Journal of Sustainable Mining 18 (2019) 226–246

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Journal of Sustainable Mining

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Review article

A review of the beneficiation of copper-cobalt-bearing minerals in the T

Democratic Republic of Congo
Michel Lutandula Shengoa,∗, Meschac-Bill Kimeb, Matanda Pascal Mambwec,d,
Trésor Kilwa Nyemboe
a
Inorganic Chemistry Unit, Department of Chemistry, Faculty of the Sciences, University of Lubumbashi, Likasi Avenue, PO BOX 1825, City of Lubumbashi, Haut-Katanga
Province, Democratic Republic of the Congo
b
Department of Metallurgy, University of Johannesburg, Doornfontein Campus, PO BOX 17911, Johannesburg, 2028, South Africa
c
Economic Geology Unit, Department of Geology, Faculty of the Sciences, University of Lubumbashi, Kasapa Road, PO BOX 1825, City of Lubumbashi, Haut-Katanga
Province, Democratic Republic of the Congo
d
Department of Exploration Geology, Tenke Fungurume Mining S.A., Airport Road, TFM Building, Lubumbashi, Haut-Katanga province, Democratic Republic of the Congo
e
Research Centre of Minerals Processing, Higher School of Applied Techniques in Lubumbashi, Haut-Katanga Province, Democratic Republic of the Congo

ARTICLE INFO ABSTRACT

Keywords: Copper and cobalt (Cu–Co) are strategic metals for the Democratic Republic of Congo (DRC), and nearly 20% of the
Copper-cobalt beneficiation country's GDP is supported by their exports. At present, the country classifies itself as the leading copper producer in
Froth flotation Africa with an output in the region of a million tonnes and possesses nearly 60% of the world's reserves of Co; a metal
Gravity separation techniques exclusively exported in the form of salts or semi-finished products. Concentrators play a very important role in the
Tailings reprocessing
growth of Cu–Co metal production, which is needed in order to meet rapidly growing global demand and to increase
Reagent suites
government revenues through mining royalties. This article reviews the major process flow sheets and reagent suites
Environmental management
in practice at concentrators operated in the DRC for the beneficiation of Cu–Co values from various ore types. The
comprehensive compilation of pertinent laboratory and industrial data is intended to provide practising specialists,
metallurgists, and academics conducting research on Congolese Cu–Co ores with a single well-detailed reference
source. Emphasis is placed on froth flotation as the major technique for the beneficiation of Cu–Co minerals.

1. Introduction
The Democratic Republic of Congo (DRC) is a country, which has
among the world's richest mineral endowments and earns most of its
revenues from the mining sector. The southwestern region of this
country (former Katanga province) is particularly rich in copper and
cobalt (Cu–Co) mineral resources. It is home to around 5% of the
world's Cu and nearly more than half its Co. Since 2012, the DRC has
positioned itself as the first African producer of Cu, with an annual
output estimated at 900,000 tonnes (Umpula & Amisi, 2012, pp.
14–29). The Belgians opened up industrial mines in the 20th century
(Gorham & Knight, 1977; Julihn, 1928, pp. 27–32; Kalenga, 2014;
Meditz & Merrill, 1994; Verlinden & Cuypers, 1956) and, during the last
decade small and big mining entities appeared all over the Katanga
province. In fact, the UMHK (in French “Union Minière du Haut Ka-
tanga”), created, in 1906 and renamed in 1967, the Générale des Car-
rières et des Mines (Gécamines), which regularly produces about
285,000 tonnes of Cu a year through the operation of the Shituru and
Luilu hydrometallurgical plants (Crowson, 2007; Gorham & Knight,
1977; Meditz & Merrill, 1994; Takeuchi, Strongman & Maeda, 1986, pp.
129–130). This capability was facilitated by the near-surface avail-
ability of Cu–Co oxidised ores, which were mainly in the form of ma-
lachite. At the turn of the 1990s, the Congolese state owned mining
company “Gécamines”, a once world renowned Cu–Co mining opera-
tions leader collapsed after many years of dictatorship, war, and the
country's economic downfall (Lydall & Auchterlonie, 2011; Meditz &
Merrill, 1994; N'Sakila, 2008). Since 2000, the Congolese government,
in collaboration with financial backers, has implemented a series of
large-scale reforms, beginning with the adoption of the new Mining
Law in 2002, conceived to encourage foreign direct investment (FDI) in
the country (Lydall & Auchterlonie, 2011). This has led to the emer-
gence of small and medium private metallurgical plants. In general, the
new plants are built in some old mines which were abandoned by Gé-
camines. Because of the depletion of surface-rich minerals, mining is

Corresponding author.
∗

E-mail addresses: lutandulashengo@gmail.com, shengolutandulamichel@yahoo.fr (M.L. Shengo), meschackime@gmail.com (M.-B. Kime),

pmambwe@cmoctfm.com, p.mambwe@sciencesunilu.ac.cd (M.P. Mambwe), nyembokilwa305@gmail.com (T.K. Nyembo).

https://doi.org/10.1016/j.jsm.2019.08.001
Received 4 February 2019; Received in revised form 30 May 2019; Accepted 5 August 2019
Available online 26 August 2019
2300-3960/ © 2020 Central Mining Institute. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/BY-NC-ND/4.0/).
M.L. Shengo, et al.
Fig. 1. Central African Copperbelt (From the base Map KCB and prepared by Mambwe et al., 2017a,b).
increasingly taking place at depths where ores contain about 70%
oxidised minerals and 30% sulphide minerals. It is important to note
here that oxidised Cu–Co ores are the product of extensive weathering
of the primary in-depth sulphide ore and host-rock, followed by a re-
mobilisation of Cu–Co (Decrée et al., 2010). The H2SO4 leaching effi-
ciency of oxide-sulphide Cu ores rarely exceeds 75%, mainly due to the
difficulty of dissolving the sulphides in sulphuric acid at atmospheric
pressure. This means that the leach residues will contain sulphides that
would trigger acid mine drainage (AMD) and a significant amount of
recoverable metals. Highly acidic leachate loaded with metals may also
eventually migrate into hydrogeological networks and contaminate the
environment and the aquifer.
Currently, the leach/solvent extraction/electrowinning and leach/
precipitation technologies are the most widely used processes for
treating oxidised Cu–Co ores in the Katanga Cu–Co processing industry
(Chadwick, 2008; Fisher, 2011, pp. 237–258; Könighofer, Archer, &
Bradford, 2009; Kordosky, 2007; Mapeta, 2013, pp. 31–64; Mulaba-
Bafubiandi & Bell, 2005). Firstly, oxidised Cu–Co ores are leached using
sulphuric acid under reducing conditions (Kime, Kanowa, Mulaba-
Bafubiandi, & Diyambi, 2016; Kime & Makgoale, 2016; Ntakamutshi,
Kime, Mwema, & Ngenda, 2017). The leach liquor obtained is purified
by solvent extraction; Cu–Co metals are recovered either by electrolytic
extraction or by precipitation. However, the preferred beneficiation
technique for treating oxidised Cu–Co ores remains surface sulphidi-
sation followed by actual flotation (Clark, Newell, Chilman, & Capps,
2000; Countois, Maurice, Arpin, & Demers, 2003; Kime, Ntambwe, &
Mwamba, 2015; Kongolo, Kipoka, Minanga, & Mpoyo, 2003; Umpula &
Amisi, 2012, pp. 14–29; Wimberley et al., 2011, pp. 87–111;
Ziyadanogullari & Aydin, 2005). In some cases, gravity separation is
also implemented as a preconcentration step and is used to remove
sufficiently depleted gangue materials from the circuit. Gravity se-
paration is also used to extract rich concentrates from downstream
process tails. The gravity separation techniques commonly used in the
beneficiation of Cu–Co oxide ores in Katanga include spiral con-
centration, table concentration, and heavy media separation. In gen-
eral, gangue materials consist of quartz, dolomite, muscovite, chlorites,
mica, talc, and clayey minerals (Kanda, 2013; Shengo, 2013). Gangue
material removal prior to the actual processes is of paramount
227
Journal of Sustainable Mining 18 (2019) 226–246
importance as they are responsible for most of the reagents over-
consumption. Gangue materials also affect the operation of processes.
For example, the leaching of high silica-containing ores may result in
the formation of silica gel, which increases the viscosity of the aqueous
sulphuric acid solution and thus causes difficulties in the clarification of
the liquors (Kime, 2017). This may further lead to disturbances in the
steps of solvent extraction and electrowinning (Mapeta, 2013, pp.
31–64; Nambia, 2015, pp. 40–56; Phetla & Muzenda, 2010).
Despite the fact that the DRC has been a major hub for Cu–Co
production for several years, too little organized information is
available in the literature on the past and present status of the mi-
neral beneficiation techniques used. Apart from a few pieces of data
published on mining exploration and metal extraction by mining
operators, a kind of blackout has existed for many years on the
technological advances made and how they have influenced the
Cu–Co processing industry (Lydall & Auchterlonie, 2011). This ar-
ticle will review advances in the beneficiation of Cu–Co minerals in
the DRC, including developments in the flotation of oxidised Cu–Co
ores after sulphidisation; methods for treating Cu–Co ores; reagent
suites, gravity separation techniques; and future methods for
meeting rising environmental standards and metal production from
low-grade ore complexities.
2. Geological setting
2.1. Geology of the Katanga Supergroup
The Congo Copperbelt is about 300 km long and 30 km wide and is
entirely located in the southwestern part of the DRC. It is one of the
richest metal-producing areas in the world (Kampunzu, Cailteux,
Kamona, Intiomale, & Melcher, 2009; Saad et al., 2013; Selley et al.,
2005; Theron, 2013). Its discovery dates back to the end of the 19th
century and mining operations began in 1911, after the establishment
of a rail link with South Africa (Verlinden & Cuypers, 1956). The
stratiform to stratabound Cu–Co deposits of the Katanga Copperbelt are
mainly hosted in the lower part of the Neoproterozoic Katanga Super-
group as can be seen in Fig. 1 (Roan Group, ~880–730 Ma) (François,
1973; Kampunzu et al., 2009; Muchez et al., 2008; Zientek et al., 2014).
M.L. Shengo, et al.
The Roan Group consists of a succession of alternating carbonate (do-
lostone) and detrital (shales, siltstones, sandstone and conglomerate)
rocks. These groups are overlain by the Nguba (635–~573 Ma) and
Kundelungu groups (~730–635 Ma). The lithology of these later groups
is predominantly characterised by the deposition of detrital rocks
(shales, siltstones, sandstone) and the carbonate rock (dolostone, stro-
matolite, oolitic dolostone) with Cu mineralization (Haest, Muchez,
Dewaele, Franey, & Tyler, 2007, Haest et al., 2009; Mambwe et al.,
2017a, b).
In the Roan Group, the hypogene stratiform Cu–Co sulphide mi-
neralization is early-to syn-diagenetic (Dewaele, Muchez, Vets,
Fernandez-Alonzo, & Tack, 2006; El Desouky, Muchez, & Cailteux,
2009; Muchez et al., 2008) and occurred around 800 Ma (Muchez,
Andre-Mayer, El Desouky, & Reisberg, 2015). It is followed by the late
diagenetic, syn-orogenic-to late orogenic Lufilian mineralization
(Cailteux, Kampunzu, Lerouge, Kaputo, & Milesi, 2005; Decree et al.,
2014; El Desouky et al., 2009; Kampunzu et al., 2009; Mambwe,
Muchez, Lavoie, Kipata, & Dewaele, 2019). The early stage of Cu–Co
mineralization precipitated during the rifting development at ~800 Ma
(Muchez et al., 2015). Carrollite (CuCo2S4), siegenite ((Ni,Co)3S4) and
linnaeite (Co2+Co3+ 2S4) are the most abundant Co ore minerals. The
post-orogenic mineralization is poorly investigated and controlled by
the faulting within the breccias. Moreover, Cu is associated with the Pb,
Zn, Ag, etc. (Chabu & Boulègue, 1992; Haest & Muchez, 2011; Mambwe
et al., 2017a). During this Neoproterozoic time, the Lufilian fold-and-
thrust belt underwent various stages of weathering and erosional epi-
sodes. As a result, the sulphide ore deposits are now oxidised, usually
down to a depth of ~100 m (Ngongo, 1975). It has been demonstrated
that the Katanga Cu–Co oxidised ore, among other oxidised deposits in
the area, is the result of a (Mio-)Pliocene weathering/oxidizing episode
(SIMS U–Pb age of the heterogenite is dated at 3.4 ± 0.8 Ma; Decrée
et al., 2010). This weathering process is economically significant be-
cause it strongly concentrated Co in the supergene ore, when compared
to the primary ore (64% Co for heterogenite versus 39% Co for car-
rollite). Many studies highlight that heterogenite was formed in oxi-
dizing conditions under the surface, while Cu migrated deeper down
and precipitated as malachite near the water table (De Putter, Mees,
Decrée, & Dewaele, 2010; Decrée et al., 2010). Heterogenite capsules
can therefore be considered a residual deposit, similar to iron-rich la-
terites.
2.2. Mineral resources
The Gécamines in the Congo Copperbelt is primarily organized into
three operational businesses, divided by ore type: the South Group
(Lubumbashi and Kipushi), the Centre Group (Likasi and Kambove),
and the West Group (Kolwezi). This organisation is used in this work to
describe the different mineralization of the Congo Copperbelt.
- The Cu–Zn ores extracted from the Kipushi mine have average
grades of 2–4% and 8–13%, of Cu–Zn, with essentially dolomitic
gangue. The ores contain, in varying proportions, the following
minerals: chalcopyrite CuFeS2 (35.5% Cu), bornite Cu5FeS4 (63.3%
Cu), blende ZnS, galena PbS, pyrite FeS2, renierite Cu3(Zn, Fe, Ge)
(S, As)4, briartite Cu5(Zn, Fe)GeS4, gallite CuGaS2, enargite
3Cu2S.As2S5 (48.3% Cu), chalcocite, covellite, and sometimes
complex copper and iron minerals associated with arsenic and an-
timony, such as tetrahedrite 3Cu2S.Sb2S3 (46.7% Cu), more gen-
erally expressed as sulfoantimonide 5Cu2S.2(Cu, Fe, Zn)S.2Sb2S3
(GCM/Géo, 1981). In many sulphide ores, small quantities of mo-
lybdenite (MoS2; generally less than 0.08%), silver (Ag) and gold
(Au) at variable levels, and rhenium (Re) associated with mo-
lybdenite are present. There are also complex Cu˗Pb˗Zn and Cu–Ni
sulphide ores, wherein the ratio of Cu to other useful metals is much
lower than 1. These minerals are usually accompanied by appreci-
able quantities of precious metals: Ag, Au and sometimes platinoids.
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Journal of Sustainable Mining 18 (2019) 226–246
- Unlike the Kipushi deposit, the minerals of the central and western
groups of the Gécamines are cupocobaltiferous. They are of the se-
dimentary type and constituted of dolomitic schists from the series
of mines in the Katanga system (GCM/Géo, 1981). They have
average grades of 2–4% Cu and 0–1% Co. There are generally three
categories of minerals:
a) Oxidised ores in the superficial and altered part (within the first
100 m from the surface), which may be either dolomitic or si-
liceous gangue, depending on the degree of weathering. The
main valuable minerals are malachite and chrysocolla for Cu and
heterogenite for Co. These minerals are disseminated in the
gangue and occur in fractures;
b) Mixed ores in the transition zone, which consists of oxidised and
sulphide minerals. The gangue is generally dolomitic;
c) The sulphide ores located at depth and made up of chalcopyrite
and bornite as Cu minerals, and carollite as a Co mineral. These
minerals also occur as fine grains disseminated in the dolomitic
gangue.
It is important to mention that traces of nickel, manganese, and iron
are sometimes found in these minerals.
3. Beneficiation techniques
Beneficiation processes for Cu–Co ores in the DRC usually include
either a complex four-stage flotation, or gravity separation, or both.
3.1. Gravity separation
Gravity separation is the most well proven and accepted technique
for concentrating minerals and has been used as a primary form of
mineral concentration for centuries. Due to its high efficiency and low
cost, gravity separation is often the first choice in any flowsheet de-
velopment program and often features in any flowsheet where there is
sufficient differences between the specific gravity of the valuable and
gangue minerals (Ancia, Frenay, Dandois & Piette, 1997). Despite the
advent of flotation, gravimetric concentration techniques are still used,
and are effective when applied over a narrow range of particle sizes.
Moreover, the need to adapt to new mining constraints, particularly the
mineralogical complexity and low-grade of ores requiring further lib-
eration of particles to dimensions less than 50 μm, and the environ-
mental constraints are factors encouraging the choice of gravity se-
paration methods during the processing of ores. Gravity concentration
methods use the combined effect of mass, volume, and the shape of
particles to separate different mineral components in a static or moving
liquid medium.
In the past, various studies were carried out by Gécamines (UMHK)
regarding beneficiation by the gravity separation of different Cu–Co
ores. The gravity concentrator of Panda was built and commissioned in
1919 by Wheeler from the Anaconda Cu mine (Montana, USA)
(Verlinden & Cuypers, 1956). The gravity separation circuit comprised
trommels, various screens, Hancock jigs, and Wilfley shaking tables
(Verlinden & Cuypers, 1956). Between 1921 and 1926, it enabled the
upgrading of Cu grades from 8.5–9.5% to 24–27%, with recoveries of
approximately 50–54%. Washeries were later built at different con-
centrators for the beneficiation of different Cu–Co ores; including
Ruashi (1926), Luisha (1926–1930 and 1939–1945), Kambove and
Shangolowe (1937–1943), Mutoshi (1950), and Kamoto (1942). In
general, the handling capacity was between 30 and 80 t/h and the
concentrates grade in copper of approximately 24–30%, with recoveries
of approximately 70–75% (Verlinden & Cuypers, 1956).
At present, in the Katangan Cu–Co industry, the use of gravity se-
paration is mostly confined to the pre-concentration stage where its
purpose is either to remove from the circuit waste streams when they
are sufficiently depleted or sometimes to extract rich concentrates with
subsequent treatment of the discharges. The gravity separation
M.L. Shengo, et al.
techniques commonly used in the beneficiation of Cu–Co ores in
Katanga include spiral concentration, table concentration, and heavy
media separation.
3.1.1. Heavy media separation (HMS)
The Heavy Medium Separation (HMS) or Dense Medium Separation
(DMS) mineral beneficiation technique is simple and uses only one fi-
nely pulverized solid as the reagent. In Katanga, a number of HMS
plants have been installed and are currently being used to upgrade
Cu–Co ores prior to their main processing stage, which may be by
milling, leaching, or flotation. The reason for using HMS can be ex-
plained by the fact that the major gangue materials of Cu–Co ores are
often quartz (d = 2.65), talc (d = 2.75), dolomite (d = 2.85), or limo-
nite (d = 2.7–4.3); which are relatively light compared to Cu–Co mi-
nerals (the density of the latter generally varies between 3.6 and 4.1).
HMS is therefore used upfront to reject large quantities of gangue be-
fore downstream operations. This results in reduced time, energy, and
costs associated with processes such as milling, leaching, and flotation
(Creswell, 2001).
HMS involves treating crushed and screened ore, which is fed as
pulp in a pseudo-liquid medium of defined density. The specific density
of the media slurry is maintained so as to allow the low-density gangue
material to float and the high-density desired minerals to sink. The most
common medium used for base metal ores is granular ferrosilicon
(Fe–Si, d = 6.7–7.0). The pseudo-liquid medium should be hard, stable
and unlikely to slime, as this would affect the medium viscosity. The
density of the medium is controlled by varying the concentration of
solids in the water (Woollacott & Eric, 1994). It should be noted that
density and stability appear to be two opposing concepts for which a
compromise must be made for optimal separation performance. Fe–Si
alloys require a minimum of 82% Fe for HMS purposes. A higher Fe
content will cause corrosion of the alloy and a lower Fe content will
reduce its density and magnetic susceptibility. The medium is also
manufactured in a range of shapes and size distributions depending on
its applications. The biggest portion of the operating cost of the HMS
process comes from the recovery and cleaning of the medium that
leaves the separator with sink and float products. Losses usually occur
from adhesion to the ore particles after draining and washing, and by
the medium remaining in the final effluent after the medium recovery
process (Napier-Munn et al., 1995). Medium reclamation circuits are
therefore included as part of the HMS procedure so that the solid
component can be recycled from the concentrate and waste products
(Burt, 1984; Woollacott & Eric, 1994).
Separation is accelerated using a dense medium cyclone (DMC) to
form two products: overflow (tailings) and underflow (concentrate).
HMS is mostly applied when the density difference is of a coarse par-
ticle size (typically between 0.5 and 40 mm), as the efficiency of the
separation decreases with size due to the slower settling rate of the
particles (Wills & Napier-Munn, 2006). Feeds to the cyclones are nor-
mally deslimed at approximately 0.5 mm to avoid contamination of the
medium and to minimise medium consumption (Dunglison, 1999). This
is the smallest particle size generally acceptable for producing efficient
separation (Burt, 1984). Particles less than 0.5 mm are also more sen-
sitive to changes in the medium rheology, and clay material con-
tamination within a cyclone contributes to an increased effect of the
medium; both these factors contribute to reduced separation efficiency
(Davis & Napier-Munn, 1987; He & Laskowski, 1994). The plant may
include a battery of spirals to process the fine particles.
Fig. 2 shows a typical HMS flowsheet designed and commissioned
by Gécamines for the processing of Cu–Co ores. The Kamfundwa HMS
plant has been set up with installed capacity for the treatment of 6000
tonnes per day of ROM ore feed (2.5% Cu and 0.2–0.3% Co) to produce
about 375 tonnes per day of Cu–Co rich concentrate (about 10–15% Cu
and 1.5–5% Co). The main valuable mineral is malachite
(d = 3.6–4.05) and the gangue is constituted of quartz (d = 2.65), do-
lomite (d = 2.85), calcite (d = 2.71), limonite (d = 2.71), and talc
229
Journal of Sustainable Mining 18 (2019) 226–246
(d = 2.71). The Fe–Si medium used has a d100 of about 150 μm. The
concentrate produced by the HMS plant is treated by hydrometallurgy
at Gécamines's Shituru plant, for conversion into Cu cathodes and
granulated Co. Average recovery of about 65.63% is attained for Cu,
while only marginal recovery is obtained for Co in view of its low
content in the ore treated. The tailings from HMS operations yield ap-
proximately 2–3% Cu and are stockpiled for further treatment in the
future using other techniques.
The HMS plant has three sections, namely the crushing-washing
section, the spiral section, and the DMC section. In the first section, the
ROM is crushed using a jaw crusher and a cone crusher, in a closed
circuit with a washer-scrubber and a double deck screen. The compo-
sition of Kamfundwa mine ore is given in Table 1.
The intermediate fraction (−19 mm + 1 mm) is fed to the DMC
section, while the fine fraction (−1 mm) is fed to the spiral section. The
intermediate fraction is further washed using a powerful water jet to re-
move any particles smaller than 1 mm. The fine fraction collected in low-
density pulp is also sent to the spiral section. Before cycloning the ore, it is
directed to the “mixer box” (Fig. 3) which also receives the medium.
The shape of the mixer is such that the ore and the medium mix
intimately before cycloning. In the mixer, the ore is admitted by gravity
and the medium by injection under pressure in two directions; one
parallel and the other transverse to the fall of the ore. The transverse
current carries the ore to the mixing zone while the parallel current
ensures the homogenization of the mixture due to the turbulence am-
plified by the suction of the cyclone pump. The residence time in the
mixer is reduced in order to limit the settling phenomena, which is
likely to occur given the specific masses of the suspended solids. In the
DMC section, the intermediate fraction undergoes cycloning to yield a
Cu–Co concentrate (under flow) and the tailings (overflow).
In order to recover the medium, both the DMC concentrate and the
tailings are passed successively and separately onto a static screen and
vibrating screen with a mesh size of 0.8 mm, where more than 90% of
the separating medium in the products is recovered and pumped back
through a sump into the separating vessel. The circuit for the dense
medium is given in Fig. 4.
The static screen is slightly inclined in order to facilitate the flow of
products to the vibrating screen. On the static screen, the products are
freed by draining a considerable part of Fe–Si that returns by gravity to
the medium tank via a collector provided at their lower parts. The
medium collected from the vibrating screen is diluted due to the water
washing spray. The diluted medium is freed from water, mud, and
adhered fines, purified and densified before it is recycled to the medium
tank. The purification of the diluted medium is done with the help of a
low-intensity magnetic separator drum with permanent magnets that
retain the ferromagnetic Fe–Si, which is then recovered from its surface
by scraping and then returned to the medium tank via a demagnetizing
coil. The clean medium is then thickened to the required density
(d = 2.3–2.65, 35% solid) using a densifier. The non-magnetic fine
particles are carried away by the water passing through the magnetic
separator towards the effluent tank.
In Katanga, HMS is also used at the Kalukuluku open pit to pre-
concentrate the talcaeous, clayey and rich in dolomite ores. The con-
centrate produced by the HMS plant is treated in CHEMAF's processing
plant at the Usoke site (in Lubumbashi), for conversion into Cu cath-
odes and Co product (Mthembu-Salter, 2011; Shengo, Kitungwa, Mutiti,
& Mulumba, 2017). The CHEMAF's Kanshinshi gravity concentrator
(Fig. 5) uses HMS and spiral concentration to preconcentrate 0.15–2%
Cu ROM to 6% Cu, maximum 1% Co concentrate. The concentrate
produced is also treated in CHEMAF's processing plant at the Usoke site.
Anvil Mining also implemented HMS until 2004 for the processing
of the mixed Cu–Co ores from the Dikulushi mine (Mawson West Ltd,
2011, 2015, pp. 1–56). Boss Mining, a subsidiary of Eurasian Resources
Group (ERG), also processes oxidised Cu–Co ores from Mukondo mine
(Table 2) located near the mining city of Kambove (Haut-Katanga)
using HMS.
M.L. Shengo, et al. Journal of Sustainable Mining 18 (2019) 226–246

Fig. 2. Kamfundwa gravity concentrator simplified flow sheet (After Shengo, 2008).

Table 1 oxidised Cu ores (~2.85% Cu) from Tshifufia, Tshifufiamashi, and

Chemical composition of a copper ore from the Kamfundwa deposit. Kinsevere Hill mines (Loshi, 2012, pp. 21–44). The HMS plant was
Element or compound Proportion (%) Element or compound Proportion (%)
designed with an annual handling capacity of 100, 000 tonnes (Booth,
Cameron, Fahey, & Lawlord, 2010).
Total Cu 2.10 Soluble MgO 0.004 Tiger Resources Limited also implemented HMS and used a spiral
Oxidised Cu 2.07 SiO2 65.17 concentration plant during the first stage (2011–2014) of the Kipoi Cu
Total Co 0.26 Al2O3 2.58
Total CaO 2.81 Fe 1.04
project (located 75 km from Lubumbashi) (Black, Zammit, Dorling, &
Soluble CaO 0.14 Mn 0.20 Readett, 2011; Chadwick, 2013; Warwick, 2014; Yager, 2012, 2013,
Total MgO 0.004 Ni 0.001 2016). The plant was designed to process 900,000 tonnes per year of
high-grade oxidised Cu ores (3.25–7% Cu), and over the three years, it
produced approximately 120,000 tonnes of ~25% Cu concentrates
(Black et al., 2011; Warwick, 2014; Yager, 2012, 2013, 2016). It was
decommissioned in 2014.

3.1.2. Spiral and shaking table concentrations

In general, the separation efficiency of the gravity concentration
methods using spirals and shaking tables is better suited for coarse
particles than fine particles because the gravity force is more effective
on coarse particles. The purpose of the separation is to get the max-
imum grade of metallic ore with minimal possible mass recovery. The
concentration is often carried out on deslimed ores (−38 μm). The final
concentrate grades are approximately 6% Cu with recoveries of about
32%.
The examples above show that the use of gravity separation prior to
Fig. 3. HMS mixing box.
leaching or flotation is gaining momentum in the Katanga Cu–Co in-
dustry. This trend is due to declining feed grades and the increasing
complexity of ores, coupled with increasing metal demand. There is,
therefore, a constant need to reject a large part of the gangue materials
before subjecting the ores to actual processes. This will increase mineral
processing plant capacities and help optimise performance. Gravity
separation techniques are also increasingly considered for reprocessing
the large Cu–Co tailings stockpiled at a number of plants in Katanga
(Chadwick, 2008; Lutandula & Maloba, 2013; Mbuya, Kime, &
Tshimombo, 2017).

3.2. Froth flotation

Fig. 4. Dense medium circuit.
Kakanda Concentrator (KDC) which is also owned and operated by
Boss Mining, uses HMS to produce ~14% Co concentrates with re-
coveries of about 50%. HMS was also used at the Kinsevere plant
(Fig. 6), operated by the Minerals and Metals Group (MMG), to treat
Froth flotation is one of the most commonly used concentration
steps in mineral processing and the Cu–Co industry is no exception.
After the valuable minerals have been liberated from the waste rock,
froth flotation is used to selectively concentrate and separate the va-
luable ore from the gangue material. In the Cu–Co processing industry
of the DRC, flotation is generally used as a precursor to

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M.L. Shengo, et al. Journal of Sustainable Mining 18 (2019) 226–246

Fig. 5. Kanshinshi gravity concentrator simplified flow sheet (After Shengo, 2008).

Table 2 H2O + n%H2O hygroscopic. The crystalline or cryptocrystalline char-

Chemical composition of copper-cobalt oxide ores from the acter of the heterogenite varieties can be easily evidenced by either X-
Mukondo deposit. ray diffraction or polarized light microscopy. In the latter case, the
Element or compound Proportion (%) distinction between the two varieties is established, respectively, due to
the presence or absence of reflection and anisotropy pleochroism and
Total Cu 2.44 on the intensity of the reflection power that is clearly higher for well-
Total Co 1.46
crystallised varieties. Consideration should also be given to the state of
Total CaO 2.18
Soluble CaO 0.14 the dissemination of the various minerals mentioned in the gangue.
MgO 6.92 This last factor is often responsible for a significant part of the diffi-
Fe2O3 1.14 culties encountered in flotation. The dissemination of minerals can af-
Al2O3 3.45 fect both the most abundant mineral, namely malachite, as well as
P2O5 0.15
SiO2 27.65
secondary minerals and in particular, Co hydrated oxides.

hydrometallurgical or pyrometallurgical treatment (Kugeria, Mwangi,
Wachira, & Njoroge, 2018). The beneficiation of oxidised Cu–Co ores
may present difficulties due to their relatively complex mineralization.
In these ores, several minerals frequently occur and they do not have
the same flotation properties. Cu minerals can be present as carbonates
(malachite, sometimes cobaltiferous), basic phosphates (pseudoma-
lachite), oxides (cuprite and tenorite), hydrated silicates (chrysocolla),
and native Cu with, possible, traces of secondary sulphides (chalcocite,
covellite, digenite or bornite). The mineralogy of Co is itself very
complex. It consists of hydrated oxides which may be either crystalline
(CoO·OH or Co2O3.H2O), or cryptocrystalline or amorphous. These
contain significant quantities of impurities; mainly Cu, but also bivalent
Co, Ni, Fe and Mn. Their formula is of the type (xCo2O3. yCoO.zCuO)
3.2.1. Zeta potentials of Cu–Co minerals
The solid-liquid (S-L) interface is the most important interface in
flotation. It is characterised by both the electrical and absorption phe-
nomena. The electrical phenomenon is characterised by the zeta po-
tential (ζ), which is an important parameter for the flotation and the
floatability of minerals. It defines the adsorption density of a collector
on the surface of a mineral. The knowledge of the zeta potential of the
minerals allows the prediction of the conditions needed to produce
acceptable grades and recoveries in each respective process. The zeta
potential is influenced by the pH (acid pH ζ > 0, basic pH ζ < 0; ζ = 0
corresponds to the pH of charge zero), the mineral, the substitution
element in the mineral, the ions determining the zeta potential, the
common ion, the activating ions, the concentration of the indifferent
electrolytes, the collectors, and the length of the carbon chain.

Fig. 6. MMG Kinsevere HMS plant flow sheet (After Booth et al., 2010).

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M.L. Shengo, et al. Journal of Sustainable Mining 18 (2019) 226–246

malachite, which is influenced by the pH. The major ions determining

the potential are OH− and H+. The concentration of Cu ions in the
solution does not affect the position of the isoelectric point of un-
conditioned malachite. For activated malachite, isoelectric points are
shifted backwards and the surface charges are alternated.

3.2.2. Reagent options

The reagent options for Cu–Co ores can be quite varied but generally
fall within one of the following broad groups of reagents:

- Xanthates or alkyldithiocarbonates are sodium or potassium salts of

dithiocarbonic acid that are used as collectors in the flotation of
sulphide ores or oxide ores after sulphidisation. They have as a
general formula: ROCS2 M+ (R = alkyl; M+ = Na+, K+). Most often,
the xanthates are in the form of a fine and highly hygroscopic
powder. Their colours vary between bright yellow and dark orange.
Xanthates are very soluble in water where they form alkaline solu-
Fig. 7. Average zeta potential of cobalt-bearing minerals as a function of pH. tions. This solubility depends on the length of the hydrocarbon
chain. The longer the chain, the less soluble they are.
- Thiophosphates (aryl- and alkyl-dithiophosphate) or aerofloats are
Adsorption is probably very important at the S-L interface. It depends
chemical compounds and anions with the general chemical formula
on the concentration of reactants, the length of the carbon chain, the
PS4 x O3x (x = 0, 1, 2, or 3) and related derivatives where organic
temperature, the chemical adsorption pH, and the presence of oxygen.
groups are attached to one or more O or S. They are generally used
Fig. 7 illustrates the average zeta potential of Co minerals as a function
as collectors in the flotation of sulphide ores or oxide ores after
of pH.
sulphidisation. Their stability is greater, especially in the pH range
As visible in Fig. 7, all the curves follow a similar trend. The iso-
from 4 to 12. In the flotation of the noble metals, short chain
electric point lies at neighbouring values for minerals of the stanierite
compounds are preferred. Their advantage resides in their applica-
type. It was found that the conditioning time needed to reach the
tion in the acid pH range. In addition to application in flotation,
electrokinetic equilibrium varied between one and 4 h for stanierite-
aliphatic dithiophosphates are used in the precipitation of cadmium
type minerals. The shortest conditioning times were observed for well-
from a hot concentrated phosphoric acid solution. Aromatic di-
crystallised Co oxide minerals. Furthermore, it was experimentally
thiophosphates are used preferentially for the flotation of lead mi-
observed that the addition of NaCl did not affect the zero charge point
nerals, often containing silver.
or the sign of the surface charge. For amorphous Co minerals, the zero
- Thiocarbamates are a family of organosulfur collectors. There are
charge point was not reached due to the electrical instability occurring
two isomeric forms of thiocarbamate esters: O-thiocarbamates,
at acidic pH. The addition of Cu2+ in the ore pulp may be sufficient for
ROC(=S)NR2, and S-thiocarbamates, RSC(=O)NR2. O-thiocarba-
the activation of this type of Co oxides.
mates can isomerise to S-thiocarbamates.
Fig. 8 presents the zeta potentials of malachite as a function of pH. It
- Potassium amyl xanthate ~350 g/t (PAX: min 92%, density:
is shown that unconditioned malachite has an overall positive surface
0.50 kg/L) is used as the primary collector of oxidised Cu–Co ores.
charge for pH values between 3 and 10.4. The isoelectric point of un-
- Potassium ethyl xanthate (PEX: min 95%, sulphates: max 3%) is
conditioned malachite is measured at approximately pH 10.4. The
used as the primary collector of sulphide Cu–Co ores.
crystalline structure of the mineral is of paramount importance in the
- Fatty acids (fatty acid: 93.5–94.5, rosin acid: 3.5–4%, unsaponifi-
identification of the potential determining ions. In the case of mala-
ables: max 2.5%) are used as secondary collectors for oxidised
chite, the structure is based on Cu2+, OH−, and CO32− bonds. The
Cu–Co ores.
isoelectric point coincides with the pH (10.4) for which the species
- A mixture (150 g/t) of gasoil (93–94%) and Rinkalore (6–7%) is also
CuOH+ and Cu(OH)42− are in equilibrium (Kanda, 2013). The oxy-
used as the secondary collector.
hydroxide complexes of Cu are related to the dissolution of the
- Sodium silicate also called water glass ~250 g/t (Na2O.xSiO2 with x:
2.1–2.2, Na2O: 30–32%, SiO2: 66%) is a well-known reagent which
is typically used as a dispersant of gangue minerals. It also has the
virtue of modifying the viscosity of the pulp.
- Sodium carbonate ~50 g/t (NaCO3: 97–98, NaCl: 0.5–1.6, Fe2O2:
0.002–0.005, H2O: 0.1%, insoluble: 0.1) is typically used as a pH
modifier.
- Sodium sulphydrate ~3500 g/t (NaSH: 70–72%, Na2S: max 2%,
Na2S2O5: 0.70–1.2%, Na2SO3: max 0.3%, Na2CO3: max 0.25%, Fe:
8–16 ppm, polysulphides: 0.5–0.9) is used for the surface sulphidi-
sation of oxidised Cu–Co ores.
- Sodium cyanide (NaCl: 96–98%, humidity: max 0.1%, NaOH: max
0.7%, Na2CO3: max 0.03%, S: max 3%, insoluble: max 0.01%) is
used as a depressant of blende in the flotation of copper-zinc-bearing
ores.
- Senfroth G41 (≈10 g/t) is used as a frothing agent for the flotation
of sulphides and oxides by sulphidisation.

3.2.3. Flotation of Cu–Co ores

3.2.3.1. Flotation of Cu–Co sulphide ores. The flotation of sulphide ores,
Fig. 8. Average zeta potential of malachite as a function of pH (Kanda, 2013). such as chalcopyrite and molybdenite ores, is a relatively easy

232
M.L. Shengo, et al.
operation when compared to the flotation of oxides, silicates and
complex salts (Bulatovic, 2007; Klimpel, Hansen, Leonard & Fee,
1991, pp. 1–30). However, while it may be easy to float
monometallic sulphide ores, even if the gangue consists of iron
sulphides such as pyrite (FeS2), marcasite (FeS2), and pyrrhotite
(Fe7S8), the selective flotation of complex sulphide ores may be
challenging. The most commonly used collectors for sulphide are
sulfhydryl collectors, particularly xanthates and dithiophosphates.
The latter are more selective, but more expensive and therefore, less
used in the mineral processing industry. Because pyrite is easy to float
with xanthates, other collector types are used when one desires to float
selectively a sulphide mineral with respect to the pyrite. Most
recommended collectors have critical pH values below 6 for the
flotation of pyrite (Wills & Napier-Munn, 2006). Thiocarbamate
collectors may also be used. They are selective and very useful for
selectively floating activated Cu–Zn sulphides from a pyrite gangue.
The flotation of Cu sulphide ores is well conducted when the feed is
finely ground to 70–80% passing 75 μm, which corresponds to the size
comprised between fine and coarse particle and this enables achieving
larger recovery rates (Feng & Aldrich, 1999). In the case of porphyry Cu
sulphide ores, in which pyrite is less active, a feed flotation grind size of
35% passing 75 μm is recommended. Flotation becomes inefficient for
secondary Cu sulphides such as bornite and covellite due to the
activation of pyrite by Cu ions released in the aqueous phase during
the grinding stage. This may also result in reagent losses due to the
partial oxidation of sulphide minerals. In this case, a more complex
reagent suite is recommended.
3.2.3.1.1. Depression of sphalerite, pyrite and flotation of Cu
sulphides. In the selective flotation of complex sulphides, the first step
is often the flotation of Cu sulphides (chalcopyrite, chalcocite, etc.) and
lead (galena) with xanthates at a slightly basic pH with the depression
of sphalerite and pyrite by adding cyanide ions (Wang & Forssberg,
1996). Compared to other sulphides (chalcopyrite, chalcocite, covellite,
marcasite, galena), pyrite is the mineral that is easily depressed at a
lower pH by the addition of cyanide ions to the pulp. Moreover, its
depression is substantially improved when the ore undergoes oxidation
beforehand. In the literature, well-known mechanisms of the depression
of pyrite using cyanide include (Wang & Forssberg, 1996):
- reactions of cyanide ions with metallic xanthates to form more
stable cyanide-metal complexes;
- the preferential adsorption of cyanides on the surface of minerals
with the formation of cyano-metal complexes which prevent the
adsorption of xanthates on the surface of the minerals;
- in the particular case of pyrite from pH 6.5, ferric ferrocyanide
Fe4[Fe(CN)6]3 is formed on the surface of the mineral which offsets
the positive charged sites of the surface and, therefore, the zeta
potential becomes negative and the xanthates are then repelled.
Depression of sphalerite by cyanide ions is most effective when used
in an admixture with Zn2+ ions which are often supplied as a zinc
sulphate solution. Zn2+ ions are involved in the displacement of the
equilibrium of the activation of sphalerite by heavy metals. Zn2+ ions
are added at concentrations at least 1000 times higher than those of
other heavy metals accidently present in the solution and are capable of
activating the surface of ZnS.
3.2.3.1.2. Activation and flotation of sphalerite. Sphalerite does not
float very well in the presence of xanthates because zinc xanthates are
relatively soluble in water compared to the xanthates of other heavy
metals (Wills & Napier-Munn, 2006). There is an optimum flotation at
pH close to 3.5. Beyond this pH, there is no or very little flotation.
Flotation of sphalerite requires activation by Cu2+ ions (Wang &
Forssberg, 1989). Activation of sphalerite by Cu2+ ions can be
explained by the substitution of zinc atoms on the surface, or near
the surface, by Cu ions according to the following equation:
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Journal of Sustainable Mining 18 (2019) 226–246
+
ZnS(s) + Cu 2(aq )
+
CuS(s) + Zn 2(aq ) (1)
Sphalerite is then recovered with a more stable film of Cu sulphide
(covellite) which floats easily. This, therefore, results in effective acti-
vation. Activation of sphalerite by Cu2+ ions is also accompanied by the
activation of iron sulphides when flotation is done at neutral or slightly
basic pH (Boulton, Fornasiero, & Ralson, 2001; Shen, Fornasiero, &
Ralston, 1998; Wang, Forssberg, & Bolin, 1989). Iron sulphides can be
depressed during conditioning at strongly basic pH (pH 11). This leads
to the formation of ferric hydroxides on the surface of these minerals,
which inhibit Cu sulphate activation and collector adsorption (Boulton
et al., 2001). Other reagents may be used to prevent the flotation of iron
sulphides, these being: sodium sulfite (Shen, Fornasiero, & Ralston,
2001), thioglycolic acids (Chmielewski & Wheelock, 1991), diethylene
triamine and gaseous oxygen (Shen et al., 1998). Several varieties of
polymers such as polyacrylamides also produce a good depression of
iron sulphides and non-sulphurous minerals in the gangue (Bogusz,
Brienne, Butler, Rao, & Finch, 1997; Nagaraj, 1997; Xu & Aplan, 1994).
The use of specific Cu collectors such as thionocarbamate and thiourea
has a positive impact on the flotation of sphalerite and a negative one
on that of iron sulphides (Boulton et al., 2001; Shen et al., 1998).
The Ancient Concentrator in Kipushi (ACK) is a typical plant de-
signed for the processing of polymetallic sulphide ores extracted from
the Kipushi mine (Fig. 9). It is situated within an old Gécamines’ facility
in Kipushi, a small town 30 km from Lubumbashi.
Processing of the Kipushi Cu–Zn sulphide ore started in 1935.
Initially, the plant treated about 20,000 tonnes of ore per month using a
single flotation circuit with conventional reagents such as xanthates
and pine oil. Over the period 1937 to 1940, the concentrator was ex-
tended to allow the differential flotation of Cu–Zn. A further extension
was completed in 1950 for a capacity of 60,000 tonnes of ore per
month. In 1980, the concentrator had reached a capacity of about
120,000 tonnes per month. In 1993, due to severe economic instability
that affected the country, the concentrator ceased to operate on a
regular basis. The Cu–Zn ore treated analyses 2–4% Cu and 8–13% Zn.
The main Cu minerals are chalcopyrite (CuFeS2), bornite (Cu5FeS4),
and covellite (CuS) (Habashi, 1997; Kelly, Bennett, & Smith, 2012, pp.
1–2; Nujoma, 2009). Zn is mainly in the form of sphalerite (ZnS). The
ore also contains minor amounts of galena (PbS), pyrite (FeS2), the
renierite (Cu3(Zn,Fe,Ge)S,As)4), briartite (Cu5,(Zn,Fe)GeS4), and gallite
(CuGaS2). The main gangue material is dolomite. The differential flo-
tation of Cu–Zn was carried out in two stages as follows:
- Cu flotation using xanthates as collectors, after depression of
Fig. 9. ACK simplified flow sheet (modified from Kaniki & Ntumba, 2019).
M.L. Shengo, et al.
Fig. 10. KCC flowsheet (modified from Wimberley et al., 2011, pp. 87–111).
sphalerite and pyrite with a solution of sodium cyanide (NaCN) and
zinc sulphate (ZnSO4). The frothing agent used was MIBC (methyl
isobutyl carbinol ((CH3)2CH–CH2–CHOH–CH3) and the pH was
maintained between 6 and 9.5 with lime;
- Zn flotation was performed using xanthates or dithiophosphates,
commonly called aerofloats as collectors of sphalerite after activa-
tion by Cu sulphate (CuSO4). The frothing agent used is pine oil.
Lime was utilised both as a pH regulator and as depressor of pyrite
(Bulatovic, 2007; Kaniki & Tumba, 2019). The pH was kept between
10 and 11 with the lime in order to limit the flotation of the pyrite.
Sphalerite was recovered in a concentrate analysing 49–54% Zn and
3–6% Cu.
Flotation of Cu sulphide ores was also done at the Kamoto Copper
Company (KCC) (Fig. 10), which is owned by Gécamines in partnership
with Glencore International. Sodium isopropylxanthate (SIPX) and
Sinfroth G41 were used as collector and frother, respectively
(Wimberley et al., 2011, pp. 87–111).
With the depletion of the superficial oxidised ores, mining is in-
creasingly taking place at depth and most companies are considering
treating sulphide ores. The Kamoa deposit is a typical example that
contains sulphide ores. In 2013, it was ranked as the world's largest
known undeveloped high-grade sulphide Cu, with Cu occurring mainly
as bornite, chalcopyrite, and chalcocite (Nkuna, Naidoo, & Amos,
2016). KDC (Fig. 11), owned by ERG, periodically processes Cu sul-
phide ores from the South Kabolela deposit (Ilunga, 2012, pp. 16–43).
Flotation is conducted using sodium isobutylxanthate (SIBX) and
normal potassium xanthate as the primary and secondary collectors,
respectively.
3.2.3.2. Flotation of oxidised Cu–Co ores. In general, base-metal oxide
minerals such as smithsonite (ZnCO3), cerusite (PbCO3), cuprite
(Cu2O), tenorite (CuO), and azurite (Cu3(CO3)2(OH)2) are not
effectively amenable to flotation with the traditional collectors used
for sulphide minerals. This can be explained by the following reasons:
- they are more hydrophilic because of the predominantly un-
saturated ionic or atomic bonds that react with the polar molecules
of the water (Drzymala, 2007; Lee, Nagaraj, & Coe, 1998). The
hydration of oxide ores releases polyvalent metal ions in the water
of the pulp. This may lead to the exaggerated consumption of the
flotation reagents (Bessière, El Housni, & Prédali, 1991; Davidson,
2009);
- their gangue materials have a structure similar to that of recoverable
minerals which makes the mode of action of the flotation reagents
less selective;
- they have an increased tendency to produce fines and gangue ultra
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Journal of Sustainable Mining 18 (2019) 226–246
fines during fragmentation, which reduces metallurgical perfor-
mance when concentrated by flotation.
Although hydrometallurgy based on solvent extraction and elec-
trowinning (SX/EW) is the most used process for treating oxidised
Cu–Co ores in the Katanga Cu–Co industry (Chadwick, 2008; Kordosky,
2007; Mulaba-Bafubiandi & Bell, 2005), the preferred concentration
technique for treating malachite and heterogenite remains surface
sulphidisation followed by actual flotation (Clark et al., 2000; Countois
et al., 2003; Kongolo et al., 2003; Ziyadanogullari & Aydin, 2005).
Flotation is mainly done using xanthates or fatty acids. Based on the
Katanga mining statics of 2011 (Umpula & Amisi, 2012, pp. 14–29), the
beneficiation of Cu–Co ores by flotation is performed at more than 38
mining companies. In 2011, approximately 37,328 and 193,011 tonnes
of Cu and Cu–Co concentrates, respectively, were produced by flotation
(Umpula & Amisi, 2012, pp. 14–29). The choice of specific reagents is
dictated by the mineralogical characterisation of the ore, the costs of
the reagents, and the objectives set by the concentrator in terms of the
desired grade and recovery (Kabuya, 2015, pp. 31–51; Kanda, 2013;
Katwika, 2012, pp. 4–16; Shengo, 2013; Shengo, Gaydardzhiev, &
Kalenga, 2014).
3.2.3.3. Flotation of Cu oxidised ores with xanthates after sulphidisation
3.2.3.3.1. Xanthate collector adsorption mechanisms. There are
primarily two possible mechanisms by which sulfhydryl collectors
adsorb on mineral surfaces. These include physical adsorption and
chemisorption at metal ion sites on a surface (Bulatovic, 2007). The
former consists of physically fixing a collector on the surface of a
mineral, which results in the electrostatic attraction between the
effective ions of this collector and the activated mineral surface. For
the latter, the adsorption of the collector is based on a chemical
mechanism. However, several interpretations arise from the role of
oxygen on adsorption and the role of metal xanthates. Electrochemical
investigations of collectors’ adsorption were conducted by a number of
researchers with an interest in the anodic oxidation of ethyl xanthate to
diethyl dixanthogen on platinum, gold, copper, and galena electrodes.
One concluded that mineral flotation with xanthate collectors proceeds
through the electro-oxidation of xanthate, with oxygen being required
to provide a cathodic process. Fig. 12 shows that the stability of Cu2S,
CuX, Cu(OH)2, and X2 species in the flotation of chalcocite strongly
depends on the pH and redox potential.
Optimum recovery was obtained at pH 6 and a potential of
+0.45 mV. Under these conditions, Cu xanthate was the stable species
on the surface of chalcocite. With an additional increase in pH, Cu(OH)2
increases and therefore, the recovery dropped. The recovery curve be-
haves as if it is reluctant to enter the stability zone of Cu(OH)2 and X2.
This indicates that flotation ceased as soon as the surface of the
M.L. Shengo, et al.
Fig. 11. KDC flowsheet (modified from Kilumba, 2010, pp. 17–30).
Fig. 12. Effect of pH on the stability of Cu2S, CuX, Cu(OH)2, and X2 species in
the flotation of chalcocite.
chalcocite was covered with hydroxide. This also indicates that dix-
anthogen was not responsible for the flotation of chalcocite. It is be-
lieved that xanthate was chemisorbed on the chalcocite mineral surface
through the formation of chemisorbed monolayers of Cu xanthate CuX,
their precipitation in aqueous solution, and their adsorption on mineral
surfaces.
Rao and Finch (2003) reported that flotation without prior sulphi-
disation of base metal oxides (Ni, Cu, Zn, and Fe) with long carbon
xanthates strongly depends on the pH of the pulp. This flotation is
carried out according to an electrostatic mechanism because the re-
covery efficiency is related to the isoelectric point of each oxide.
3.2.3.3.2. Sulphidisation mechanism. Sulphidisation is the
superficial treatment of oxide minerals with an aqueous solution of
sulphide or sulphydrate ions in order to form sulphide surfaces on base-
metal oxide minerals that are then amenable to the conventional
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Journal of Sustainable Mining 18 (2019) 226–246
sulphide flotation practice (Davidson, 2009). This technique has been
applied to the flotation of a range of base-metal oxide minerals, most
notably malachite and heterogenite (Bastin, Frenay, & Philippart, 2003;
Mwema & Mpoyo, 2001; Shungu, Vermaut, & Ferron, 1988).
Sulphidisation can also be done using thermal methods. This will be
further elaborated on in this review under the section on the flotation of
Cu–Co silicate ores. In their works, Bustamante and Castro (1975), and
Leppinen and Mielczarski (1986) stated that sulphidisation can be
explained by ion exchange reactions. In turn, Chander (2003) and
Wright and Prosser (1965) suggested that sulphidisation results in
sulphides precipitation onto the surfaces of oxidised minerals. The
sulphidisation of an oxidised mineral is a two-step reactional process
(Davidson, 2009; Zhou & Chander, 1993). The first step, characterised
by fast kinetics, leads to the formation of a primary sulphidisation layer
(MS) via direct mineral-sulphidising agent contact. The second step is
characterised by slow kinetics that is imposed by the rate of the
diffusion of metal ions of the mineral through the primary
sulphidisation layer. This leads to the formation of a metal-sulphide
deficient (MxS). Sulphidising agents do not impart hydrophobicity to
the surface of oxidised minerals. In fact, it is the action of the collectors
that makes the surfaces hydrophobic. In practice, dedicated
sulphidising agents such as sodium hydrosulphide, sodium sulphide,
and hydrogen sulphide are used to create sulphide films on the surfaces
of recoverable oxide minerals to allow the fixation of sulphydric acid. In
aqueous solutions, the sulphidisation of base-metal oxide minerals
proceeds according to the following reaction:
MO(s) + S2(aq) + 2H+(aq) MS(s) + H2 O (2)
The formation of the sulphide films can be described by the fol-
lowing reactions:
NaHS(s) + H2 O NaOH (aq) + H2 S(aq) (3)
NaOH (aq) Na +(aq) + OH(aq) (4)
H2 S(aq) = H+(aq) + HS(aq) , k1 = 1.02 × 10 7 (pk1 = 6.99) (5)
M.L. Shengo, et al.
Fig. 13. Chemical species dissociated from NaHS (modified from Garrels &
Naeser, 1958).
HS(aq) = H+(aq) + S2(aq) , k2 = 1.2 × 10 13 (pk 2 = 12.92) (6)
Since the dissociation constants of equations (5) and (6) are very
small, and that of equation (4) is very high, the concentration of OH−
increases faster than that of H+ in the pulp. Suffice to say that the
nature of the active species present in soluble sulphide salt solutions
depends strongly on the pH. Below pH 6, hydrogen sulphide is domi-
nant, while above pH 11 sulphide ion is dominant. For pH ~8.5 and 10,
hydrosulphide ion is dominant and thus considered the active site
during sulphidisation (Crozier, 1992; Garrels & Naeser, 1958). Con-
centrations of HS− and S2−in the pulp depend on the dosage of the
sulphidising agent used, as well as on secondary reactions that can
consume the sulphidising agent.
Fig. 13 shows the dissociated chemical species as a function of pH.
The following reaction will take place within the site of Cu during
sulphidisation by the sulphide ions present in the pulp:
Cu2 + + S2 CuS (7)
The presence of oxygen in the pulp causes the oxidation of the HS−
and S2− as well as that of the surface film formed on the surface of the
oxidised ores. Studies by Newell and Bradshaw (2007) and Clark et al.
(2000) indicated that removing the dissolved oxygen from the sulphi-
disation conditioning stages would significantly reduce the consump-
tion of sulphidising reagent by up to 70%. Possible reactions with
oxygen are as follows:
2NaHS +2O2 Na2SO4 + H2 S (8)
CuS + 2O2 CuSO4 (9)
CuSO4 + H2 S CuS + H2 SO4 (10)
2NaHS + 4O2 Na2SO4 + H2 SO4 (11)
The concentration of the sulphidising agent decreases as it is in-
troduced into the pulp through the following reactions:
- the formation of sulphide film onto oxide mineral grains;
- the oxidation of the sulphide ions by oxygen and the formation of
colloidal Cu sulphide and a range of sulfoxy compounds due to the
reaction between the cu2+ released during the sulphidisation and
HS− and S2−.
The adsorption of a collector primarily depends on the collector
concentration in the pulp, but also on the surface state of the mineral. A
direct reaction between sulphide ions and dissolved oxygen is, rela-
tively, very slow in the absence of a catalyst. The surface of the minerals
plays a catalytic role in the oxidation reaction of sulphide species to
sulphates and thiosulphates (Crozier, 1992). The consumption of excess
236
Journal of Sustainable Mining 18 (2019) 226–246
sulphide ion will be dependent on the presence of a mineral with cat-
alyst activity and the availability of dissolved oxygen. Sulphidisation is
often conducted in neutral or alkaline medium to avoid the decantation
of the sulphidising agent. At very high pH (pH > 11), colloidal Cu
sulphide is formed, which is detrimental to flotation. It also affects the
stability of sulphide films formed and therefore decreases the efficiency
of sulphidisation. It is for this reason that sodium sulphide is not widely
used as a sulphidising agent because it makes the pulp very alkaline.
Optimal sulphidisation of oxidised Cu–Co ores is achieved in the pH
range of 8.5–9.5. The pH is thus the primary flotation regulator as it
affects the collection, by allowing competition amongst sulphide ions
and by acting on the mineral surface properties.
Decreasing the excess of sulphide ions by using the playing on
oxidation is not always advantageous. In fact, oxidised species such as
thiosulphates strongly depress the flotation of certain minerals, such as
chrysocolla, by destroying the sulphide layer formed. There is also a
risk of oxidizing the freshly formed sulphide film (Castro, Soto,
Goldfarb, & Laskowski, 1974). In industrial practices, the sulphidisation
process is closely monitored during conditioning. In fact, any excess in
sulphidisation will degrade the recovery of useful metals (Bila, 2006,
pp. 13–35; Shengo, 2013; Zhou & Chander, 1993). Sulphidisation is
monitored using the Controlled Potential Sulphidisation (CPS) tech-
nique. This technique relies on the use specific sulphide ionic electrodes
that control the potential of reactions (Malghan, 1986). This informa-
tion is crucial as good recovery is achieved at a fixed sulphide ion
electrode potential (Es) with a number of oxide ores (Jones, 1990;
Jones & Woodcock, 1978a, b, 1979a, b). Knowledge of the potential
will help the operator to respond adequately to a change in S2− con-
centrations. Therefore, the CPS electrode should be robust enough to
withstand the conditions of use in pulps and it should not interfere with
other species (Malghan, 1986). The CPS technique has been successfully
applied in Katanga at the Dikushi concentrator (operated by Anvil
mining) in the control of the sulphidising flotation of oxidised Cu–Co
ores based on the flowsheet depicted in Fig. 14 (Brabham,
Winterbottom, Abbott, & De Klerk, 2014; Mawson West Ltd, 2011,
2015, pp. 1–56).
The CPS technique has also been used since 2014 at the Kapulo
copper project in the flotation of the Safari deposit ores located in Haut-
Katanga (Brabham et al., 2014; Warries et al., 2011, pp. 50–53). The
Kishiba Concentration at Sakania (Haut-Katanga) as well as at the KCC
at Kolwezi (Lualaba) also implemented this technique during the flo-
tation of copper ores.
Fig. 14. Dikulushi concentrator flowsheet.
M.L. Shengo, et al.
Fig. 15. Effects of the sulphidising agent type and dosage of the flotation of
oxidised copper-cobalt ore with xanthates (modified from Kongolo et al., 2003).
3.2.3.4. Flotation of well oxidised and carbonate Cu–Co ores after
sulphidisation. Malachite and heterogenite contained in the Cu–Co
oxidised ores of Katanga are generally sulphidised using sodium
sulphide (Na2S), ammonium sulphide (NH4)2S), or sodium
sulphydrate (NaSH) in order to make them suitable for collection
with sulphydryl-type collectors (Barbaro, Herrera Urbina, Cozza,
Fuerstenau, & Marabini, 1997).
Fig. 15a and b shows the results of the flotation of oxidised Cu–Co
ore using xanthate collectors, after the superficial activation of the
valuable minerals with different sulphidisation agents. It can be seen
that sulphidisation type and dosage significantly affect the flotation of
oxidised Cu–Co ores and therefore the recovery of Cu–Co. Unlike in the
case of cuprite and tenorite, the sulphidisation and flotation of mala-
chite using xanthates is an operation relatively easy (Drzymala, 2007;
Samsonova, Gutsalyuk, & Aitalieva, 1974). Sulphidisation of malachite
is carried out at a relatively constant sulphidising rate in the pH range
of 8–11 (Bulatovic, 2007). The optimum sulphidisation rate is generally
reached at about 60 °C, and takes place according to the following
chemical reaction:
CuCO3 . CU(OH)2 + HS CuS + Cu2 + + HCO3 + 2OH (12)
Fig. 16 shows the effect of sulphidising agent dosage on the flotation
of malachite using KAX.
It is shown that any excess in sulphidisation will degrade the re-
covery of useful metals (Bila, 2006, pp. 13–35; Zhou & Chander, 1993).
Xanthate flotation is widely used because of its greater selectivity
compared tofatty acid flotation. In addition, xanthates flotation is not
very gangue sensitive. However, it is expensive and very difficult to
control (Hughes, 2005; Lee et al., 1998; Malghan, 1986). It is worth
noting that xanthates are the primary sulphide collectors. Oxidised
Cu–Co ores are sulphidised before subjecting them to xanthate flota-
tion. The purpose of sulphidisation is to form sulphide films on mineral
surfaces in order to float them with xanthates. Pulp operating condi-
tions must be well monitored. In fact, at low concentrations the sul-
phidising agent acts as an activator, but at high concentrations it de-
presses the newly sulphidised minerals (Castro et al., 1974).
237
Journal of Sustainable Mining 18 (2019) 226–246
Fig. 16. Effects of the sulphidising agent dosage on the flotation of malachite
with KAX (modified from Bila 2006, pp. 13–35).
Sulphidising agents are generally added sequentially and high initial
dosages of sulphidisation agents are recommended (Gush, 2005; Phetla
& Muzenda, 2010). This helps to regulate the concentration of sulphide
and/or sulphydrate ions present in the pulp (Gush, 2005; Phetla &
Muzenda, 2010). In the pH range of 7–14, the potential measured in the
pulp varies proportionally to the sulphide ion concentration (Chander,
2003).
During the sulphidising flotation of oxidised minerals, part of the
sulphidisation agents also reacts with the oxygen from the air injected
into the pulp (Gush, 2005; Shengo, 2013). This can lead to the forma-
tion of oxysulphide ions and to an overconsumption of the sulphidising
agents. Therefore, sulphidising agents are used in excess to maintain the
correct level of sulphide ions available to sulphidize useful oxidised
minerals (Davidson, 2009; Gush, 2005). However, it should be noted
that an excess of sulphide or sulphydrate ions disturbs the smooth ad-
sorption of collectors on active sites of useful oxide minerals in lowering
the redox potential of the pulp (Shengo, 2013). Sulphydrate and sul-
phide ions compete with the collector and hinder their adsorption via
the electrostatic repulsion of xanthate ions (Wills & Napier-Munn,
2006). The addition of ammonium sulphate (NH4)2SO4 to the pulp
helps to remove excess sulphur and improve the flotation of useful
minerals. This technique was used in Katanga at the New Concentrator
in Kipushi (NCK) in the sulphidising flotation of Luiswishi Cu–Co oxide
ores. The action of (NH4)2SO4 on the excess of sulphidising agents re-
sults from its influence on the alkalinity of the pulp through acid hy-
drolysis of the ammonium ion released by its dissociation in water as
shown by chemical reactions (Shengo, 2013):
2NH+4(aq) + SO24(aq)
(NH 4 ) 2 SO4(s) (13)
NH+4 + 2H2 O = NH 4 OH + H3 O+ or NH+4 + H2 O = NH3 + H3 O+
(14)
H3 O+ + OH = 2H2 O and HS + H2 O = H2 S + OH (15)
CuCO3 . Cu(OH)2 + 2H+ Cu2 + + CO2 + H2 O + Cu(OH) 2 (16)
CuCO3 . Cu(OH) 2(s) + (NH 4 ) 2 SO4(sol) 2Cu 2(aq)
+
+ SO24(aq) + CO2(aq)
+ 2H2 O+ 2NH3(aq) (17)
Cu2(aq)
+
+ 4NH3(aq) = Cu(NH3 )24+ (18)
Cu(OH) 2 + nNH3 = Cu(NH3)2n+ + 2OH (19)
The promoting effect of (NH4)2SO4 on the recovery of the desired
minerals is the result of its influence on the surface charge of minerals
via reactions (13–19) which makes the sulphidisation and collection by
a direct adsorbent-adsorbate reaction easy.
However, the sulphidisation of oxidised Cu–Co minerals and their
flotation with xanthates remains a delicate and costly operation. It re-
quires an optimal concentration of sulphide and sulphydrate ions in the
pulp for the better flotation of useful minerals (Barbaro et al., 1997;
M.L. Shengo, et al. Journal of Sustainable Mining 18 (2019) 226–246

Table 3
Reagents suite and regime implemented at the NCK.
Reagents type and grade Dosage (g/t)

Oxide oresa Mixed oresb

Slimes depressor - Sodium silicate - 20% 300 180

Frother - Dowfroth (D250) - 100% 165
Frother - Sasfroth G41 – 100% 175
Promoter - Ammonium sulphate - 30% 390 100
pH regulator - Citric acid - 20% 800 200
pH regulator – Lime – 20% Pulp pH kept at
10
Sulphidiser - Sodium hydrosulphide - 36% 7600 400
Primary collector – Potassium amylxanthate - 840 100
10%
Secondary collector - Mixture of gasoil (90%) 150
and tall oil (10%)
Fig. 17. Mineralogical characteristics of the ores from the Luiswishi deposit
(modified from Shengo, 2013). a
Exclusively made of oxide minerals (2010).
b
Blend of 70% sulphides and 30% oxides (2015).
Gush, 2005). In addition, the acquisition of sulphidisation agents to-
gether with other flotation reagents is the most significant expense of sodium sulphydrate (10,000 g/t) during the roughing stage for the
item, after milling, in terms of the operating costs of a concentrator. better sulphidisation of malachite and heterogenite minerals. The re-
Moreover, oxidised minerals do not respond in the same way to sul- covery was essentially based on Co, which was the more economic
phidisation (Rio Echevarría, 2007, pp. 5–16). Chrysocolla, in particular, coproduct targeted in the final concentrate considering its high price on
is known to respond poorly to flotation using xanthates with sulphidi- the metals’ market. The Cu–Co bulk concentrate obtained was
sation (Barbaro et al., 1997; Kanda, 2013; Ndalamo, 2008). Several grading25–30% Cu and 7–8% Co.
concentrators operating in Katanga used the sulphidisation of Cu–Co
ores and their flotation using xanthates. These include Kipushi, Kam- 3.2.3.5. Sulphidisation of silicates, sulphates, and basic chlorides and
bove, Kakanda, Kisenda, Comika, Comilu, Dikulushi and Kamoto con- sulphates of Cu. The sulphidisation of oxidised silicate Cu–Co ores like
centrators (Chadwick, 2015; Countois et al., 2003; Katwika, 2012, pp. chrysocolla (Cu₂H₂Si₂O₅(OH)₄)is difficult and should ideally be done
4–16). using thermal methods (Valenta & Mulcahy, 2016). Thermal
The NCK is installed in the facility of the former Kipushi con- sulphidisation has been successfully tested on a laboratory scale by
centrator, which was once operated by Gécamines. The plant received many researchers, particularly for chrysocolla (Gonzalez & Soto, 1978)
the oxidised Cu–Co ore, mainly, from the Luiswishi mine, with grades in as well as lead and zinc oxide minerals. Ziyadanogullari and Aydin
metals of about 3.33% Cu and 1.34% Co. The main valuable minerals in (2005) investigated the thermal sulphidisation of a Cu oxide ore from
the ROM ores are malachite [(CuCO3.Cu(OH)2], pseudo-malachite, the Ergani Copper Mining Co, in southeast Turkey. The ore sample used
chrysocolla (CuSiO3.2H2O), heterogenite (CoO.3Co2O3.CuO.7H2O), and contained 2.03% Cu, 0.15% Co, and 3.73% S. The valuable minerals
spherocobaltite (CoCO3). In the ROM ores, one finds also the gangue present were chrysocolla, chalcopyrite, and native copper. The gangue
made of quartz, talc and graphite (Fig. 17). A large part of the gangue comprised pyrite, carbonate, calcite, and clay minerals. The ore (of a
material is removed at the pre-concentration stage. The flotation size up to −149 μm) was beneficiated using the sulphidisation and
flowsheet of NCK is given in Fig. 18. xanthate flotation method. Sulphidisation was carried out in an
The reagents regime (Table 3) was based on a strengthened dosage autoclave (110 °C) under a gaseous atmosphere of H2S (30.7–38.3 g/

Fig. 18. NCK flow sheet (modified from Shengo, 2013).

238
M.L. Shengo, et al. Journal of Sustainable Mining 18 (2019) 226–246

kg) and steam (200–250 g/kg). Flotation was done using potassium
amyl xanthates and the pH was set at pH 8.7 using lime. Grades of
approximately 10% Cu and 0.55% Co were obtained, with recoveries of
approximately 77% Cu and 75% Co.
Omarov, Bekturganov, Yusupov, and Antonov (1994) treated oxi-
dised minerals of Cu such as malachite, antlerite (Cu3(SO4) (OH)4),
brochantite (Cu4SO4(OH)6), atacamite (Cu2Cl(OH)3) and chrysocolla
using elemental sulphur in a steel crusher in the temperature range of
60–70 °C in the presence of iron. They reported sulphidisation rates of
40–60% when synthetic malachite, antlerite and brochantite (<50 μm),
natural atacamite (100–125 μm) were ground for 40 min with steel
balls. In the case of natural chrysocolla (100–125 μm), the sulphidisa-
tion rate of about 16% was obtained under the same conditions.
However, thermal sulphidisation of oxidised Cu–Co ores is not yet
industrially implemented in Katanga, despite the potential it may have
for the flotation of chrysocolla-rich ores extracted from mines like
Kamfundwa.
3.2.3.6. Flotation of oxidised Cu–Co ores with xanthates without prior
sulphidisation. The flotation of oxidised Cu–Co ores without prior
sulphidisation can be successfully carried out if a large amount of the
collector is used (Drzymala, 2007).
Fig. 19 shows the flotation of azurite with long-chain hydrocarbon-
based xanthates with and without sulphidisation (Samsonova et al.,
1974). Unsulphidised malachite can also be floated with long hydro-
carbon chain xanthates. Rao and Finch (2003) stated that the flotation
of unsulphidised base metal oxides (Ni, Cu, Zn, and Fe) with long hy-
drocarbon chain xanthates strongly depends on the pH of the pulp.
3.2.3.7. Flotation of oxidised Cu–Co ores with fatty acids. This flotation
type is carried out with collectors, which are constituted of fatty acid
mixtures that are added to pre-conditioned pulps. The mixtures, which
are often used, are made of unsaturated fatty acids and saturated fatty
acids whose roles are foaming and collection of minerals of interest,
respectively. The composition of mixtures generally depends on the
manufacturers. However, they are generally based on a mixture of
hydrolysed palm oil and gasoil. As a preparation, the mixture is
emulsified in hot water (32–34 °C) in the presence of sodium
carbonate, which increases the stability of the emulsion. In Katanga,
the flotation of oxidised Cu ores by means of fatty acids dates back to
1930. The fatty acid used for collecting minerals at Gécamines (UMHK)
is palm oil reconstituted at 75%. This means that the hydrolysed palm
oil is mixed with crude palm oil to an acidity of 75%. The reconstituted
palm oil is then mixed with gasoil and tall oil in the proportions of 72%,
24%, and 4%, respectively. The mixture is emulsified in slightly
carbonated hot water. Palm oil as a collector has become scarce in
Katanga and must be imported. Gécamines (UMHK) abandoned using
fatty acids for the flotation of oxidised Cu–Co ores due to the scarcity of
palm oil and water vapour that induced extras (40%) on the overall
operating cost of the process. Fatty acids are currently replaced by
synthetic fatty acids from petroleum refining such as Rinkalore 10 and
840 that are used as secondary collectors or boosters.
The quality of the water used in the concentrators is of paramount
importance when fatty acid collector types are used. Ca2+, Mg2+ ions,
and alkaline-earth salts contained in water, consume fatty acids
through the formation of insoluble soaps. They also have a flocculating
effect on the pulp. In order to remove the hardness of the water, sodium
carbonate (1–1.2 kg/t) is added during the conditioning of the pulp. In
turn, sodium silicate (0.8–1.2 kg/t) is used as a dispersant of gangue
and as a depressant. The order in which sodium silicate depresses
Cu–Co ore minerals is as follows: quartz and chrysocolla; cuprite and
hematite; malachite; calcite, dolomite, and talc. Since calcite, dolomite,
and talc are the least depressed, they are often collected before mala-
chite, which is why the fatty acid process is not suitable for talc or
dolomitic ore. Talc and dolomite gangues can be pre-floated before
subjecting Cu–Co oxidised ores to actual flotation with fatty acids. In
the depression scale of minerals by sodium silicate, heterogenite is
placed between gangue and malachite. This suggests that Co minerals
could be recovered, to some extent, after malachite when differential
flotation is performed. Hence, a Cu-rich concentrate is first obtained,
followed by Cu–Co concentrate. However, it should be noted that fatty
acids display good collecting power for malachite in an alkaline
medium because their affinity for this mineral is great. The collection is
also satisfactory for heterogenite and pseudomalachite, but relatively
poor for chrysocolla. The optimum pH for the flotation of oxidised
Cu–Co ores with fatty acids is often between 8 and 10. For talc and
dolomitic Cu–Co ores, flotation by means of xanthates after superficial
sulphidisation is the preferred method because it allows good results to
be obtained regardless of the nature of the gangue encountered.
However, it should be noted that for non-dolomitic and non-talc Cu–Co
ores, flotation with fatty acids leads to recoveries of the same order as
xanthates. Because of the prohibitive price of xanthate collectors,
concentrators in the Katanga Cu–Co industry are increasingly con-
sidering the optimisation of the flotation of Cu–Co minerals with fatty
acid collectors, such as Rinkalore, which is currently one of the more
tested reagents at various concentrators in Katanga. Fatty acids are also
environmentally friendly when compared to xanthates (Countois et al.,
2003; Wimberley et al., 2011, pp. 87–111).
Kambove concentrator, a business unit of Gécamines, was a typical
plant that used fatty acids for the flotation of Cu–Co ores. It was pro-
cessing about 120,000 t/month of both Cu–Co sulphide and oxidised
ores. The plant received three different types of Cu–Co ores, mainly
from three mines (Table 4): Shangolowe, with metals contents of ap-
proximately 2.90% Cu and 0.12% Co; Kamfundwa, with average grades
Table 4
Chemical composition of the ROM ores processed at the KVC.
Element/ Proportion (%)
compound
Ore from the Ore from the Ore from the
Luisha deposit Kamwale deposit Shangolowe deposit

Total Cu 4.77 4.44 4.17

Oxidised Cu 4.37 4.06 3.75
Total Co 2.21 1.29 0.09
Mn 0.11 NA 0.46
Ni 0.05 0.75 0.01
Total MgO 19.60 12.00 4.84
Soluble MgO 0.83 6.96 0.31
Total CaO NA 7.73 3.12
Soluble CaO NA 7.47 0.22
SiO2 39.34 38.25 32.03
Al2O3 NA 3.60 6.47
Fe2O3 5.05 5.05 8.46
Fig. 19. Flotation of azurite using xanthates, with and without sulphidisation
(modified from Samsonova et al. 1974). NA: data not available.

239
M.L. Shengo, et al.
Fig. 20. KVC simplified flow sheet (modified from Shengo, 2013).
of 2.5% Cu and 0.3% Co respectively; as well as Kamoya Sud II with
2.7% Cu and 0.5% Co (Kanda, 2013). Fig. 20 shows the simplified
flowsheet of the Kambove concentrator.
The concentrator has adopted a “hybrid” process in the bulk flota-
tion of Cu–Co (Lutandula & Maloba, 2013). The process was based on a
reagents regime (Table 5) where the most expensive reagent, i.e. the
sulphidising agent (NaSH), was partially replaced by a mixture of
synthetic fatty acids (Rinkalore 10).
This allowed concentrates, with approximatively 11% Cu, to be
obtained since the process was essentially based on the recovery of Cu
(Lutandula & Maloba, 2013). The concentrate obtained was either sold
or processed by hydrometallurgy or pyrometallurgy (Kugeria et al.,
2018).
3.2.3.8. Flotation of Cu oxidised ores using chelating collectors. At
present, many studies are being carried out on the use of chelating
collectors for the flotation of various mineral commodities. The
chelating collectors have been used successfully in the flotation of
various oxide minerals such as cassiterite, Cu oxide, and rare earth
oxides (Fuerstenau, Herrera-Urbina, & McGlashan, 2000; Lee et al.,
1998; Marinakis & Kelsall, 1987; Quast, 2000; Ren, Lu, Song, & Niu,
1997; Sreenivas & Padmanabhan, 2002). Flotation using chelating
collectors would be attractive in many respects as:
- chelating collectors have at least two functional groups in their
molecular structures that could form coordination bonds with metal
ions on the ore surface of the mineral;
- they are less dependent on pH than xanthates and fatty acids that act
through electrostatic interactions;
Table 5
The reagents regime used at the KVC.
Reagent type and grade Dosage (g/t)
Oxide oresa
Slimes depressor- Sodium silicate – 30% 250
Frother – Sinfroth G41 – 100% 10
pH regulator – Sodium carbonate – 30% 50
Sulphidiser – Sodium hydrosulphide – 36 or 24% 3000–3500
Primary collector - Potassium amylxanthate – 10% 300–350
Secondary collector – Mixture of gasoil (90%) and 150
Rinkalore 10 (10%)
Froth mineraliser - Tail oil as - 100%
a
Oxides from the deposit of Kamfundwa processed in 2007.
b
Blend of oxide ores (50%) from the deposits of Kamfundwa and Mukondo
and processed in 2014.
Journal of Sustainable Mining 18 (2019) 226–246
- they are highly selective in that they form specific chelate com-
plexes with targeted metals (Lee et al., 1998; Rio Echevarría, 2007,
pp. 5–16).
Alkyl hydroxamates have recently been developed for extensive use
in the flotation of oxidised Cu ores and tailing reprocessing (Hughes,
2005; Lee et al., 1998). Hydroxamates are chelating molecules that
consist of mixtures of cis-trans isomers of which only the trans-isomer is
active as a collector in the flotation of oxide minerals (Hughes, 2005).
They behave like weak acids with a molecular structure that may be
regarded as a carboxylic acid molecule inserted into a hydroxylamine
group. Potassium n-octyl hydroxamate (AM2) is the most efficient col-
lector amongst alkyl hydroxamates and its synergetic action with con-
ventional collectors of sulphide minerals has been demonstrated during
numerous flotation tests (Hughes, 2005). However, it is worth pointing
out that a decrease in flotation efficiency is observed when the alkyl
chain of alkyl hydroxamates is composed of more than nine carbon
atoms (Bulatovic, 2007). Their performance strongly depends on the
length of the hydrocarbon chain, their alkyl radicals, and the level of
fine particles in the pulp. The literature indicates that alkyl hydro-
xamates are adsorbed by the surface of minerals by a mechanism
combining surface reactions and chemisorption(Davidson, 2009). In
addition, the alkyl hydroxamates adapt to changes in mineralization
resulting from the depth of a given ore deposit. They can be used in the
flotation of oxide ores and secondary Cu sulphides, such as chalcocite.
Theoretically, they possess the ability to recover Cu from mixed ores
(Hughes, 2005; Rio Echevarría, 2007, pp. 5–16). During the flotation of
oxide ores, AM2 is often used at a concentration of 20% in a dilute
sodium hydroxide solution (pH = 10) (Hughes, 2005).
Chrysocolla can be successfully floated (at a recovery rate of 95%)
without sulphidisation in a slightly acidic medium (pH = 6) in the
presence of chelating collectors, such as salicylaldoximes (Hughes,
2005). In this case, the flotation of chrysocolla takes place via a com-
plex between the collector and Cu ions from the mineral surface (Lee
Oxide oresb et al., 1998). The chelating collectors selectively react with Cu ions
from the oxidised mineral surface rendering it hydrophobic and se-
300
parable from the gangue without activation (Fuerstenau et al., 2000).
100
Hughes (2005) also studied the flotation of Cu sulphide ores using
3000 hydroxamate as a “booster” of a conventional thiocarbamate collector
300 and obtained yields well above 75% (Fig. 21).
400
Hydroxamic acid/hydroxamate collectors have the potential to re-
40
place conventional collectors, such as xanthates, for the flotation of
oxidised Cu–Co ores and secondary sulphide Cu–Co ores, in particular
chalcocite (Rio Echevarría, 2007, pp. 5–16). The first attempts for using
hydroxamates in the flotation of Cu–Co oxidised ore in Katanga date
240
M.L. Shengo, et al.
Fig. 21. Flotation of chrysocolla with hydroxamates (modified from Hughes
2005).
back to1971 at the Kamoto Concentrator (Lualaba). They were used in
combination with xanthates during the flotation of oxidised ores and
significant improvements in the selectivity and recovery of Cu–Co were
observed (Evrard & De Cuyper, 1975). Gayer (1981), cited by Bulatovic
(2007), also reported attempts to use alkyl hydroxamates for the re-
covery of malachite at the Kolwezi concentrator (KZC). The ore feed
consisted of ROM ores with dolomite as the major gangue mineral. The
metallurgical research units at the NCK and KDC concentrators have
considered the possibility of using AM2 in the flotation of Cu mixed ores
(oxides and sulphides) from the deposits of Luiswishi and South Ka-
bolela. In the Kabolela deposit, Cu–Co mineralization mainly occurs as
the fine dissemination of sulphides (pyrite with inclusions of chalco-
pyrite, and bornite, chalcopyrite enriched in chalcocite) in RSC lens
(rich in carrollite). In some areas, the grades of Cu–Co may reach 45%
Cu and 10% Co, respectively (Lefebvre, 1976). The KDC successfully
carried out the flotation of Cu mixed ore from the south Kabolela de-
posit using an “Eagle” alkyl hydroxamate collector manufactured in
China.
There is a great incentive to use chelating collectors in the flotation
of the Congo Copperbelt ores due to lower recoveries, lower grades, and
the increasing complexity of the mineralogy. The use of alkyl hydro-
xamates in combination with fatty acids is considered an option for the
reduction of the high reagent costs. However, it should be noted that
they have not yet been adopted in the commercial flotation of Cu–Co
ores, and further research is ongoing at various institutions for their
industrial application.
3.2.3.9. Differential and bulk flotation of mixed sulphide-oxidised Cu–Co
ores. Copper complex ores contain profitable amounts of more than one
valuable mineral. They are extensively mined in the Zambian
Copperbelt. They belong to the more complex Cu deposits in which
sulphides occur in a mixture with oxide minerals. In the Congo
Copperbelt, mixed Cu ores are mainly mined from Musoshi, Kinsenda,
Kimpe and Lubembe deposits (Zientek et al., 2014). Differential
flotation is applied to complex minerals containing several mineral
species of metallurgical interest that are not to be collected in an overall
concentrate to facilitate subsequent operations. The differential
flotation of oxide ores is much more difficult than that of sulphide
ores, as the modifications of the collection are less selective. Mixed
sulphide-oxidised ores undergo two-stage differential flotation. Mixed
sulphide-oxidised Cu–Co ores with a high proportion of sulphide
minerals are treated by selective flotation according to the following
order: copper and Co minerals, or by bulk flotation, followed by the
separation of the Cu–Co minerals. In general, the preferred method of
treatment is selective flotation for optimal recovery of Cu–Co in their
respective concentrates. Lime is often added to the flotation system to
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Journal of Sustainable Mining 18 (2019) 226–246
maintain the pH of 10–11 in the flotation circuit, and the pulp is
conditioned for 10–15 min with the addition of a small amount of
sodium cyanide at 25 g/t. Large amounts of cyanide tend to depress Cu
minerals. Alcohol type frothers, such as Aerofroth 70, and a
dithiophosphate collector, with Aerofloat 208 or 238 and Aero 3501
promoter, are preferred and are then added for the selective flotation of
Cu sulphides. After the flotation of the Cu, the pulp is conditioned for
15 min with sulphuric acid to reach a pH of 8–9, with small amounts of
Cu sulphate; isopropyl xanthate and a suitable frothing agent are added
to float Co.
The Kinsenda concentrator (KICC), owned by Jinchuan Group
International Resources Co Ltd, was commissioned in 2015. It was de-
signed with a handling capacity of 100,000 tonnes per month of ores
from the high-grade Cu deposit of Kinsenda (~5.1%) (Albert, 2015, pp.
15–17; Chadwick, 2007). It produces Cu sulphide concentrates (~40%
Cu) and Cu oxide concentrate (~32% Cu) using selective flotation
(Albert, 2015, pp. 15–17; Chadwick, 2007). The sulphide concentrate is
sold to smelters, and the oxide concentrate is subjected to the sulphuric
acid leaching in order to produce Cu cathodes as suggested for the
Ruashi Mining hydrometallurgical plant, which is also owned by the
Jinchuan Group International Resources Co Ltd (Albert, 2015, pp.
15–17). The Musoshi concentrator, which is currently out of use and
partially dismantled, was operated by the “Société de Dévél-
oppementMinière du Congo” (SODIMICO), previously owned by the
Japanese consortium led by Nippon Mining (Takeushi et al., 1986, pp.
129–130), was processing mixed ores with Cu occurring as chalco-
pyrite, bornite, cuprite, malachite, chalcocite and azurite. At the Mu-
toshi concentrator, the ores were subjected to sulphidisation with NaHS
prior to flotation by means of xanthates (Kaniki & Tumba, 2019). The
Cu sulphide concentrates produced by the Mutoshi concentrator, during
the processing of high-grade Cu ores from the Kinsenda deposit and the
chalcopyritic ones from the deposit of Musoshi, were transported
through Zambia, Namibia and Botswana, for their dispatch to Japan
from a South African port (Ellis, 1979, pp. 1061–1066).
Another processing technique dedicated to the extraction of Cu from
the mixed ores is encountered in Mexico. It is based on the flotation of
sulphide minerals in combination with the sulphuric acid leaching of
oxide minerals (Zhan-fang, Hong, Guang-yi, & Shu-juan, 2009). This
technique is viewed as away to bypass the weaknesses showed by the
sulphuric acid leaching of the ore when chalcopyrite is the main
bearing mineral of Cu. Thus, chalcopyrite is floated at pH 8 by means of
butylxanthate (100 g/t) after sulphidisation of the ores with sodium
sulphide (160 g/t). The “Companie Minière de Luisha” (COMILU) pre-
sently utilises the aforementioned processing technique during the
processing of mixed ores from the deposit of Luisha located nearly
80 km from the city of Lubumbashi in the Haut-Katanga province.
Commissioned in 2014, the concentrator operated by the COMILU
processes mixed ores of Cu (±2%) using sulphidisation by NaHS and
flotation by means of xanthates in the presence of MIBC as a frother. It
produces commercial-grade Cu sulphide concentrates (24–28% Cu). As
for tailings from the flotation of Cu sulphides, they are conditioned with
NaHS prior to re-flotation by means of xanthates in order to produce Cu
oxide concentrates (5–8%) which are subjected to sulphuric acid
leaching at the hydrometallurgical plant of the COMILU with the aim of
producing Cu cathodes.
The processing technique, essentially, based on the flotation of Cu
sulphides followed by the sulphuric acid leaching of oxides, will also be
implemented by the Jinchuan Group International Resources Co Ltd
during the processing of the mixed ores from the Kinsenda deposit. At
Kinsenda, the mineralization consists mainly of Cu sulphides (75–80%)
accompanied by oxides (25–20%).
In the bulk flotation of Cu–Co minerals, isopropyl xanthate and a
dithiophosphate collector are recommended as collectors while oper-
ating at a natural pH. After washing, the overall product concentrate is
fed into the separation circuit in which the pulp is conditioned with
lime, and a small amount of sodium cyanide is recommended for
M.L. Shengo, et al.
depressing Co. Cu sulphide minerals are then selectively floated. The
main ordinary Cu sulphide minerals may contain different levels of iron
sulphides of various types, which generally include pyrite (FeS2).
However, Cu liberated from chalcopyrite will activate pyrite, which
increases the difficulty of separating chalcopyrite and pyrite. Methods
for the separation of Cu sulphides may involve elongated pH values, a
process with organic inhibitors, the electrochemical control method,
and the cyanide process. Some research has found a method of se-
paration of chalcopyrite and pyrite. In a research conducted by Zhong
et al. (2015), BKY-1 was used as a dispersant over a wide pH range, and
xanthate can be used as a collector to selectively float chalcopyrite. It
has been demonstrated that sodium silicate successively depresses non-
dolomitic gangue, oxidised minerals of Co and malachite contained in
Cu–Co ores when the flotation is conducted using fatty acids as col-
lectors. Therefore, by a sequential addition of the silicate and the col-
lector to the pulp, a Co concentrate (the most abundant constituent) is
floated at the top, followed by a Cu–Cu concentrate containing the
remainder of Cu–Co.
In the former Katanga region, Cu is recovered from its mixed ores,
with the gangue composed of dolomite, through sulphidisation and
flotation by means of xanthates. At Kolwezi, in the Lualaba province,
the mixed ores of Cu ores are subjected to sulphidisation using sodium
hydrosulphide and floated in the presence of potassium n-butylxanthate
(PNBX) and Sinfroth G41, respectively, as a collector and frother.
Moreover, a blend of gasoil (80%) and tall oil (20%) is added to pulp as
the promoter (Countois et al., 2003; Wimberley et al., 2011, pp.
87–111).
4. Reprocessing of concentrator tailings
In the Katanga province of the DRC, many tailings from the flotation
of oxidised Cu–Co ores are stockpiled in settling ponds for further
treatment in the future through the use of other techniques, while the
wastewater from the concentrators is sent to the rivers. The tailings
consist of gangue minerals and unrecovered metals of interest. In some
cases, tailings may contain Cu-Coat economically viable concentrations
for recovery (Mbuya et al., 2017). Lutandula and Maloba (2013) carried
out a series of flotation tests on the Kambove Concentrator tailings
(3.31% Cu and 2.22% Co) and recovered approximately 44.80% Cu and
88.30% Co. Recovery of Cu–Co from tailings could boost overall metal
production and provide an additional source of revenue for the country.
Moreover, their treatment may ensure no pollution of the environment.
It could also contribute to the conservation of resources through the
recovery of metals from the waste of mineralogical processes.
5. The future of the Cu–Co ore processing industry
Low-grade ore deposits are of increasing interest in mineral pro-
cessing owing to dwindling resources of high grade, easily exploited
ores. For Cu–Co ores in the DRC, oxidised ore deposits have historically
been the main source of Cu–Co as they are relatively simple to process,
mainly by leaching/solvent extraction/electrowinning. As high-grade
oxidised Cu–Co ores become depleted, importance is placed on the
mining of low-grade disseminated ores. These deposits commonly dis-
play complex mineralogy in terms of mineral composition and texture,
the understanding of which is important in the processing of the ore.
Maintaining recovery and sustainability while keeping costs under
control then becomes challenging. Mining is also gradually taking place
at depths where there are increased sulphide deposits. This means most
ores currently mined are mixed sulphide-oxidised ores. The flotation
and physical separation methods therefore appear to be the right can-
didate processes for meeting the market's demand.
As far as flotation is concerned, there is a need to invest in funda-
mental flotation research to improve separation efficiencies when
treating complex and low grade ores, in order to reduce the costs of
reagents, develop reagents which are stable over a wide pH range, and
242
Journal of Sustainable Mining 18 (2019) 226–246
to take advantage of the role of synergism in the use of mixtures of
collectors. The use of fatty acid collectors is growing and they are being
considered a replacement of costly Rinkalore mixtures. Although sul-
phidising flotation is successfully applied in the flotation of oxidised
Cu–Co ores, recovery is still relatively low at about 81–82% and
55–60% at the roughing and cleaning stages, respectively, accompanied
by the overconsumption of sulphidising agents. Implementation of
Controlled Potential Sulphidisation (CPS) schemes in the flotation of
oxidised Cu–Co ores would enhance the flotation efficiency and sig-
nificantly reduce the consumption of sulphidising agents and, conse-
quently, the overall processing cost.
Preconcentration of low-grade Cu–Co ores using gravity separation
methods is also of growing importance for a number of concentrators in
the DRC, as it contributes to making the beneficiation of previously
uneconomic ore deposits possible, and significantly reduces the pro-
cessing time and costs. HMS and spirals are now installed at a number
of concentrators. With the need to process even low-grade finely dis-
persed ores (e.g. down to product sizes of less than 50 μm), the use of
centrifugal gravity separation is promising and could be integrated into
the beneficiation circuits to improve metal recoveries.
Table 6 summarises the main concentrators in Katanga using their
characteristics (owner, age, status, concentration method, and source of
fed ore).
6. Conclusion
This article reviewed the past, present, and future of the bene-
ficiation of Cu–Co minerals in the DRC. Sulphidisation followed by
froth flotation using xanthates remains the widespread beneficiation
technique for oxidised Cu–Co ores. Sulphidisation is essential for im-
proving the recoveries of Cu–Co. In particular, the addition of initial
high dosages of sulphidising agents to the pulp helps to significantly
improve Cu–Co recoveries. However, it should be noted that the use of
sulphidising agents adds about 40% to the overall operating costs. The
integration of CPS systems into the flotation circuits can help minimise
the overconsumption of sulphidisers.
With the need to process finely disseminated Cu–Co minerals in
complex gangue matrices, gravity separation is gaining momentum as a
preferential beneficiation technique for Cu–Co ores. It is often im-
plemented before flotation to remove a large amount of the gangue
materials to reduce processing time and cost. Sometimes gravity se-
paration is sufficient for producing concentrates that are sold to smel-
ters in the country or exported to countries like Zambia and China for
further processing. Gravity separation is also increasingly used in the
reprocessing of tailings.
Mining is also increasingly taking place at depths where sulphide
bodies prevail, and therefore the ores processed are a mix of sulphide
and oxidised minerals. It is therefore important to reinvent the design of
grinding and beneficiation circuits. This also relates to the need to
adopt reagent suites that are tailored for mixed ores. Application of
differential or selective flotation would also help mining companies to
efficiently produce separate oxide and sulphide concentrates.
Finally, it is important to note that there is a lack of fundamental
research on the beneficiation of Cu–Co ores from the DRC. Most re-
search and data in the literature is related to the optimisation of circuits
using specific reagent suites. With the processing of low-grade ore with
ever changing mineralogy, there is a need to invest in research in order
to improve the understanding of their behaviours with respect to cur-
rently used reagents, and eventually newly manufactured ones.
Ethical statement
Authors state that the research was conducted according to ethical
standards.
M.L. Shengo, et al. Journal of Sustainable Mining 18 (2019) 226–246

Table 6
Major copper ores concentrators in the Great Katanga.
Concentrator name Owner Age Present Status Process Feed sourced from the deposits of

Kakanda Concentrator Boss Mining – Operational F Mukondo/South Kabolela

Ancient Concentrator in Kipushi Gécamines 1935 Abandoned F Kipushi polymetallic
Kolwezi Concentrator Gécamines 1941 Operational F Kilamusembo/Mutoshi tailings
Kambove Concentrator Gécamines 1963 Operational F Kambove, Kamwale, Luisha and shanguruwe
Kamoto Concentrator Gécamines 1968 Operational F Kamoto
Musoshi Concentrator Sodimico 1972 Abandoned F Musoshi, Kinsenda, Lubembe and Kimpe
New Concentrator in Kipushi Gécamines 1994 Temporary stopped F Luiswishi and Kasombo
Dikulushi HMS plant Anvil Mining 2004 Decommissioned GS Dikulushi
Ruashi Concentrator Ruashi Mining 2006 Decommissioned F Ruashi/Tailings
Kinsevere gravity concentrator MMG 2006 On care and maintenance GS Kinsevere, Tshifufia and Tshifufia mashi
Dikulushi Concentrator Mawson west Ltd 2008 On care and maintenance F* Dikulushi
Kakanda gravity concentrator Boss Mining 2008 Temporary stopped GS Mukondo
Kipoi gravity concentrator SEK (Tiger) 2008 Decommissioned GS Kipoi central
Sakania Concentrator Frontier S.A. 2011 Operational F Kishiba
Kinsenda Concentrator KICC/Metorex 2012 Operational since 2017 F Kisenda
Kamfundwa gravity concentrator Gécamines 2013 Operational GS Kamfundwa
Kapulo Concentrator Mawson west Ltd 2014 On care and maintenance F* Shaba and Safari
Kalukuluku gravity concentrator CHEMAF 2014 Operational GS Kalukuluku and Kansonga
Kanshinshi gravity concentrator CHEMAF 2014 Operational GS Kanshinshi
Luisha Concentrator COMILU 2014 Operational F Luisha
Comika Concentrator COMIKA 1916 Operational F Kamoya
Lupoto Concentrator IVERLAND 1917 Operational GS Lupoto
Kawama Concentrator CDM 1918 Operational F Luiswishi

F: flotation; F*: flotation with the CPS implementation; GS: gravity separation using HMS (FeSi as heavy medium) and spiral.

Conflicts of interest
None declared.
Funding body
No funding from anybody or organisation.
Acknowledgements
We are grateful to the following colleagues and mineral processing
practitioners for their assistance in data collection: Pierre Kalenga Ngoy
Mwana, Mwema Mutamba Dibwe, Marcel Lenge Masangu Mpoyo,
Kongolo Kitala, Jimmy Kalenga Kasongo Kaunde, Christian Katwika
Ndolwa, Jean-Marie Kanda Ntumba and Onésime Kadianga. We are
indebted to Banza Maloba, Kanku Mutaka, Kilumba Mwenze, Ilunga
Mpanga, Kabondo Lenge, Mbala Kanyinda, Mbaya Kasongo, Mwamba
Mbuyu,Kasongo Kyamubele and Umba Ndolo for their outstanding
contribution to the writing of this article. We must also acknowledge
the priceless involvement of the managing staffs of NCK, KVC, KCC,
KDC, Dikuluishi and Kapulo concentrators in the article preparation for
access to the concentrators circuits' technical data and notes via our
probationers welcome.
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