Use of sulphur dioxide as reducing

agent in cobalt leaching at Shituru

hydrometallurgical plant
by M.D. Mwema*, M. Mpoyo, and K. Kafumbila

metabisulphite, which were necessary, also

induced an increase in operating cost.
Synopsis Consumption of these reagents averaged 0.8
(metric) ton of Na2S2O5 and 1,2 ton of copper
Copper oxide ores deposits in the Katanga province of the powder per ton of dissolved cobalt,
Democratic Republic of Congo (DRC) contain at variable level cobalt
representing approximately 47% of the total
oxide minerals. In contrast to copper oxide minerals which readily
operating cost per ton of cobalt metal
dissolve in the sulphuric acid solution, the cobalt oxide bearings are
difficult to dissolve, especially if cobalt is present in the third produced.
oxidation state (Co2O3). This species become soluble after reduction Many reducing reagent has been proposed
of Co+3 in Co+2. In practice, the use of reducing agent is therefore to leach cobalt III from oxide ores. The sulphur
necessary in order to transform the insoluble minerals into soluble dioxide seems to be the most used in the
cobalt sulphate species. The following reducing agents are currently cobalt and manganese leaching plant (1-3).
used at the Shituru plant: ferrous ions, which are present in leach Laboratory test works have been
solutions, pulverised copper or sodium meta bisulphite (MBS). performed at Gcamines Metallurgical
Due to the high consumption of reducing agents (0,8 t MBS/t of Research Department to investigate the use of
solubilized Co; 1,2 t Cu/t-Co), cobalt production is expensive. The
sulphur dioxide as reducing agent during the
use of sulphur dioxide as reducing agent was then investigated in
leaching of copper and cobalt ores. Thereafter,
order to reduce operating cost. This reagent also presents the
advantage of sulphuric acid production during the leaching process.
plant trials have been conducted at Shituru.
It has been added in the leaching vessel (tank). Interesting results have been achieved and it
From the laboratory and industrial tests, selective leaching of has been demonstrated that sulphur dioxide
cobalt (78%) has been performed. The cobalt leaching kinetic represents an economical alternative as
depend on sulphur dioxide dosage. Dissolution of copper, iron and reducing agent, which can replace both
manganese remained very low. No emanation of SO2 gas was Na2S2O5 and copper powder.
observed during the process. This paper reports the possibility of
sulphur dioxide use at Shituru plant and its
impact on the copper-cobalt flow sheet of the
plant.

Introduction Laboratory test work

Cobalt oxide minerals, which are present in

Experimental procedure
copper oxide ores in Gcamines concession,
are leached in sulphuric acid solution with Laboratory test works were performed at 40C
more than 90% efficiency. If present in the and pH 4.05. The ore (density of 2.77
third oxidation state (abundance of superior kg/dm3), assaying 4.02% Cu, 1.72% Co,
oxide Co2O3), reduction of Co3+ to Co2+ is 5.09% Fe... was finely ground to 80%200
necessary in order to dissolve it. The common mesh (74 m) and mixed with spent
reducing agents used at the Shituru electrolyte from the Shituru plant which
Hydrometallurgical Plant are: contained copper 14.69 g/l, cobalt 8.79 g/l and

Ferrous ions which are present in

solution as result of ore leaching and
other from acid leach of iron scrap * Gcamines Metallurgical Strategies Direction,
Copper powder Likasi, Democratic Republic of Congo.
Sodium metabisulphite (Na2S2O5). Gcamines Metallurgical Research Department,
Likasi, Democratic Republic of Congo.
In order to increase cobalt production, it
The South African Institute of Mining and
has been recommended to proceed to a direct
Metallurgy, 2002. SA ISSN 0038223X/3.00 +
leaching of cobalt rich oxide ores without 0.00. This paper was first presented at the SAIMM
previous concentration. In this case, however, Conference: Copper cobalt nickel and zinc recovery,
the high dosages of copper powder and sodium 1618 July 2001.

The Journal of The South African Institute of Mining and Metallurgy JANUARY/FEBRUARY 2002 1
Use of sulphur dioxide as reducing agent in cobalt leaching
Table I
Variation of pH and redox potential (Ag/AgCl) as
function of sulphur dioxide injection time

Time Temperature Redox potential

pH
min C mV

0 40 4.05 325
30 40 2.68 232
60 40 2.65 189
90 40 2.53 173
120 40 2.37 159
150 40 2.07 192
180 40 1.98 198

iron 1 mg/l to form a pulp of density 1.6 kg/l. A volume of

1000 ml of the pulp was used in each test. Gas, 20% SO2 in Figure 1Copper and cobalt leaching recovery as function of time
air, was blown in the pulp at 100 l/h through a perforated (laboratory test)
agitation disc. The test was performed in a period of 3 h
without further pH regulation. Samples of liquid and solid
were taken and analysed by atomic absorption spectrometry. cobalt was selectively leached, while copper and iron solubi-
lization remained at very low level. After 3 h, cobalt recovery
Results and discussions was nearly 86%, copper 11% and iron 7%.
The temperature of pulp, the pH and the redox potential were
monitored as shown in Table I. Industrial test
From these data, it was observed that the temperature of
Experimental
the pulp is not influenced by the reaction, while the pH of the
pulp as well as the redox potential continuously decrease. The industrial test works conducted at the Shituru plant
The results shown in Figure 1 clearly indicated that aimed:

1. Liquid SO2 (1 t) 2. Manometer 3. Flexible pipe 4. Ramp 5. Flow meter 6. Valves 7. Pipe 8. Cobalt ore pulp 9. Agitation system
10. Storage tank (Capacity: 291 m3) 11. Agitator electrical motor 12. Centrifugal pump 13. Centrifugal pump motor 14. Pulp pipe
15. Modulating valves 16. Pulp flow meter 17. Sulphur dioxide absorption column 18. Tray 19. Perforated iron sheet 20. Joint 21. Chimney

Figure 2Schematic of the sulphur dioxide injection system to be installed at the Shituru plant

2 JANUARY/FEBRUARY 2002 The Journal of The South African Institute of Mining and Metallurgy
Use of sulphur dioxide as reducing agent in cobalt leaching
to investigate the application of the technique of liquid
SO2 injection in the pulp, with respect of environmental
regulations and personal security
To find out the optimal conditions of liquid SO2
absorption for maximum cobalt recovery.
The experimental device used is illustrated in the Figure
2. Liquid SO2 of 99.9% purity was stored in cylinder tanks 1
containing 1 t SO2 each at 280 KPa. From there, liquid SO2
was sent through pipe 4 to the absorber column 17. The ore
pulp flowed through pipe 14 to the absorber column from top
to the bottom in counter current movement with the gas.
From the storage tank 10, with 291m3 capacity, the pulp was
allowed by a centrifugal pump to continuously circulate at
100 m3/h through the pipe 14, the absorber column and back
to the storage tank 10. Since SO2 used was liquid, the
absorber column chimney remained closed during the Figure 4Leaching recovery as function of time (industrial test)

experiment. After 12 h pulp conditioning as previously

described, 30 m3/h of the pulp stream was sent through
After 13 h, impurities leaching were 5.63% for MgO, 10.7%
modulating valve 15 to the cobalt leaching (cobalt leach
for Fe and 53.9% for Mn.
circuit).
Herewith it was demonstrated that an industrial use of
The ground ore (density of 2.93 kg/dm3), assaying
sulphur dioxide as reducing agent in cobalt ores leaching is
3.95% Cu, 1.11% Co, 3.75% Fe... was mixed with spent
feasible. This method induces selective cobalt leaching
electrolyte from the same plant which contained copper 9.46
towards most impurities (copper, iron, magnesium), but
g/l, cobalt 8.25 g/l and iron 0.5 mg/l to form a pulp of
manganese, which is an important impurity in cobalt electro-
density 1.34 kg/l. The in-plant tests were performed at 32C
winning, is dissolved to a great extent.
and pH 4.3.
Environmental considerations
Results and discussions During the plant test, it was important to check the
Variation of temperature, pH and redox potential emanation of SO2 gas over the storage tank and over the
leaching reactor for environmental considerations. No
In the course of experiment, it was observed that variation of sulphur dioxide was detected over the storage tank during
temperature, pH and redox potential exhibits the same the test works. But, after 10 h of SO2 absorption in the pulp
behaviour as in the laboratory test (Table I). The test was and full flow (100 m3/h) re-circulating in the storage tank,
run in a period of 13 h. The pulp temperature in the storage 30 m3/h of pulp were sent to the pachucas where oxidation
tank remained almost unchanged at 3233C, while the pH acidic conditions are prevailing, SO2 gas was detected around
varied from 4.30 to 2.06 and the redox potential from 215 to and the test was stopped. This SO2 emanation can be
133 mV as shown in Figure 3. explained by the fact that the pulp was saturated in SO2 gas
Leaching performances and the more acidic conditions prevailing in the leach
reactors were favourable to the SO2 emission.
The result of the leaching test is represented in Figure 4,
which clearly indicates that a significant cobalt leaching has
been achieved. Cobalt leaching was performed to an extent of
Conclusions
approximately 80%, while that of copper remained negligible. From the above, it has been demonstrated that substitution
of conventional reducing agents used in Gcamines
hydrometallurgical plants (copper powder, sodium
metabisulphite) by sulphur dioxide in leaching of trivalent
cobalt is possible. Selective cobalt leaching can be achieved at
high recovery level. In contrast to most impurities,
manganese is leached to a significant extent.
The obtained results, so far, showed that the absorption
of SO2 gas can be operated, with respect to environmental
regulation, if SO2 absorption does not reach the saturation
level in the pulp.
The selective cobalt leaching which applying this method
can perform induces an important modification of the copper
cobalt classical flow sheet. Instead of simultaneous
dissolution of copper and cobalt, selective leaching of both
species is possible. First, cobalt can be leached in reducing
conditions with the use of sulphur dioxide. The second stage
Figure 3pH and redox potential (Ag / AgC l) in leach pulp as function of
will be conducted under oxidation conditions to dissolve
copper and rest of cobalt.
time (industrial rest)

The Journal of The South African Institute of Mining and Metallurgy JANUARY/FEBRUARY 2002 3
Use of sulphur dioxide as reducing agent in cobalt leaching
Acknowledgements References
1. BERTINI, M. MAREZIO and DUBY, P.F. Novel leaching applications of the
SO2/O2 system, XXI International Mineral Processing Congress, July 2000.
The authors would like to express their gratitude to the Rome (Italy).
management of Gcamines for permission to present this 2. MILLER, JAN D. and WAN, RONG YU . Reaction kinetics for the leaching of
MnO2 by sulfur dioxide, Hydrometallurgy, May 1983.
paper and the financial support. They also thank Dr Eng. K.
3. GILL, J.B., GOODALL, D.C. and JEFFREYS, B. New leaching agents for oxides,
Kongolo for valuable suggestions. Hydrometallurgy, December 1984.

4 JANUARY/FEBRUARY 2002 The Journal of The South African Institute of Mining and Metallurgy