removal of cobalt from the feed to the circuit (~9 g/L Co, primarily diluted due to
wash waters added in Mg leach circuit), by precipitation with MgO to <100 mg/L Co
in the barren (will limit loss to around 1%);
 Limiting the deportment of Mg to the final Co cake, to achieve <2% Mg in the solids
(to be reduced to <1% in Mg leach);
 Producing a Co hydroxide cake with as high as possible a Co content (around 40%);
 Other base metals present in the feed to the circuit, i.e. Al, Si, Fe, Ni, Cu, Zn, will
precipitate in the pH range at which the plant was operated. Deportment of these was
monitored.

5
6.3 Experimental

6.3.1 Laboratory test work

A schematic diagram of the CP and Mg unit operations as they were evaluated during the
laboratory test work is given in Figure 6.2. The Mg Leach is discussed in detail in
Chapter 7.

MgO NaOH

Cobalt
Iron Free PLS Precipitation
600C
Wash Water

S Waste Stream
L

Magnesium
Leach
600C Wash Water

S
L

Figure 6.2 CP and Mg Leach laboratory schematic layout

Laboratory tests were done in a 5 litre mechanically-agitated vessel. The PLS solution
(4.5 L) was placed in the reactor and the reactor was heated to 60 0C. The temperature
was maintained at this level for the duration of the test. pH and Eh measurements were
taken hourly and recorded. Kinetic samples were taken at the specified pH intervals,
filtered, washed and submitted for ICP OES analyses. The effective precipitation
retention time was 6.0 hours from first contact with MgO.

6
Bulk tests were done in heated, mechanically agitated 40 L fibreglass reactors. The PLS
(23 L) was heated to 60 0C prior to introduction of MgO. A residence time of 6 hours
was allowed. The MgO was added by screening the powder through a 212 μm screen,
and attempting to limit its contact with air.

For the small scale tests 4.5L of solution was heated to 60

6.3.2 Continuous mini plant campaign

A detailed description of the equipment and general operating strategy followed during
the mini plant campaign is provided in Section 6.2.1. Experimental conditions are
summarized in Table 6-1.

Table 6-1 Experimental conditions: mini plant campaign

o
Temperature C 60
pH control no pH control in CP1 to CP3
40 g/L NaOH in CP4 to CP6
MgO addition as a dry powder, screened into reactor
through 220 μm aperture screen
Flowrate of solution from mL/min 40
Mg Leach
Flowrate of slurry (Mg mL/min 140 (into CP1, gravity flow to the next
Leach solution + recycled reactor across the rest of the reactor-train )
slurry) into train
Residence time hours/stage 0.6
hours/circuit 3.6

6.4 Results and discussion

6.4.1 Laboratory test work

7
Detailed operating condtions, results and mass balances are provided in Appendix 6.1

The composition of the synthetic solution used for the laboratory test work is given in
Table 6.2. This solution represented the Co stream anticipated after Fe removal. Some,
Fe, Cu, and Al were included in the solution in order to evaluate their deportments.

Table 6.2 Composition of synthetic solution for laboratory test work

Co Mn Mg Fe Zn Cr Cd U3O8 Ni Cu Ca Cl Al H2SO4
mg/L
12 2.9 2.5 0.05 0.11 0.1 5 0.06 0.05 0.05 0.5 0.2 0.5 7.2
4

Three small scale and 4 bulk tests were done. The details around of each test were as
follows:

Test 1: Only MgO as precipitant, pH 7.2, 7.5, 8.0, 8.2 and 8.5
Test 2: Only MgO as precipitant, pH7.2, 7.5, 7.8, 8.0, 8.5
Test 3: pH7.5, 7.8 and 8.0 with MgO, and pH 8.2, 8.3, 8.4, 8.5 with 1M NaOH
Bulk Test 1: pH7.5, 7.8 and 8.0 with MgO and pH 8.2, 8.3, 8.5 with 1M NaOH
Bulk Test 2: pH7.5, 7.8 and 8.0 with MgO and pH 8.3, 8.5 with 1M NaOH
Bulk Test 3: pH7.5, 7.8 and 8.0 with MgO and pH 8.2, 8.3, 8.5 with 1M NaOH
Bulk Test 4: pH7.5, 7.8 and 8.0 with MgO and pH 8.2, 8.3, 8.5 with 1M NaOH

Bulk Tests 1-3 were done by the same procedure as Test 3 but in bigger volumes (23 L)
to produce a precipitate product of sufficient mass for subsequent Mg Leach test work.

Local AR grade MgO was used for all the tests, except for Bulk Test 4 where “EMAG
45” was employed as precipitant. This MgO was sourced from Queensland Magnesia,
Australia as “EMAG45” product on instruction from the client. The typical “EMAG45”
composition is given in Table 6.3.

8
All solid products from the precipitation tests were sealed in nitrogen-purged plastic bags
without drying, in an attempt to prevent oxidation of Co which would be insoluble under
the conditions of leaching in the Co Precipitate Resolution (CPR) unit operation. A small
sample was taken for moisture determination and for elemental analysis. The washed,
moist cobalt precipitation cakes from Bulk Tests 3 and 4 were used for Mg Leach test
work (Chapter 7).

The results obtained with the various tests are summarised in Table 6.3. When only MgO
was used as precipitant, the consumption was high at 1.44 kg/kg Co. This is about 180%
stoichiometric addition. When MgO was added to precipitate the bulk of the Co, the
addition was close to stoichiometry, with an average of 0.75 kg/kg Co. In test 4, MgO
was overdosed, which can be seen in the consumption as well as the fact that no NaOH
was used. The NaOH consumption was relatively high per mass of Co precipitated (by
NaOH), as the target Co concentration was low.

High Mg contents, and concomitant relatively low Co contents, were obtained during the
small scale tests. On the bulk tests the Mg content was reduced to on average 2.0 %. The
Co content of the cakes produced during the bulk tests was 39.6%. Mn concentrations
varied between 4-6%.

The moisture contents of the cakes indicate that the material was difficult to filter in the
laboratory. Co losses were generally very low, except for 2 tests where it was around
1%.

Table 6.3 Summary of laboratory test results

Test 1 Test 2 Test 3 Bulk 1 Bulk 2 Bulk 3 Bulk 4
Residence time, h 6.0 7.5 7.5 7.0 7.0 7.0 7.0
MgO additiona
kg/kg Co ppt 1.44 1.05 0.81 0.72 0.76 0.76 1.12
NaOH additionb
kg/kg Co 9.9 8.9 12.7 11.2 0
Solid composition
Co, % 26.3 32.0 32.0 37.8 41.0 39.2 40.5
Mn, % 5.6 6.0 4.8 5.2 6.3 5.6 4.0

9
 Mg, % 11.5 4.8 6.0 2.4 1.6 2.0 2.1
Moisture content, % 70 67 65 71 78 77 61
Final Co
concentration, mg/L 2 7 20 94 33 34 139
Co loss, % <0.1 <0.1 <0.2 <1 <3 <3 <1.2
a – 0.78 kg MgO/kg Co is stoiciometric addition at the purity of EMAG45
b – kg NaOH per kg of Co precipitated by NaOH only

The deportment of Co to the solids, at the intermediate pH values in approach to the

targeted pH, during the small scale and bulk tests are given in Figures 6.3 and 6.4
respectively. The apparent higher precipitation obtained during test 1 was due to an
overdose of MgO, as can be seen in the Mg content of the final solids (Table 6.3).

Cobalt Solid Deportment in Lab Tests

120%

100%

80%

60%

40%

20%

0%
7 7.2 7.4 7.6 7.8 8 8.2 8.4 8.6
pH
TEST 1 TEST 2 TEST 3

Figure 6.3 Co deportment to solids, small scale tests

10
 Cobalt Solid Deportment in Bulk Tests
120%

100%

80%

60%

40%

20%

0%
7.4 7.6 7.8 8 8.2 8.4 8.6
pH
BULK 1 BULK 2 BULK 3

Figure 6.4 Co deportment to solids, bulk tests

The Mn deportment during the small scale and bulk tests are given in Figures 6.5 and 6.7
respectively, at the various intermediate pH values in approach to the targeted pH value.
The high degree of Mn precipitation at lower pH values for test 1 was again due to the
overdose of MgO, which could have caused localized precipitation. In the bulk tests, it
can be seen that Mn precipitation increased significantly at pH values of 8 and higher.

Based on the Co and Mn deportment to the solids (recovery), the optimum pH for
recovery of the Co would be around 7.7-7.9, where the majority of the Mn is rejected, but
the Co is still recovered efficiently.

11
 Manganese Solid Deportment in Lab Tests
120%

100%

80%

60%

40%

20%

0%
7 7.2 7.4 7.6 7.8 8 8.2 8.4 8.6
-20%
pH

TEST 1 TEST 2 TEST 3

Figure 6.5 Co deportment to solids, bulk tests

Manganese Deportment in Bulk Tests

90%
80%
70%
60%
50%
40%
30%
20%
10%
0%
-10%7.4 7.6 7.8 8 8.2 8.4 8.6
pH
BULK 1 BULK 2 BULK 3

Figure 6.6 Co deportment to solids, bulk tests

The Co content of the solids at the various pH intervals for the small scale and bulk tests
are given in Figures 6.7 and 6.8 respectively. The Co content in the solids also decreased
at a pH higher than 8, due to the co-precipitation of mostly Mn and probably some Mg.

12
 Cobalt Concentration in Solid Lab Tests
50.00%

45.00%
Concentration

40.00%

35.00%

30.00%

25.00%
7 7.2 7.4 7.6 7.8 8 8.2 8.4 8.6
pH
TEST 1 TEST 2 TEST 3

Figure 6.7 Co deportment to solids, bulk tests

Cobalt Concentration in Solid Bulk Tests

45.00%
43.00%
41.00%
Concentration

39.00%
37.00%
35.00%
33.00%
31.00%
29.00%
27.00%
25.00%
7.4 7.6 7.8 8 8.2 8.4 8.6
pH
BULK 1 BULK 2 BULK 3

Figure 6.8 Co deportment to solids, bulk tests

13
6.4.2 Continuous mini plant campaign

Detailed operating conditions, results and mass balances are provided in Appendix 6.2.

The feed solution to the cobalt precipitation step consisted of the combined filtrate and
wash waters from the Mg Leach unit operation. An average composition of this solution
is provided in Table 6.4. It can be seen that a relatively large dilution was introduced
across Mg Leach, which received its feed liquor from FeREM (just under 12 g/L Co).

Table 6.4 Feed solution composition (mg/L) [a]

Mg Al Si Ca Ti V Cr Mn Fe
1 780 16 17 479 <2 <2 <2 1 564 6
Co Ni Cu Zn Mo Pb S As
9 051 14 1 <2 <2 4 8 401 13
[a] the detection limit for the analytical method employed, ICP-OES, was 2 mg/L

EMAG 45, supplied by Queensland Magnesia, was used as MgO precipitant. An analysis
of the MgO powder is provided in Table 6.5. The calculated purity of the solids,
assuming all Mg is present as MgO, was 91%. The main impurities in the MgO solids
were Al, Si, Ca, Mn, and Fe.

Table 6.5 Composition of MgO (%) [a]

Mg Al Si Ca Mn Fe
54.8 0.06 0.5 2.0 0.09 0.17
Co Ni Cu Zn Pb
<0.05 <0.05 <0.05 <0.05 <0.05
[a] the detection limit for the analytical method employed, ICP-OES, was 0.05%

The pH in each stage was monitored throughout the campaign. The pH values in CP1 to
CP3 were not controlled, but allowed to achieve a natural value, from the addition of

14
MgO. The pH values in CP4 to CP6 were automatically controlled at the desired pH
value by the addition of 40 g/L NaOH. The average pH profile across the reactors, for
the duration of the mini plant campaign, is listed in Table 6.6. The average pH in the Mg
Leach unit operation was around 6.4. The higher pH in CPREP could be attributed to
entrained solution in the 80-minute slurry thickener underflow that was recycled from
CP6, as this entrained solution would have been at a pH value of 7.5.

Table 6.6 Average pH profile across the CP unit operation

CPREP CP1 CP2 CP3 CP4 CP5 CP6
6.7 6.9 6.9 7.1 7.3 7.6 7.5

Temperature
The temperature in each of the reactors was automatically controlled, with steam passed
through a steam coil in each reactor. The desired temperature was 60 oC. The average
temperatures for the different stages are shown in Table 6.7. No changes were made to
the temperature profile during the mini plant campaign. The temperature remained fairly
constant throughout the campaign.

Table 6.7 Temperature profile across Co precipitation circuit (oC)

CPREP CP1 CP2 CP3 CP4 CP5 CP6
59 59 60 59 59 59 60

Extent of precipitation
The average composition of the CP6 solution and solid phases are provided in Table 6.8
and Table 6.9, respectively. The compositions listed in both tables were averaged over
the duration of the continuous mini plant campaign.

Table 6.8 CP6 solution, average composition (mg/L) [a]

Mg Al Si Ca Ti V Cr Mn Fe
4 335 3 25 575 <2 <2 <2 597 1

15
 Co Ni Cu Zn Mo Pb S As
147 <2 <2 <2 <2 1 7 910 <2
[a] the detection limit for the analytical method employed, ICP-OES, was 2 mg/L

Table 6.9 CP6 solids, average composition (%) [a]

Mg Al Si Ca Ti V Cr
2.4 <0.05 0.4 0.3 <0.05 <0.05 <0.05
Mn Fe Co Ni Cu Zn Pb
4.6 0.2 41 0.1 <0.05 <0.05 <0.05
[a] the detection limit for the analytical method employed, ICP-OES, was 0.05%

The extent of precipitation of the main metals of interest is listed in Table 6.10. These
values were based on the difference in the mass of metal in the feed and barren (CP6)
solutions.

Table 6.10Extent of precipitation across Co precipitation circuit (%)

Al Mn Fe Co Ni Cu
91 72 97 99 100 100

Ca remained at saturation level in the solution. Any Fe, Ni, and Cu that entered the Co
precipitation circuit, co-precipitated as a hydroxide and reported to the final solids. The
Al in the feed solution was low, at ~16 mg/L, of which 91% was precipitated. .

The feed solution contained ~1.5 g/L manganese, of which 72% was precipitated. The
barren solution from the Co precipitation circuit, CP6, contained 597 mg/L Mn. This
translated to 28% deportment of the incoming Mn to the barren solution. Since the barren
solution would be a waste stream, the extent of Mn deportment to this stream is critical as
it is the major exit of Mn from the Co refining circuit.

Precipitation of cobalt was efficient, at 99%, from a feed solution containing ~9 g/L Co,
down to 147 mg/L Co in the CP6 solution. The feed to the Fe removal circuit contained
12 g/L Co, but this was diluted by the addition of wash waters from both the Fe removal
and Mg Leach cakes, to result in the lower concentration of 9 g/L entering the Co

16
precipitation circuit. The specification of <100 mg/L Co in the barren solution was
achieved during 12 out of the 23 profiles. A barren solution concentration of 147 mg/L
cobalt translated to a loss of cobalt of ~1.6%, based on the Co in the feed to the Co
precipitation circuit

The Mg concentration increased from 1.8 g/L in the feed solution to 4.3 g/L in the barren
solution.

The final solids contained on average 41% cobalt and 2.4% magnesium, indicating fairly
good utilisation of the MgO solids for cobalt precipitation. This was somewhat higher
than the Mg levels obtained during the laboratory investigation, and might be related to
the method of addition during the pilot plant campaign. The other major elements that
reported to the final solids were Mn (4.6%), Si (0.4%), Ca (0.3%), Fe (0.2%), and Ni
(0.1%).

The Fe content of the final solids (CP6) was ~0.2%. This could be attributed to
contamination from the MgO solids used, and the inefficient Fe removal in FeREm
circuit although the Fe in the feed solution to CPR was low, at 6 mg/L. The
concentrations of Al, Si, Ca, and Mn in the final solids (CP6) could also have originated,
partly, from contamination via the MgO solids. The MgO solids contained 0.06% Al,
0.5% Si, 2.0% Ca, and 0.09% Mn, as listed in Table 6.5.

A solution profile for the main metals of interest across the cobalt precipitation circuit,
including CPREP and CP1 to CP6, is provided in Figure 6.9. This profile was taken at
02:00 on 31 October 2006.

17
 8000 700
7000 600

Mg, Mn, Co (mg/L)

Ca, Si, Al (mg/L)

6000 500
5000
400
4000
300
3000
2000 200
1000 100
0 0
CPREP CP1 CP2 CP3 CP4 CP5 CP6
Reactor number

Mg Mn Co Al Si Ca

Figure 6.9 Solution profile across Co precipitation circuit

The magnesium concentration increased from 3.3 g/L in the CPREP solution to 5.1 g/L
Mg in the CP6 solution. Simultaneously, the Co concentration decreased from 6.7 g/L
Co in CPREP to 0.06 g/L Co in CP6. The manganese concentration decreased from 1.7
g/L to 0.7 g/L Mn, across the circuit. Fe, Ni, and Cu concentrations fell to <2 mg/L in
CP1, which suggest complete precipitation of these metals. Si and Ca concentrations
remained constant across the circuit. The aluminium concentration decreased from 16
mg/L to 5 mg/L across the circuit.

A solid profile across the circuit, for the same period (02:00, 31 October 2006), is
illustrated graphically in Figure 6.10.

18
 50 0.6

Ca, Si, Fe, Ni, Cu (%)

40 0.5

Co, Mn, Mg (%)

0.4
30
0.3
20
0.2
10 0.1
0 0
CPREP CP1 CP2 CP3 CP4 CP5 CP6
Reactor number

Mg Mn Co Si Ca Fe Ni Cu

Figure 6.10 Solid profile across Co precipitation

The cobalt concentration in the solids increased slightly across the circuit, from 42.6% in
CPREP to 44.5% in CP6, due to Mg leaching towards CP6.

The magnesium concentration increased from 1.7% in CPREP to 4% in CP1, where MgO
addition took place. It increase slightly to CP2 (6%), and then decreased across the rest
of the circuit, with 1.9% Mg present in the CP6 solids. The Mg concentrations in the
solids and solution were stable in CP4 to CP6, indicating that complete utilisation of the
MgO solids had taken place by the time the slurry left CP4. This translated to a residence
time requirement of an additional 1.8 hours (0.6 hours per stage in CP2, CP3 and CP4)
after addition of the MgO solids in CP1, to allow for complete utilisation of the reagent.

Si and Ca remained constant in the solids across the circuit, at 0.3% and 0.4%,
respectively. All the Fe, Ni, and Cu precipitated in CP1, and the concentration of these
metals in the solids remained constant across the rest of the circuit.

Reagent consumption
The two reagents used in the CP unit operation were MgO solids, to effect precipitation
of cobalt as cobalt hydroxide, and a 40 g/L NaOH solution, to ensure final polishing of

19
the solution at the desired pH in the last three reactors by maintaining the pH at 7.5 in
CP4 to CP6.

MgO was added to the first reactor, CP1, as a dry powder. The flow and consumption of
Mg and MgO is illustrated by presenting data from 7 different 24-hours periods, across
the runtime of the mini plant campaign. The relevant cobalt and magnesium
concentrations in the feed and CP6 solution and solids, as well as MgO consumptions are
listed in Table 6.11.

Table 6.11 Mg deportment and MgO consumption

Profile no 1 2 3 4 5 6 7
Feed:
Mg mg/L 1487 1727 1676 1676 2147 2249 1752
Co mg/L 6799 7885 7374 7374 10734 11584 11134
CP6
solution:
Mg mg/L 3387 3400 3915 3598 4500 4902 5178
Co mg/L 73 83 347 101 92 318 177
CP6 solid:
Mg % 2.47 2.53 2.02 4.37 3.21 1.93 2.88
concentration
MgO kg MgO/kg Co 1.12 0.84 0.81 0.94 0.63 0.67 0.62
addition
mol MgO/mol 1.6 1.2 1.1 1.3 0.9 1.0 0.9
Co

The average MgO addition to the cobalt precipitation circuit was 0.8 kg MgO per kg Co
in the feed. Excess MgO remained unreacted and reported to the final (CP6) solids. The
stoichiometric MgO requirement, for Co precipitation only, is 0.78 kg MgO per kg Co (at
the purity of EMAG45.

20
The NaOH consumptions were determined over a 24 hour period. The total NaOH
consumption across the last 3 reactors, CP4 to CP6, was calculated to be:

0.3 kg NaOH/kg Co throughput

5.8 g NaOH/liter feed solution treated

Cobalt balance
Due to the continuous nature of the mini plant operation, it was not possible to construct
an accurate total mass balance, accounting for metals in both solids and solutions. A
cobalt balance was done, calculating the average flow of cobalt through the plant in g
Co/hour. The results are listed in Table 6.12.

Table 6.12 Cobalt balance across cobalt precipitation circuit (g/hour)

IN OUT OUT/IN
Co, Mg Leach Co, CP6 solution Co, CP6 solids
solution
56 0.7 35 0.6

Approximately 56 g Co entered the cobalt precipitation circuit hourly, as solution from

the Mg Leach circuit. The majority, 35 g Co/hour, reported to the portion of CP6 solids
(40-minute slurry) exiting the plant to the Mg Leach unit operation, while a small
amount, 0.7 g/hour, reported to the CP6 solution. This translates to a Co loss of <1.5%,
based on Co in CP6 slurry.

The inaccuracy in the balance (63%) can be largely attributed to difficulties experienced
in obtaining accurate solution volumes and solid masses during a continuous mini plant
campaign.

6.4.3 Thickening and filtration data

This section will be inserted, but the detailed report is provided in Appendix 6.3.
Testwork on the filterability and washing efficiency of the material was done by MacOne

21
Agencies. For this purpose, 15.4 kg of CP6 overflow slurry was provided to MacOne on
29 October 2006.

6.5 Conclusions

6.5.1 Laboratory test work

 99.0 – 99.9% Co precipitation is achievable under the conditions employed during

the test campaign: pH values up to pH 8.5, using MgO alone, and MgO + NaOH

 All iron and copper were polished out of the solution at a pH above 7.2

 80% of Mn co-precipitated with the Co during bulk precipitation tests at pH

values of 8.5.

 40% Mn rejection could be possible at pH 8.2 with Co losses of ca 150 mg/L

(ca.1.25%).

 Mg content of the CP cake could be limited to 2%, which was reduced to < 1% in
the Mg Leach.

 The rate and method of MgO addition determined the quality of the final product
in terms of Mg content.

 Filtration of Cobalt precipitate was extremely difficult and time consuming with
from 60%+ moisture in the filter cake

 MgO consumption was on average 0.80 kg/kg Cobalt.

 The Co product contained on average about 40% Co.

6.5.2 Continuous pilot plant campaign

The feed to the cobalt precipitation unit operation of the mini plant campaign contained
~9 g/L Co. It was possible to remove the cobalt from solution, by precipitation with
MgO powder, to ~147 mg/L Co in the barren solution, across 6 stages. This translated to

22
a Co loss of ~1.6%, which is relatively high and should be possible to reduce to less than
1%. The final solids contained, on average, 41% Co and 2.4% Mg. The targets of <100
mg/L Co in the barren solution and <2% Mg in the final solids were achieved on a
number of profiles during the continuous mini plant campaign, but not consistently.

The other major elements that reported to the final solids were Mn (4.6%), Si (0.4%), Ca
(0.3%), Fe (0.2%), and Ni (0.1%).

Effective utilisation of MgO was achieved by adding the required amount of MgO to the
first stage, CP1. This allowed sufficient contact time for reaction of the MgO, thus
minimising the Mg reporting to the final solids. The MgO addition rate was 0.8 g MgO
per g Co entering the circuit.

The pH in the last 3 stages were controlled at ~7.5 by the addition of 40 g/L NaOH, to act
as a polishing step for further precipitation of cobalt metal. The average sodium
hydroxide consumption during the mini plant campaign was 0.3 g NaOH/g Co.

A residence time of 0.6 hours per stage was allowed, translating to an overall residence
time of 3.6 hours in 6 stages. Six stages, and 3.6 hours, were required to decrease the
cobalt concentration in the solution to the desired value of <100 mg/L.

The average pH in CP1 and CP2 was 6.9, while it increased slightly to 7.1 in CP3. This
was the natural pH, due to the addition of MgO in CP1 and subsequent reaction of MgO.
The pH in CP4 to CP6 was controlled, at ~7.5, by the addition of 40 g/L NaOH.

The cobalt precipitation was run at a temperature of 60 °C. The effect of temperature was
not tested. The value of 60 °C was prescribed by the engineering consultant for the client,
based on his previous experience.

23
 APPENDIX 6.1

LABORATORY CP TEST WORK

DETAILED OPERATING CONDITIONS,

RESULTS AND MASS BALANCES

24
 APPENDIX 6.2

CONTINUOUS CP PILOT PLANT CAMPAIGN

DETAILED OPERATING CONDITIONS,

RESULTS AND MASS BALANCES

25
 APPENDIX 6.3

THICKENING AND FILTRATION

(Report by A. MacDonald)

26
MAC ONE AGENCIES RANDBURG.
PHONES: +27-11-794-2982 +27 082 882 5276.

FIRST QUANTUM. FOR ATTENTION Mr GRENVIL DUNN.

KOLWEZI : LIQUID: SOLID SEPARATION
KOLWEZI Co PRECIP
All data on sheet “FQ KOL CRRR” of File FQKOLWEZI.xls.

1. SEDIMENTATION:
1.1. FLOCCULANT SELECTION: Magnafloc 338 related in qualities to
Magnafloc 1011 and 155 was found to be more suitable and was used for all
the tests reported for the 1006 Kolwezi work because it was faster than 155
and gave better clarities than 1011.
1.2. DATA: The solids SG was assumed to be 3.7, liquid measured at 1.026 and
slurry at 1.0506. The experimental data are recorded on sheet Co PRECIP of
file FQKOLWEZI.xls.
1.3. DOSAGE CURVE: A dosage curve was done with the slurry at three feed
densities. The responses to dosage were not as large as the responses to feed-
well density.

Table 1. Summary of dosage versus thickener area required.

Dosage, g/t. 59g/t 29g/t

Feedwell solids, % Thickener area required m2/t.h.
3.2%. 20.776 20.599
1.9%. 8.257 9.016
1.3%. 13.187 12.071

Kolw e zi Co Pre cipitate : Fe e dw e ll de ns ity ve rs us Thick e ne r

are a at tw o dos age s .

22
area, sq.m. per hourly ton.

20
59g/t
18
29g/t
16
14
12
10
8
6
1.0 1.5 2.0 2.5 3.0 3.5
Fe e dw e ll s olids , %

27
Figure 2. Dosage versus thickener area required.

1.4. DISCUSSION OF RESULTS:

1.4.1. At the two dosages tested for each feed density, there was not much difference
in settling rates. With the thickener test at 2.04% solids, however, the dosage
was varied to achieve a good sized floccule, not too large (to avoid holding
water). At 50g/t the behaviour was satisfactory and then at this dosage, the
pilot test feed was installed and run.
Table 2. Feedwell solids versus indicated solids flux.

Flocculant dosage, g/t 29.378 58.756

Feed-well solids, % Solids flux indicates, t.h/m2
3.200 0.049 0.048
1.900 0.111 0.121
1.3 0.083 0.076

Kolwezi Co Precipitate: Feed-well density versus solids flux

0.13
0.12
Solids flux: t.h/sq.m.

0.11
0.10
0.09
0.08
0.07
29.378
0.06
58.756
0.05
0.04
1.0 1.5 2.0 2.5 3.0 3.5
Solids, %

Figure 3. Feedwell solids versus indicated solids flux at two dosages.

1.4.2. Table 2 . Summary of pilot thickener test results.

THICKENER SUMMARY FILE
RUN NO/DATE 1
ORE SAMPLE NAME CoPRECIP
FLOC NAME MAG 338
RUNTIME RISE RATE M/H 5.77

28
TOT DOSAGE G/T 50.6
U/FLO DETENTION TIME,MIN. 15
RAKE SPEED RPM 1.50
FEED % SOLID INCL. FLOC 2.037
UNDERFLOW DENSITY 1.129
CLARITY @ 300MM BED CWLINES 46+
FINAL % SOLID 12.74
SOLIDS LOADING T.H/M² 0.12223
AREA USED, M².HR/TON 8.181

1.4.3. INFERENCES: The cylinder and pilot tests confirmed one another in regard
to dosage, area requirement, solids flux and terminal density achieved.
1.4.4. SUPERNATE: The Supernate was very clear.
1.4.5. BED BEHAVIOUR: There was a slight, not serious amount of bed rotation
as a doughnut .
1.4.6. UNDERFLOW DENSITY: The received density of this material was 3.24%
solids. The pilot thickener feed density was 2.04% The underflow density at
15 minutes detention was 12.74% solids. This was the same as the cylinder
test performance.
1.4.7. DOSAGE: The dosage of 50g/t seemed to be best for water release and
floccule formation.
1.4.8. FEED DENSITY: The sensitivity to feed density was huge. The received
density of 3.24% solids required 2.5X the area required at 1.9% solids. On the
other side of the curve, the 1.3% solids slurry required 1.6X the area of 1.9%
slurry requirement.
1.4.9. SOLIDS FLUX: The solids flux managed by the pilot thickener was 0.122
t.h/m2. The area used was 8.18m2.h/t. These two parameters agreed fairly
well with the cylinder tests, confirming our spreadsheet factor of safety at
2.5X net cylinder indications to depict the real world for this material.
1.5. RECOMMENDATIONS: If this material is to be thickened:
1.5.1. FEED DENSITY: The feed-well should be fed at 1.7 to 2.0% solids.
1.5.2. DOSAGE: A dosage of between 30 and 50g/t should be provided for. Best
clarity will be achieved with multiple dosages, at least 2 doses, split 50/50.
1.5.3. THICKENER AREA: The thickener should provide at least 8m2/t.h. with
additional capacity for operation outside the close density specifications. Any
deviation from the optimum density will be up steep curves both ways, so
please provide double the area for safety and ensure a good density control.
The thickener should be a full standard or 4m height regardless of diameter to
provide for mud-line level fluctuations, and provide clear overflow.
1.5.4. FLOCCULATION: Due to the possibility of a high population of fine
particles, the flocculant should be blended into the slurry in good blenders,
preferably in-line blenders. We suggest that the blenders should be two but-
welded right angled “z” formations in closed HDPE pipelines, not launders.
The dosage is injected just upstream of each blender. The doses are at least 10
seconds apart and the last dose is right at the feed-well with delivery
tangential, under the liquid level of the feed-well.
1.5.5. FEEDWELL: Although the settling rates are good, it is always advisable to
have deep feed-wells to deliver the flocculated slurry at the bottom of the

29
 thickener at the level where the cone meets the cylinder. There should be a
baffle below the feed-well to prevent new feed kicking up the bed.

1.6. FILTRATION: HV Belt filtration tests were done on the thickener underflow
of this product. The test with no additional flocculation was as good as the test
flocculated with 274g/t of Magnafloc 338. Another test with Magnafloc 155
required more filter area than the un-flocculated test. The test data reports the
filter areas required at various wash ratios from 2.0 m3/ton to 4.0m3/ton dry
solids. No assays were done. The areas represent total form, wash and dry
areas all together. The drying oven was adjusted to a high temperature
overnight by shift workers. This over-baked the filter cakes to record 74%
moisture. A repeat test was done and dried at 60ºC. This test produced the
same dry weights as the original and so the results were kept as good.
NB. The areas quoted are 3X the net area achieved with -73kPa vacuum reading,
to allow for inferior vacuum on industrial plant.

Table 3. HVB filter test data.

Filter flocculant dosage, g/t zero floc 274mag338 274mag155
Wash ratios L/kg Dry Solid Filter area required 3X net , m2.h/t
4.00 18.6 18.8 24.1
3.00 16.7 16.0 20.9
2.00 14.4 13.7 18.0
Moisture in cake, % 74.48 73.47 74.63

Co precip : Wash ratio versus belt filter area with various

floc dosages.

26
zero floc
24 274m ag338
Filter area. sq.m.h/ton

22 274m ag155

20

18

16

14

12
2.0 2.5 3.0 3.5 4.0
Wash ratio: L/kg

Figure 4. HVB Filtration data.

30
 1.6.1. DISCUSSION OF RESULTS: The above data are from thickener underflow
filtered on the HVB simulator. Filtrates were clear and the filtration times were in a
normal class for belt filters. The result without re-flocculation is an acceptable result.
A 14m2 filter should be big enough for one ton per hour.

1.6.2. INFERENCES:
1.6.2.1. FILTER AREA: This product, as thickened, would require no further
flocculation and would require a filter area of 14m2 for 1.0 ton/h solids
at a wash ratio of 2L/kg. The inverse of the above indicates 71 kg/m2.h
capacity for a belt filter unit operation at a wash ratio of 2L/kg.
1.6.2.2. UNTHICKENED FILTER FEED: Filtering the unthickened product
would increase the filter area to an unspecified size due to the increased
form time to dewater from 3% solids instead of 12%. The material
would not have the benefit of thickener flocculation and this might
increase the form, washing and drying times as well.
1.6.3. RECOMMENDATIONS: The following recommendations are offered.:
1.6.3.1. THICKENING: The material should be thickened at 40 to 50g/t to
maximum density with as long a detention as possible in the thickener.
Consider any flocculant used in the thickener as a filter aid as well. A
peristaltic pump for transferring underflow to the filter would preserve
the flocculated nature of the thickener sediment for filter duty
enhancement.
1.6.3.2. FILTRATION: The thickener underflow should be filtered without
flocculation, but provision should be made for single dose flocculation
with the general flocculant used on the plant. The flocculator dosing
point should be just upstream of a right- angled butt welded “z” in the
HDPE feed pipe to act as a line-blender as near the filter feed distributor
as possible. The dosing point should have a spring loaded (figure 10)
stainless non-return valve to prevent backflow of product slimes into the
flocculant feed pipe.

1.7. PRESSURE FILTRATION: Messrs. Larox have done a pressure filtration test
on thickener underflow product. No report is to hand, but a spreadsheet is
available for comment.
1.8. WASH RATIOS: Tests were done at wash ratios of Zero, 4.0 and 6.1 L/kg dry
solids.
1.9. FILTER TEST RESULTS: The filter press performance data are as follows.
1.9.1. Table 4. Summary of filter press results.
Wash ratio L/kg 0.0 4.0 6.1
2
Capacity solids kg/m .h 59.3 52.5 47.2
2
Capacity filtrate L/m .h 240 204.5 188.2
Cake moisture, % 56.65 57.35 57.63

1.10. INFERENCES: The area specific capacity of the press is 60% of the belt filter
capacity. This is near enough to belt filtration so that the choice is even,
depending on capital and operating cost differences. Practical wash ratios are

31
 possible and the final cake moisture is also much better than the vacuum filter,
taking less solutes with it to downstream process at any chosen wash ratio.
1.11. RECOMMENDATIONS: The choice of final filtration system depends only
on Opex and Capex comparisons. It is possible that an extended press may be
able to handle the whole operation without the thickener. This would have to be
tested on flocculated and unflocculated process streams.

32