Review

Sustainable Use of Copper Resources: Beneficiation of

Low‐Grade Copper Ores
Silpa Sweta Jena 1, Sunil Kumar Tripathy 2,*, N. R. Mandre 1, R. Venugopal 1 and Saeed Farrokhpay 3

1 Department of Fuel, Minerals and Metallurgical Engineering, Indian Institute of Technology (ISM),
Dhanbad 826004, India; [email protected] (S.S.J.); [email protected] (N.R.M.);
[email protected] (R.V.)
2 Research and Development Division, Tata Steel Ltd., Jamshedpur 831007, India

3 College of Engineering and Technology, American University of the Middle East, Egaila 54200, Kuwait;

[email protected]
* Correspondence: [email protected]

Abstract: The global market has announced copper as a modern energy metal and finds its extensive
utilization in the construction industry, electrical wiring, power transmission lines, alloying, anti‐
corrosive coating, heat exchangers, refrigeration tubing, etc. Copper ore is primarily beneficiated
from sulphide mineral deposits. Due to high‐grade copper sulphide deposit exhaustion, the focus
has now shifted towards recovery from different lean‐grade oxide and mixed ore deposits. The pre‐
sent paper summarizes the utilization of copper as a clean energy mineral and its importance in the
current renewable energy sector. Extensive research has been carried out on the flotation of copper
sulphide ore as compared to copper oxide and mixed type ores. Besides flotation, other beneficiation
techniques (selective flocculation and gravity separation) are also discussed in the present review.
A few novel pretreatment methods are currently being studied for copper ore to intensify the sepa‐
ration for higher productivity.
Citation: Jena, S.S.; Tripathy, S.K.;
Mandre, N.R.; Venugopal, R.; Keywords: copper ore; flotation; mixed collector; gravity separation; battery minerals
Farrokhpay, S. Sustainable Use of
Copper Resources: Beneficiation of
Low‐Grade Copper Ores. Minerals
2022, 12, 545. https://doi.org/10.3390/
1. Introduction
min12050545
Red metal “copper” is currently visualized as a clean energy metal. Specific proper‐
Academic Editor: Andrea Gerson ties such as conductivity, ductility, efficiency and recyclability are primary drivers for
Received: 22 March 2022 qualifying copper as a critical material for renewable energy (solar and wind technology).
Accepted: 23 April 2022 It also has significant energy storage usage (flow battery, lithium‐ion battery and sodium
Published: 27 April 2022 battery) in the electric vehicle production sector. Again, the electricity generation from
solar and wind energy uses four to six times more copper than fossil fuel (non‐renewable
Publisher’s Note: MDPI stays neu‐
tral with regard to jurisdictional
resources), which partially reduces the non‐renewable energy consumption [1,2]. A wind
claims in published maps and institu‐
turbine system of three megawatts (MW) power capacity consists of 4.7 tons of copper,
tional affiliations. while, in the case of the solar power system, 5.5 tons of copper is needed per MW produc‐
tion [3,4]. Again, lithium‐ion battery and flow battery for one MW of energy storage re‐
quires 44 lbs. and 540 lbs. of copper, respectively [4,5]. The utilization of electric vehicles
(EV) is becoming a trend, as it causes less/no environmental pollution and reduces/elimi‐
Copyright: © 2022 by the authors. Li‐ nates fuel consumption costs and energy independence, whose function depends heavily
censee MDPI, Basel, Switzerland. on copper (Figure 1) [1,3,5]. Thus, the increasing demand for EVs will ultimately affect
This article is an open access article copper production. By 2027, the copper requirement is supposed to be expanded by 1700
distributed under the terms and con‐ kt [5]. According to the world bank report, copper has become an imperative element due
ditions of the Creative Commons At‐ to its wide application in evolving low‐carbon technology (Figure 2) and in technology‐
tribution (CC BY) license (https://cre‐ based mitigation scenarios, which will ultimately generate a low‐carbon future [3]. How‐
ativecommons.org/licenses/by/4.0/).
ever, the International Copper Association (ICA) also listed advantage copper applica‐

Minerals 2022, 12, 545. https://doi.org/10.3390/min12050545 www.mdpi.com/journal/minerals

Minerals 2022, 12, 545 2 of 42

tions in renewable energy, climate change mitigation and adaptation and many sustaina‐
ble developments, which is impossible for any other metal or material [4,5]. Its recyclabil‐
ity without losing its inherent property after recycling provides a better economy and
strong life cycle analysis, which is impossible for other materials consumed and that be‐
come noneconomic at the end of life [4]. The importance of copper can also be visualized
from ancient history, where it lasted the whole 1000‐year era named the “Chalcolithic Pe‐
riod” or “Copper age”, from 4500 BC to 3500 BC. It has been reported that more than 80%
of the total production of copper mined throughout history is still in use [6]. Thus, copper
is a critical modern mineral for new generation technology advances [7,8].

Figure 1. Copper use by different types of vehicles (adapted) [4].

Figure 2. Mapping of minerals with their relevance in low‐carbon technology [3].

The complete dematerialization of rich‐grade copper ore and the continuously in‐
creasing demand make the processing of lean‐grade resources inevitable and mandatory
to sustain industrial growth and development. According to the global statistics, copper
Minerals 2022, 12, 545 3 of 42

is in the third position among all metals in global consumption, behind steel and alumi‐
num. Most of the copper deposits worldwide are porphyry in nature and contribute 50–
60% of the total global copper production. These deposits consist of primarily copper sul‐
phide minerals such as chalcopyrite (CuFeS2), chalcocite (Cu2S), bornite (Cu5FeS4) and
enargite (Cu3As5S4). Estimates suggest that approx. 90% of copper is derived from sul‐
phide deposits, mostly chalcopyrite, accounting for about half of all copper production
[9]. In a few deposits, copper also occurs in the form of oxide (cuprite‐Cu2O), malachite‐
CuCO3.Cu (OH)2, azurite‐2CuCO3.Cu (OH)2, chrysocolla‐CuSiO3.2H2O and a mixed form,
i.e., both copper oxide and sulphide minerals [10,11].
Copper is a non‐ferrous base metal, which comprises 50 ppm on average in the
Earth’s crust [12]. The average grade of a copper deposit for exploitation is approx. 0.4%
(open cast mines) and 1–2% Cu (underground mines), with many other valuable minerals
and gangue minerals [12]. Flotation is the most extensively used conventional technique
for copper beneficiation [13–15], particularly sulphide minerals [16,17]. Flotation has been
carried out using different reagents, which involves differences in the physical and chem‐
ical surface properties of copper minerals and gangue to separate them from each other
by using various surfactants [18–20]. Besides flotation, gravity separation [21–24], leach‐
ing [25] and selective flocculation [26–28] have also been used for the processing of copper
ore.
It is evident in the literature that there is a lack of information on copper flotation,
and most of the literature is confined to sulphide ore. The processing of oxide and mixed
ores is minimal. The aim of this paper is to review the published papers on the flotation
of copper ore with reference to different mineralogy and recently developed pretreatment
methods to intensify the separation. Different beneficiation techniques for copper ore are
discussed, and prospects for further research are identified. It should be noted that topics
such as recovery aspects of copper from secondary resources or hydrometallurgical and
pyrometallurgical processes in copper extraction are not included in this review.

2. Visualization of Recent Research Trends of Copper Using Bibliographic Analysis

Sections 4.1–8.3 will explain the detailed work on copper ore beneficiation within
different categories. Visualization and evaluation help in reviewing and assessing the es‐
sential findings and explaining reciprocity/interactions, trends and models. The current
section focuses on the present scenario of the copper ore literature, which can lead to fu‐
ture research. The bibliographic analysis involves the authors’ research interest, the total
number of papers published by the researchers and their total citations. The VOS Viewer
tool [1] was used to establish and visualize the bibliometric network of scientific literature
on copper ore processing. For a bibliographic analysis, the data was generated using the
SCOPUS search engine for the articles published in journals during the 10 years (2010–
2020) (excluded articles were published in conference proceedings, seminars or reports).
The publication data files are arranged into three categories (i.e., keyword, article author
and publishing country), contained around 427 publications. An analysis of these data
files via VOS viewer created a map of text patterns (Figure 3) to recognize the dominating
research trends, especially as per the significance and frequency of the keyword search
during a literature survey. From the mapping, it is confirmed that flotation is the most
current trending and vigorously practicing research areas in copper ore beneficiation.
Minerals 2022, 12, 545 4 of 42

Figure 3. Text pattern analysis during the last decade (2010–2020) literature survey to visualize its
scientific trends (more occurrences in larger circles).

3. Global Copper Reserve, Demand and Production and Consumption

According to the USGS (United State Geological Survey) report in 2018, Chile has the
highest copper reserve, followed by Australia, Peru, Russia, Mexico and the United States
[29]. Apart from the above major countries, Indonesia, China, Kazakhstan, DR Congo and
Zambia also contribute significantly towards the world copper reserves [29,30]. The total
copper reserve is estimated to be about 720 Mt. Again, the non‐estimated and identified
resources are calculated to be around 3500 Mt and 2100 Mt, respectively, excluding the
copper resources present in the deep marine environment. Figures 4 and 5 show the pic‐
torial representation of the world copper reserve, mine production [31] and global copper
reserves by different countries [29].
Minerals 2022, 12, 545 5 of 42

Figure 4. World copper reserve and mine production [31].

Figure 5. Global Copper Reserves as of 2019 by country [29].

The worldwide copper mine production decreased marginally from 20.4 Mt in 2018
to 20 Mt in 2019. The major factor attributed to this slight decrease in production is relo‐
cating the Grasberg and Batu Hijau mines in Indonesia to a new ore zone [32]. Due to the
off‐grade ore, unsuitable climatic conditions and workers strike, there is a decrease in
Chile’s copper production. However, the overall refined copper production increased
marginally to 25 Mt in 2019 from 24.2 Mt in 2014. In China, the production of refined
copper has declined because of the shutdown of many smelters for maintenance and de‐
velopment purposes. Zambia’s refined production was heavily affected by a new con‐
struction assignment on copper concentrate, which ultimately reduced the smelter output.
An insignificant supply of sulphuric acid fails to generate the desired electrowon copper.
The mine production of various countries is tabulated in Table 1 [32].
Minerals 2022, 12, 545 6 of 42

Table 1. The world mine production by various countries [32].

Mine Production (kt)

Country Name
2018 2019
United States 1220 1300
Australia 920 960
Chile 5830 5600
China 1590 1600
Congo [Kinshasa] 1230 1300
Indonesia 651 340
Kazakhstan 603 700
Mexico 751 770
Peru 2440 2400
Russia 751 750
Zambia 854 790
Other Countries 3540 3800
World Total (Rounded) 20,400 20,000

According to an ICSG report in 2019, the global total copper consumption increased
to 24,500 MT in 2018 from 17,888 MT in 2008 and 5000 MT in 1900, indicating a compound
annual growth rate of 3.4% a year for usage over these periods (Figure 6) [29,31]. Most of
the refined copper is consumed by China (49%), followed by other Asian countries (20%),
Europe (18%) and America (12%) [29]. As per the Fitch forecast, the world copper demand
will increase by 2.6% by 2027.

Figure 6. World copper production and usage for 1900–2020 [31].

4. Copper Mineralogy
Considerable knowledge and understanding of copper mineralogy is imperative be‐
cause of its varying geological occurrences. In the Earth’s crust, copper occurs in combi‐
nations with iron, sulphur, carbon and oxygen. Its occurrence is classified into three
groups as primary hypogene deposits, secondary group deposits and tertiary group de‐
posits [33].
Minerals 2022, 12, 545 7 of 42

Porphyry deposits are more common deposits for copper ore formed by the hydro‐
thermal fluids emanating from a magmatic chamber located several kilometers deep. The
mineralization of a hydrothermal deposit is structurally controlled with stock work of
quartz veins, vein sets, fractures and breccias containing copper sulphide with gold or
molybdenum [9]. The associated valuable minerals are pyrite, arsenopyrite, galena, sphal‐
erite, molybdenite, cobalt, pyrrhotite, hematite, magnetite, silver, gold, PGE minerals, ura‐
nium and antimony in different deposits, based on the origin. Silicates are the primary
gangue minerals (quartz, feldspar, albite, mica, etc.) in most copper deposits. Processing
such multimineral ores to produce individual mineral(s) of the desired quality is ex‐
tremely tough. The challenges during beneficiation become manifold if it contains a
higher amount of impurities. The world’s copper deposits (Figure 7), along with the asso‐
ciated minerals, are listed in Table 2. In addition, the major copper minerals are listed in
Table 3.

Figure 7. World map depicting important copper deposit [34].

Table 2. Types of major copper deposits [11,33,35,36].

Deposit Type Description Major Minerals Examples
Primary‐Chalcopyrite, bornite.
Chuquicamata and La Escondida,
Secondary‐Chalcocite, covellite, malachite, az‐
Large, low‐grade stock work dis‐ Chile; Bingham Canyon, USA;
Porphyry urite, cuprite, molybdenum.
seminated deposits Grasberg, Indonesia;
By‐product material: Rhenium, gold, silver,
Malanjkhand deposit; India
and tin.
Nchanga, Zambia;
Strata bound disseminations of Chalcocite, bornite with lesser chalcopyrite, ga‐
Lubin, Poland;
Sediment‐hosted copper minerals occurring in a lena, pyrite and hematite.
White Pine, USA;
range of sedimentary rock. By product material: zinc, silver, cobalt
Khetri deposit, India
Copper mineralization occurring
Copper sulphide (1–4% Cu) with silver and Dzhezkazgan, Kazakhstan;
Red‐bed in oxidized zones in sedimentary
rhenium. Mantos Blancos, Chile
and volcanic rocks
Mineralization hosted by subma‐ Chalcopyrite, sphalerite, pyrite, lead, gold, sil‐
Volcanic Massive Bathurst and Kidd Creek, Canada;
rine volcano‐sedimentary se‐ ver.
Sulphide [VMS] Rio Tinto, Spain
quences Cobalt, tin, manganese, cadmium, bismuth
Minerals 2022, 12, 545 8 of 42

Primarily Chalcopyrite with Pyrrhotite, Pent‐

Sulphide concentrations associ‐ Sudbury and Voisey’s Bay, Can‐
Magmatic Sul‐ landite.
ated with a variety of mafic and ada; Noril’sk‐Talanakh, Russia;
phide Minor amount of PGE, galena, sphalerite, gold,
ultramafic magmatic rocks Kambalda, Australia
silver, magnetite.
Deposit type Description Major mineral found Examples
Vein stock works and breccias as‐
El Indio, Chile;
sociated with high‐level or near Chalcocite, covellite, bornite, native gold, chal‐
Epithermal Lepanto, Philippines;
surface volcanic‐related low tem‐ copyrite
Monywa, Burma
perature hydrothermal systems
Mineralization by chemical altera‐ Ok Tedi, Papua New Guinea;
Copper Skarns tion associated with intrusions Copper (Chalcopyrite, bornite and tennanite) Copper Canyon, USA;
into carbonate rocks Rosita, Nicaragua
Mineralized structures often de‐
veloped along fractures varying Chalcopyrite, bornite, pyrite, quartz, silver, El Indio, Chile; Copper Hills, Aus‐
Vein Style from centimeters up to tens of gold, occasionally uranium, antimony and tralia;
meters wide from a variety of phosphorous. Butte, USA; Singhbhum, India
sources
Erdenet, Mongolia;
In‐situ natural secondary enrich‐
Supergene Chalcocite, covellite, bornite La Escondida, Chile;
ment of primary mineralization
Sarcheshmeh, Iran
Bodies of polymetallic sulphides
deposited from hydrothermal flu‐ Broken Hill and McArthur River,
Sedimentary Ex‐ Chalcopyrite, pyrite, sphalerite, galena, pyrite,
ids vented into sedimentary ba‐ Australia;
halative pyrrhotite, barite, silver
sins with no obvious volcanic Red Dog, Alaska
source

Table 3. Major copper‐bearing minerals, along with their physical properties [33–40].

Mineral Name Chemical Formula Cu% Specific Gravity Hardness Property

Native Copper (Cu) Cu 100 8.9 Non‐magnetic
Sulphides
Chalcopyrite (Cpy) CuFeS2 34.6 4.1–4.3 3.5–4
Chalcocite (Cc) Cu2S 79.9 5.5–5.8
2.5–3
Digenite (Dg) Cu9S5 78.1 5.5–5.7 Non‐magnetic
Covellite (Cv) CuS 66.4 4.6–4.8 1.5–2
Enargite (Eng) Cu3AsS4 49.0 4.4
3
Bornite (Bn) Cu5FeS4 63.3 4.9–5.3 Magnetic after heating
Oxides
Cuprite (Cpr) Cu2O 88.8 6.1
Tenorite (Tnr) CuO 79.7 6.5
3.5–4 Non‐magnetic
Malachite (Mal) CuCO3. Cu(OH)2 57.3 3.9
Azurite (Azu) 2CuCO3.Cu(OH)2 55.1 3.7
Silicate
Chrysocolla (Ccl) CuSiO3.2H2O 37.9 2.2 2–4 Non‐magnetic

5. Processing of Copper Ore

According to Jonathan ward, “Without copper, we would all be living in the stone
age” [12]. In the current modern 21st century, we should be thankful to copper as an es‐
sential part of many items that we use every day, such as cell phones, cars and air condi‐
tioning. From new modernized luxury to renewable energy and many countries’ integrity
in their national security systems, copper is an essential commodity. The demand for cop‐
per is even predicted to rise globally in the near future. To meet the worldwide demand,
its production must proceed towards sustainable growth. Previously, copper processing
was quite easier because of the availability of rich‐grade sulphide deposits. However, due
to their continuous excavation and exploration, we are now left with off‐grade sulphide
deposits and many oxides or mixed deposits where the processing is complicated. This
section included different ways of copper processing and its beneficiation.
Minerals 2022, 12, 545 9 of 42

For copper beneficiation, flotation is the most conventional method that has been
used since 1905. Flotation, in fact, has allowed mining of the lean and complex ore bodies
that would have otherwise been discarded as noneconomic overburdens [37]. The flota‐
tion enrichment technique for copper minerals was first applied to recover sulphide min‐
erals such as galena, sphalerite, chalcocite, chalcopyrite and pyrite [38].

5.1. Gravity Concentration or Separation

Despite achievement by flotation, gravimetric separation techniques are still per‐
formed because of their low cost of installation and higher efficiency. However, it can be
used only if there is a marginal difference between the specific gravity of the desired value
mineral and the gangue. Gecamines have performed upgrading of copper–cobalt ores
from Anaconda mines in Montana (USA) using gravity separation. The gravity concen‐
tration circuit contained Hancock jigs and a shaking table. After beneficiation, the copper
grade increased from 8.5–9.5% to 24–27%, respectively. The recovery was also increased
from 50 to 54%, respectively [41].
It should be mentioned that, for coarser size fractions, gravity separation using a table
and spiral is more suitable. However, for finer‐sized fractions, the application of enhanced
gravity separation is more appropriate [40,41]. In numerous plants in Katanga, a gravity
concentration unit is used to recover copper by reprocessing previously stockpiled cop‐
per–cobalt tailings [42,43]. Again, the concentration criterion is an essential metric for de‐
ciding whether the gravity concentration is feasible or not. Another research paper stud‐
ied the gravity separation process’s feasibility as a preconcentration step for lean‐grade
mixed copper of the Malanjkhand area using a Mozley Mineral Separator on the labora‐
tory scale [39]. The Malanjkhand deposit contained 0.48% Cu, and the copper content was
attributed mainly to chalcopyrite followed by bornite, digenite, covellite and malachite.
Further, the sample analyzed 74.12% SiO2 with quartz as the primary gangue mineral. The
concentration criterion for valuable minerals at the Malanjkhand deposit against gangue
(i.e., quartz) has been calculated and is shown in Table 4. In this case, gravity separation
is feasible, as the concentration criteria are between 1.75 and 2.73. The copper grade has
been increased from 0.48 to 5.33%, with 26.14% recovery [39]. To justify this result, the
authors have performed preconcentration via gravity separation using a bench‐scale
Wilfley table for the Malanjkhand copper sample. They found that it is possible to gener‐
ate a high‐quality feed for flotation with 52% silica rejection and 53.68% separation effi‐
ciency. A concentrate with 2.79% Cu was produced with 66.24% recovery [40]. In a few
case studies, gravity separation is rigorously used in processing copper tailings, which is
discussed in Section 6. The gravity concentration of copper ores is not effective due to the
poor liberation and finer grain size. The gravity concentration is feasible and effective at
a coarser particle size with a higher value of concentration criterion rather than a finer
particle size with the minimum concentration criterion. However, there is a scope for re‐
covering copper‐bearing minerals from low‐grade deposits by using enhanced gravity
separation, which needs further research.

Table 4. Concentration criteria between Malanjkhand constituent minerals.

Specific Gravity
Concentration Criterion (CC)
Valuable Heavy Minerals Gangue/Lighter Mineral
Chalcopyrite = 4.1 1.87
Malachite = 3.9 1.76
Covellite = 4.6 (Primarily Quartz) 2.18
Chalcocite = 5.5 Quartz = 2.65 2.73
Bornite = 4.9 2.36
Digenite = 5.5 2.73
CC > 2.5, Gravity separation is easy; CC < 1.25, Gravity separation is not feasible
ρfluid (specific gravity of water = 1); Valuable/Heavy Minerals—ρHM; Gangue/Lighter Mineral—ρLM;
𝐶𝐶 .
Minerals 2022, 12, 545 10 of 42

5.2. Selective Flocculation

In some cases, conventional flotation is inefficient to upgrade the finely disseminated
copper ores [44]. In such cases, selective flocculation may become a convenient technique
for separating the valuable minerals from undesired gangues [45]. Sresty and So‐
masundaran investigated chalcopyrite–quartz’s flocculation using hydroxypropyl cellu‐
lose xanthate, and they confirmed the effective flocculation of chalcopyrite (Figure 8)
without affecting quartz [45]. Patra and Natarajan [26] studied the separation of chalco‐
pyrite from quartz and calcite using a bio‐flocculant (Bacillus polymyxa). The adsorption
studies affirmed that a chalcopyrite surface has the highest adsorption density of bacterial
cells, and hence, it is selectively flocculated by leaving the quartz in a dispersed state (Fig‐
ure 9) [27]. Attia and Kitchener investigated copper ore flocculation tests and concluded
that the selective flocculation of copper minerals is possible by using polyacrylamide gly‐
oxal bis hydroxyanil [46].

Figure 8. Percentage of chalcopyrite and quartz settled as a function of the concentration of hydrox‐
ypropyl cellulose xanthate [47].

Figure 9. Adsorption density of Bacillus polymyxa cells in quartz, calcite and chalcopyrite as a func‐
tion of time [27].
Minerals 2022, 12, 545 11 of 42

Mweene and Subramanian studied the flocculation behavior of copper ore from the
Mpanda Mineral Field in Tanzania using Xantha gum (XG) as a flocculant and sodium
trisilicate as a dispersant (STS) [25]. The adsorption study revealed that XG adsorbs suc‐
cessfully on the chalcopyrite particles, while no adsorption was reported on the silica sur‐
face (confirming the selective flocculation of chalcopyrite by XG). Finally, the Cu grade
was increased from 0.9 to 19.8% by using 30 ppm of both STS and XG. Further, the sepa‐
ration efficiency comparison can be referred to in the literature [26]. Acar and So‐
masundaran studied the selective flocculation of fine chalcopyrite from pentlandite, using
both polyacrylamide (PAM) and polyethelene oxide (PEO) as flocculants [28]. They re‐
ported that both minerals can be flocculated using PAM, while only chalcopyrite particles
were selectively flocculated using PEO. There have been a few studies in the literature
that reported on the selective flocculation of chalcopyrite and mostly confined to synthetic
mixtures. However, the selective flocculation process with low‐grade ore (mixture of cop‐
per minerals) behaves differently from the synthetic mixture. The selective flocculation
process for recovering copper‐bearing minerals from a low‐grade deposit or tailing stream
is still a research subject. There is a lack of understanding on the selectivity and adsorption
of flocculants in copper‐bearing minerals.

6. Flotation of Copper Ore

Since the last century, froth flotation has been applied to copper minerals, and vari‐
ous new developments have brought the technology to its present level. In this section,
historical approaches that were practiced in copper flotation for sulphide, oxide and
mixed copper minerals are discussed.

6.1. Copper Sulphide Minerals

The important sulphide minerals of copper include chalcopyrite, chalcocite, bornite
and covellite. Among them, chalcocite (79.8% Cu) and chalcopyrite (34.5% Cu) can be cat‐
egorized as the most economically important minerals [31,32,37]. It is estimated that about
90% of copper is derived from sulphide deposits; mostly, chalcopyrite accounts for ap‐
proximately half of all copper production [9].
The flotation of copper sulphide ores is mainly carried out by using thiol collectors
(e.g., xanthate, dithiocarbamates and dithiophosphates), which form different surface
products in different copper sulphide minerals. An evaluation of the collector effects on
copper sulphide was performed using the criteria of recovery and flotation rate. The flo‐
tation of sulphide minerals of copper with sulphydryl collectors was found to be effective
in the following order [46,48]: Xanthate > Dithiophosphate = Thiocarbamates > Dixantho‐
gen.

6.1.1. Chalcopyrite
Chalcopyrite has a natural tendency to float [49–51]. Therefore, it can be floated by
using a frother only in an oxidizing environment. According to Mitchell et al. [52], pure
chalcopyrites exhibit an iso electric point (iep) value between pH of 5 and 6. The formation
of elemental sulphur during oxidation was mainly responsible for the surface hydropho‐
bicity and enhanced the flotation [53,54]. Thus, Gardner and Woods [53] proposed the
following chemical reaction during the oxidation process at higher pH values:
CuFeS2 + 3H2O → CuS + Fe(OH)3 + S0 + 3H+ + 3e (1)
The reaction between chalcopyrite and xanthate was studied by Allison et al. in 1972
[55]. They reported that two products might be formed, i.e., metal xanthate (MX) and
dixanthogen (X2). However, dixanthogen formation could not be detected due to the lesser
insolubility of cuprous xanthate (CuX), according to the following reaction:
CuFeS2 + X− → CuX + FeS2 + e− E0= −0.096 V (2)
Minerals 2022, 12, 545 12 of 42

According to Leppinen et al. [56], CuX can coexist with X2 during the chalcopyrite
and xanthate interaction. However, they stated that the presence of dixanthogen at‐
tributed to better flotation. They also concluded that the formation of CuX might take
place via CuS, which was formed by oxidation:
CuFeS2 + 3H2O → CuS + Fe(OH)3 + S + 3H+ + 3e E0= 0.547 V (3)
CuS + X− → CuX + S+ e− E0= −0.112 V (4)
The overall reaction by combining Equations (3) and (4) is as follows:
CuFeS2 + 3H2O + X− → CuX + Fe(OH)3+ 2S + 3H+ + 3e (5)
Oxidation of xanthate to dixanthogen: 2X →X2 + 2e
− (6)
Venugopal et al., studied the flotation characteristics of chalcopyrite ore using xan‐
thate as a collector and pine oil as a frother [57]. They performed rougher flotation tests
for the bulk feed and individual size fractions (coarser and finer). Their conclusion was in
agreement with what Ram et al., reported earlier [58]. They also observed that the flotation
performance was the maximum in the case of bulk flotation compared to that achieved
for individual size ranges, which may be attributed to a wider size distribution in bulk
feed [57,58].
Recently, Dhar et al. investigated the flotation of Nussir copper ore using three col‐
lectors: sodium Iso‐butyl xanthate (SIBX), di‐secondary butyl dithiophosphate (DBD), n‐
butoxy carbinol‐o‐n‐butyl thiocarbamate (BBT) and their mixtures [59–61]. Nussir deposit
is enriched with chalcocite and bornite as copper sulphide minerals with a liberation size
of 105 μm (80% of mass). From the flotation results (Figure 10), it is observed that Nussir
copper ore can float better in the sequence of BBT > DBD > SIBX. It was explained as due
to the highest negative zeta potential (ZP) value observed in BBT for copper sulphides,
confirming the adsorption of a negative anionic collector in metal sites that showed that
BBT is the most suitable collector for Nussir copper ore. The mixed collector
(BBT:SIBX::3:1) imparts a more negative ZP value compared to the individual collectors,
resulting in the production of concentrates with the highest grade and recovery compared
to the other mixtures [59–61].

Figure 10. Copper recovery and grade for the three collectors (BBT, DBD and SIBX) and their mix‐
tures in different proportion [59].

The effect of pulp aeration on chalcopyrite flotation in chalcopyrite–pyrite pulps of

different pyrite contents (i.e., 20 wt%, 50 wt% and 80 wt% pyrite) with sodium iso‐propyl
Minerals 2022, 12, 545 13 of 42

xanthate (SIPX) was investigated by Owusu et al. [62]. A significant increase in the chal‐
copyrite grade was observed in moderate aeration conditions, while the opposite effect
was noted at a high aeration rate. There is a positive correlation between the amount of
oxygen/air required for adequate chalcopyrite flotation and pyrite’s weight percent in the
pulp. When the weight percentage of pyrite was more that the pulp, a longer aeration time
was required to facilitate xanthate adsorption on the chalcopyrite surface and its oxidation
to form dixanthogen. The result concluded that chalcopyrite flotation was controlled by
the ratio of hydrophobic xanthate and hydrophilic metal oxide/hydroxide produced at the
solution‐mineral interface [62]. Most of the studies reported earlier involved chalcopyrite
mineral‐dominated ores. Additionally, these studies mostly focused on the recovery as‐
pects at different reagent suits. However, the surface oxidation of chalcopyrite may alter
the adsorption phenomena and indirectly influence the floatability and kinetics. These
days, there is a lot of interest in the coarse particle flotation process with different machine
designs (e.g., Reflux flotation cell, Jameson cell, Hydro float separator, etc.). Therefore,
detailed studies can be carried out on the floatability and kinetics of chalcopyrite with
these new cells (e.g., to enhance the bubble‐particle interactions in fluidized beds), as well
as alterations of the hydrodynamics inside the cell to obtain a better flotation of coarser
particles.

6.1.2. Bornite
Hangone et al., studied the individual and combined effects of thiol collectors (xan‐
thate, dithiocarbamates and dithiophosphates) on bornite‐rich copper sulphide ore from
the Okiep Copper Mine [63]. The experimental analysis found that, in the case of di‐ethyl
dithiophosphate (di C2‐DTP; Table 5), a higher recovery was obtained (Figure 11). This
was attributed to the differences in chemical reactions at the mineral surface (specifically,
the lacuna/inability to form cupric‐dithiolate while using di‐ethyl‐dithiocarbamate),
which has made it an inefficient collector for copper sulphide minerals, confirming the
findings of Finkelstein and Poling [64]. Higher copper recoveries were obtained using a
mixed collector system, i.e., Ethyl Xanthate:Diethyl Dithiophosphate and Ethyl Xan‐
thate:Diethyl Dithiocarbamate in a 90:10 ratio as compared to the recovery achieved with
only ethyl xanthate. A relatively minor enhancement in the copper recovery and grade
was observed with a mixture of Ethyl‐Xanthate:Diethyl Dithiocarbamate collector in a
90:10 ratio, respectively (Figure 12). This may be due to the enhanced flotation of slow‐
floating particles and modified froth structure of the mixed collectors’ synergistic effect
[63].

Figure 11. The total copper recovery versus collector dosage obtained with C2‐X, di‐C2‐DTP and di‐
C2‐DTC in the flotation of the Okiep copper ore [63].
Minerals 2022, 12, 545 14 of 42

Figure 12. Cumulative copper grade recovery with respect to C2‐X (individual xanthate), C2‐X
(90%):di‐C2‐DTP (10%) and C2‐X (90%):di‐C2‐DTC (10%) [63].

Table 5. Species responsible for the surface hydrophobicity of copper minerals [63].

Mineral Collector Species Responsible for Hydrophobicity

Bornite (Cu5FeS4) CuX
Chalcopyrite (CuFeS2) X2
C2‐X
Chalcocite (Cu2S) CuX, Cu(X)2
Covellite (CuS) X2, CuX
Bornite (Cu5FeS4) Cu(DTP)2
Chalcopyrite (CuFeS2) Cu(DTP)2
di‐C2‐DTP
Chalcocite (Cu2S) Cu(DTP)2, Cu(DTP)
Covellite (CuS) Cu(DTP)2
Bornite (Cu5FeS4) Cu(DTC)2
Chalcopyrite (CuFeS2) Cu(DTC), Cu(DTC)2
di‐C2‐DTC
Chalcocite (Cu2S) Cu(DTP)
Covellite (CuS) Cu(DTC)2

6.1.3. Chalcocite
In 1979, Heyes and Trahar investigated the flotation of chalcocite using xanthate as a
collector [65]. Their work revealed that the oxidation product cuprous xanthate (CuX) was
solely ascribed to flotation, as the existence of dixanthogen was thermodynamically ca‐
lamitous, which agreed with the findings of Gaudin and Schuman [66]. The following
oxidation chemical reaction between chalcocite and xanthate was advised by Harries and
Finkelstein [67]:
Cu2S + X− → CuS + CuX + e (7)
Further, the CuX formation mechanism was also proposed and described as the fol‐
lowing [67]:
Cu2S + 2X− → 2CuX + S+ 2e (8)
and
Cu2S + 2X− + 4H2O → 2CuX + SO42− + 8H+ + 8e (9)
Minerals 2022, 12, 545 15 of 42

An in‐depth study on porphyry copper ore using N‐allyl‐O‐alkyl thiocarbamate

(ATC), O‐alkyl –N‐ethoxycarbonyl thiocarbamate (ECTC) and N‐alkyl‐N‐ethoxycarbonyl
thiourea (ECTU) was carried out by Sheridan et al. [67]. In this study, the flotation effi‐
ciency using an ATC collector was compared with the ECTC and ECTU collectors. The
copper sample taken from an operating plant in South Africa contained mainly chalcocite
with minor amounts of covellite and chalcopyrite. Pyrite was the undesired mineral. This
ore contained 2% Cu, 5.5% S and 6.8% Fe. The effects of different process variables such
as collector chain length (C2, C4 and C6); collector concentration (0.01, 0.025 and 0.01
mol/t) and type of frother (Methyl Isobutyl Carbinol, DF250 and Methyl Isobutyl Car‐
binol:DF250 in a 80:20 ratio) were analyzed. The optimum result in terms of copper recov‐
ery and grade was obtained for C4 ATC, i.e., a medium‐chain length collector, which was
corroborated with the investigation of Wang [68] that xanthate with a longer chain length
produced a lower solubility compared to xanthate with two to five carbon atoms. The
predicted optimum result revealed 97% copper recovery with 33% Cu grade using 0.09
mol/t of C4 ATC as the collector and a combination of DF250:MIBC as the frother in a
65:35 ratio. Thus, ATC was established as a suitable and potential collector for copper
sulphide mineral flotation compared to ECTC and ECTU [68].
Hanson and Fuerstenau [69] studied the electrochemistry and wetting behavior of
chalcocite using diethyl dithiophosphate and ethyl xanthate as the sulphide collector and
also for chrysocolla using potassium salt of octyl hydroxamate as the oxide collector. It
was also concluded that the selective separation of copper minerals (sulphides or oxides)
is possible by carefully controlling the flotation pulp potential. The result confirmed the
promising effect of hydroxamate as a collector for non‐sulphide and oxidized copper ores
without using a sulphidizing agent [70]. Author has summarized the common reagents
used in copper sulphide flotation in Table 6.

Table 6. Common reagents for copper sulphide mineral flotation.

Ore Collector Frother pH Reference

Polypropylene Glycol
Sodiumisopropyl Xanthate (SIPX) 10.5 [62]
(Dowfroth 250; AR grade)
Methyl Isobutyl Carbinol
Isopropyl ethyl thiocarbamate 6.3–5.1 [71]
(MIBC)
Chalcopyrite Sodium butyl xanthate (SBX) Mixture of C5–C8 alcohol 8.0–8.5
[72]
N‐propyl‐N‐ethoxycarbonyl thiourea (PECTU) Mixture of C5–C8 alcohol 8.5–9.0
Sodium ethyl xanthate (NaEX) DowFroth 250 [73]
Methyl Isobutyl Carbinol
Potassium amyl xanthate (PAX) 10.0–10.5 [74]
(MIBC)
 Di‐ethyl dithiophosphate (di‐C2‐DTP) (Best)
Bornite  Di‐ethyl‐dithiocarbamate (di‐C2‐DTC) ‐ 9 [65]
 Ethyl Xanthate
 Potassium‐Octyl Hydroxamate (Best)
 Ethyl Xanthate ‐ 9.3 [75]
 Di‐ethyl dithiophosphate (di‐C2‐DTP)
Chalcocite  N‐allyl‐O‐alkyl thionocarbamates (ATC)
MIBC
 O‐Alkyl‐N‐ethoxycarbonyl thionocarba‐
Polypropylene 9.4 [68]
mates (ECTC)
Dowfroth 250
 N‐alkyl‐N‐ethoxycarbonyl thiourea (ECTU)

In general, most of the copper deposits involve chalcopyrite as the major mineral,
with the presence of other sulphide copper minerals (e.g., chalcocite and bornite) to dif‐
ferent degrees. However, most of the reported studies are limited to a particular mineral,
Minerals 2022, 12, 545 16 of 42

and very limited studies have been focused on the mineral mixture. Additionally, there is
a desire for further studies with a geo‐metallurgical approach to understand floatability
and kinetics.

6.2. Copper Oxide Minerals

In general, sulphide copper ores have been beneficiated using flotation in an eco‐
nomic way, and the oxide minerals in the sulphide deposit are ignored because of their
lower tenor and complexity in mineralogy [76]. The issue of the continual depletion of
copper sulphide deposits shifted the focus of researchers to beneficiate the low‐grade cop‐
per oxide deposit to meet its global market demand. Thus, copper oxide minerals also
play a correspondingly important role in copper production [77]. Various copper oxide
minerals often occur together in a deposit. They are generally found at a shallow depth of
the Earth’s crust, formed due to the weathering and oxidation of copper sulphide minerals
[10,11]. The most often found copper oxide mineral is malachite (CuCO3∙Cu(OH)2). The
other oxide minerals are cuprite, azurite, chrysocolla, etc. Malachite with other copper
oxide does not respond well to the conventional sulphide mineral collectors (e.g., xan‐
thate), and therefore, alternative flotation approaches are needed.
Many researchers believe that the froth flotation of oxide copper ores is a complex
method, and it needs the sulphidization stage. The oxide copper minerals have thick hy‐
dration film surfaces, which are hard to contact with air bubbles, implying that the flota‐
tion response of oxide is inferior to sulphide copper ores, technically and economically.
Moreover, oxide copper ore enrichment with low dissolution rates generally utilizes [78]:
(i) The froth flotation method after the sulphidization stage or
(ii) The mixture of flotation and hydrometallurgy or
(iii) Flotation segregation, whereas the hydrometallurgical route generally processes ox‐
ide copper ores with high dissolution rates.
Many researchers like Bulatovic have discussed a sulphidizing reagent for convert‐
ing the oxide mineral surface to sulphide to behave as a sulphide mineral and respond to
the sulphide collectors [79]. The efficiency of sulphidizing a reagent is highly dependent
on its concentration. A strict regulation of collector dosage and control is mandatory in
the plant—failing which, the flotation performance becomes poor [80–82].
Ziyadanogullari and Aydin studied the flotation of 40–45‐year‐old stockpiled ores
from Ergani Copper Mining, Turkey, which were found not suitable for the recovery of
the copper hydrometallurgical route [83]. They tried the flotation of such oxidized copper
ore by introducing sulphidizing treatment, and hence, they were treated in a sulphurized
medium containing different H2S and H2O gases ratios. The feed contained pyrite, chal‐
copyrite and oxidized copper ore with 2.03% Cu and 3.73% sulphur. The flotation of a
higher concentration of sulphurized sample gave approximately 100% recovery of copper
and sulphur. The flotation result with potassium amyl xanthate as a collector and
Dowfroth 250 as the frother at 8.7 pH produced 10% Cu with 100% recovery (Figure 13).
During the sulphurization process, some composition alterations like degradation in the
spinal structure, reduction of ions at higher state orders and differences in the crystalline
structure took place. These modifications led to the formation of a sulphide compound
and an increase in the degree of freedom. Thus, it was easier for the collector to get ad‐
sorbed by the sulphide compound to exert hydrophobicity and, finally, attach with the
bubbles and float [83]. In the present investigation, the results can be compared with the
conventional route to understand the potential of the sulphidization process. Addition‐
ally, the mechanical activation is another prominent area to alter the surface property in
such cases that can help to generate a fresh surface to enable the better selectivity of rea‐
gents.
Minerals 2022, 12, 545 17 of 42

Figure 13. The flotation recovery of Cu, Co and S at different pH values (30.63 g H2S + 200.00 g H2O)
[83].

6.2.1. Malachite
The most important industrially beneficiated copper oxide minerals are malachite
(Cu% = 57.4) and azurite (Cu% = 55.2), whereas the least important minerals are chryso‐
colla (Cu% = 36.1) and cuprite (Cu% = 88.8%). In 1972, Glembotskii et al. [84] investigated
the flotation of malachite and azurite by using the subsidization method. A feed with 1%
copper was floated and concentrated with 80% recovery and 19% grade.
The effect of five alkyl hydroxamates (Aceto hydroxamate, K‐butyl hydroxamate, oc‐
tyl hydroxamate, K‐octyl hydroxamate and tetradecyl hydroxamate) and two aromatic
hydroxamates (benzo hydroxamate and salicyl hydroxamate) were studied on the flota‐
tion of the synthetic malachite‐quartz ore mixture (Table 7). The zeta potential was taken
into consideration to understand the reagent adsorption on the surface of the mineral. It
showed that only benzo hydroxamate (aromatic) and octyl hydroxamate (alkyl) were pro‐
ductive in malachite recovery. Further, benzo hydroxamate was most selective, with a
comparatively lesser concentration than octyl hydroxamate to get the same malachite re‐
covery with slightly increased quartz, which corroborated the findings of Lee et al. [81]
and Lee et al. [85].
The effective result on the recovery of oxide copper minerals like malachite and cu‐
prite was reported by using alkyl hydroxamate as a collector, whereas finely disseminated
cuprite and chrysocolla were not effectively floated with alkyl hydroxamate [85]. The di‐
rect recovery of copper oxide minerals with different oxyhydryl collectors such as fatty
acids, amine, phosphinic acids and hydroxamic acids [81,82,86–88] was investigated. Fi‐
nally, hydroxamic acid was found to be effective in the recovery of malachite [79,81,85].
However, these findings have not been reconfirmed with real ore systems, which is still a
challenging task.

Table 7. Hydroxamate collectors used in malachite flotation [89].

Hydroxamate Abbreviation Structure Manufacturer

Sigma Aldrich (St.

Benzo BHA
Louis, MO, USA)
Minerals 2022, 12, 545 18 of 42

Alfa aesar (Haverhill,

Salicyl SHA
MA, USA)

Alfa aesar (Haverhill,

Aceto AHA
MA, USA)

K‐Butyl PBH Synthesized

Octyl OHA Synthesized

K‐Octyl POH Synthesized

Tetradecyl THA Synthesized

The effect of a chelating agent named KYL, consisting of improved ethylene phos‐
phate used as an activator, for the flotation of copper oxide from Yongshan, Yunnan, was
investigated by Yang et al. [88]. The ore contained 0.88% malachite and cuprite and 0.05%
native copper. The sample was ground to 90% passing −200 mesh in the comminution
circuit. Numerous flotation tests were conducted with sodium silicate, sodium sulphide
and KYL as modifying agents, whereas xanthate and pine oil were used as the collector
and frother, respectively. After four stages of rougher, a final concentrate of 22.87% copper
grade was obtained with 83.99% recovery from the ore containing 0.55% total copper in
the feed [90]. The performance of this study can be correlated and compared with the
locked cycle test to understand its efficiency.
The interaction between malachite and sulphide ion species has been studied by an
X‐ray photoelectron spectroscopy analysis, zeta potential determination, surface adsorp‐
tion and micro‐flotation experimentation [91]. The result of the malachite recovery was
interrelated with the contents of the sulphidization products and the residual sulphide
ion species in the pulp phase. The sulphidization of malachite in Na2S solution resulted in
the formation of copper sulphide species on the mineral surface with a negative charge.
The concentration of cuprous sulphide increased with an increase in Na2S. The cuprous
sulphide species product on the malachite surface resulted in cuprous monosulphide, cu‐
prous disulphide and cuprous polysulphide. Disulphide and polysulphide, among them,
play an active role in the sulphidization of the malachite surface. The increase in the
Minerals 2022, 12, 545 19 of 42

amount of Na2S showed a detrimental effect on the malachite flotation. The decrease in
recovery of malachite at a high concentration of Na2S was attributed to the sulphide ion
species remaining in the pulp phase leading to lesser collector adsorption on the sul‐
phidized malachite surface. Therefore, a decrease in the malachite hydrophobicity was
reduced [91].
Renfeng et al. [91] studied the effect of a new collector (ZH1, C3–5 carbon chain xan‐
thate) for increasing copper oxide recovery, mainly fine‐grained malachite (−10 μm). A
Pure copper sample (malachite and azurite) from the Dishui Copper Processing Plant of
China was used in the flotation experiments. These researchers concluded a possible bet‐
ter recovery of malachite, using ZH1, which increased from 80 to 95%, by using isoamyl
sodium xanthate (IPX) (Figure 14). Such a lower recovery by IPX was attributed to the fine
particle size distribution of malachite particles. Due to the presence of a minor amount of
alcohol in ZH1, it also produced some foam [92]. Hence it caused a sharp increase in the
recovery of fine‐grained malachite due to the rich bubble inclusions. ZH1 showed some
flocculation quality due to which fine malachite could be flocculated to produce relatively
coarse flocs to increase the probability of collision with the bubble and, thus, the better
recovery of fine‐grained particles [93,94].
Liu et al. investigated the selective flotation of a copper oxide mineral (artificial min‐
eral mixture) against quartz and calcite using three different types of synthesized Tetrazi‐
nan—a thione collector (HTT‐6‐hexyl‐1,2,4,5‐tetrazinan‐3‐thione, PrTT‐6‐propyl‐1,2,4,5‐
tetrazinan‐3‐thione and PhTT‐6‐phenyl‐1,2,4,5‐tetrazinan‐3‐thione) and octyl Hydrox‐
amic acid (OHA) [95]. Their order to impart hydrophobicity on the malachite surface was
noted as follows: HTT > OHA > PhTT > PrTT (Figure 15). From their flotation results, it
was observed that HTT results in relatively better and more selective flotation responses
of malachite against gangue minerals (i.e., quartz and calcite) as compared to the other
reagents (Figure 16). It is mainly due to the preferential adsorption of HTT on the mala‐
chite surface rather than quartz and calcite. Besides the longer heptyl group of OHA, HTT
resulted in a higher recovery and grade of malachite versus quartz and calcite, which may
be attributed to the formation of different bondings. Further, Liu et al. [96] developed a
unique chelating collector named 5‐(2,4,4‐trimethylpentyl)‐4‐amino‐1,2,4‐triazolidine‐3‐
thione (TMATT) for the improved separation of malachite from other gangue, and the
flotation responses were compared with conventional OHA. Improved flotation re‐
sponses were achieved by TMATT due to the stronger hydrophobization and higher se‐
lectivity against gangue [95].

Figure 14. (a) Relationship between the collector dosage and the recovery of fine‐grained malachite.
Distribution of malachite particles under the microscope (b) before and (c) after adding ZH‐1 [91].
Minerals 2022, 12, 545 20 of 42

Figure 15. Bubble contact angle measurement of malachite surfaces as a function of different (a) pH
and (b) collector dosages (HTT‐6‐hexyl‐1,2,4,5‐tetrazinan‐3‐thione, PrTT‐6‐propyl‐1,2,4,5‐tetrazi‐
nan‐3‐thione, PhTT‐6‐phenyl‐1,2,4,5‐tetrazinan‐3‐thione and OHA‐ octyl hydroxamic acid) [97].

Figure 16. Flotation recovery (a) and grade (b) of malachite in the presence of different reagents
(under 3 × 10−5 mol∙L−1 HTT (6‐hexyl‐1,2,4,5‐tetrazinan‐3‐thione) and octyl hydroxamic acid (OHA)
at pH ~9.4) [97].

6.2.2. Chrysocolla
Chrysocolla is a copper silicate mineral that is nonresponsive to the sulphidizing pro‐
cess and responds poorly to sulphidization‐xanthate flotation practice [98]. Laboratory
tests have been carried out on the flotation of copper oxides, and it has been concluded
that chrysocolla and malachite could be floated with a mercaptan collector. When a higher
xanthate homolog (hexyl, dodecyl‐Table 8) was used in large quantities, malachite parti‐
cles floated. Chrysocolla particles remained unfloated. The addition of a mercaptan col‐
lector in the grinding mill resulted in superior recovery. A model was developed to attach
mercaptan to the surface of chrysocolla, which included a reaction of mercaptan molecules
with a copper oxide surface site. This reaction led to insoluble mercaptide and the splitting
of a water molecule at the surface [99]. A new reagent was synthesized containing an ali‐
phatic‐aromatic structure, with a hydrocarbon chain and chelating group of an amino‐
thiophenol. It proved to be an effective collector for chrysocolla flotation in a pH range of
5.5–6. The infrared results showed that chelates of the amino‐thiophenolate were formed
on the chrysocolla surface under the best flotation conditions, which may have imparted
hydrophobicity to the oxide mineral surface [100].
Minerals 2022, 12, 545 21 of 42

The flotation of oxide copper ore containing chrysocolla and quartz with 2.13% Cu
was studied by Nagaraj and Somasundaran [100]. By using the collector emulsion con‐
taining 0.034 kg/t Tergitol and 0.5 kg/t LIX65N in hexane (3.0 kg/t), a concentrate was ob‐
tained within 4 min. of flotation and two stages of cleaning. The final concentrate con‐
tained 21.3% copper with 69% recovery [100].

6.2.3. Cuprite
The cuprite—type oxide copper from copper ore containing 1.29% Cu of Dishui Cor‐
poration, Xinjiang, China, was subjected to research work by Xiong et al. [101]. Sodium
iso‐amyl xanthate (SIAX) was used as the collector, sodium sulphide (Na2S) as the sul‐
phidization reagent, methyl iso butyl carbinol (MIBC) as the frother and ammonium sul‐
phate ((NH4)2SO4) as the modifier. The results showed that ammonium sulphate is bene‐
ficial for the sulphidization of the copper oxide ore. At the optimum flotation conditions
where 1000 g/t (NH4)2SO4, 1000 g/t Na2S, 800 g/t SIAX and 40 g/t pinitol oil were used, a
copper concentrate with 18.23% copper grade and 73.46% recovery was obtained [101].
Han et.al. studied the surface sulphidization of cuprite mineral using Na2S and con‐
cluded that the excessive quantity and/or dosage of a sulphidizer has a detrimental effect
on the cuprite flotation activity [102]. Later on, they investigated the beneficial effect of
pre‐oxidation by NaClO (sodium hypochlorite) as an oxidant on the sulphidization of cu‐
prite [103]. The direct sulphidization of the cuprite surface is ineffective because of its
inherent hydrophilic nature. The oxidant helped in the transformation of the Cu2O species
((Cu (I) low affinity towards sulphur ions) to CuO (Cu (II) active affinity towards sulphur
ions) species, which enhanced the sulphidization process using Na2S. Thus, higher flota‐
tion recovery was achieved using sodium butyl xanthate, which also corroborates Xiong
and Zheng’s results [72].

Table 8. Surfactants for copper oxide flotation.

Ore Mineral; Sample Source
Collector Remarks References
Gangue Mineral (Ore Deposit/Country)
Benzo Hydroxamate[Best]
Salicyl Hydroxamate
Aceto Hydroxamate
AMR Mineral and Metal Inc., Synthesized ore (mixture of
Malachite; Quartz K‐butyl hydroxamate [89]
Canada malachite and quartz)
Octyl Hydroxamate
K‐octyl Hydroxamate
Tetradecyl Hydroxamate
Hexyl Mercaptan, Dodecyl Mercaptan
Miami, Arizona Natural Ore [99]
Chrysocolla; Quartz (Higher Xanthate)
Miami, Arizona Aminothiophenol Natural Ore [98]
Copper
Cuprite; Quartz, calcite Company of Dishui Corpora‐ Sodium Iso amyl Xanthate (SIAX) Natural Ore [104]
tion, Xinjiang, China.
Cu Sulphide (Chalcopyrite
Synthesized ore (Mixture of
and bornite) and Sherwood Copper’s Minto
N‐octyl hydroxamate (AM28) Cu Sulphide Cu Ox‐ [81]
Cu Oxide (Malachite with mines, Canada
ide::(70:30))
small Azurite); Quartz

6.3. Mixed Copper Ore

Rule investigated an ore containing 1.77% total copper (1.67% and 0.1% as copper
oxide and copper sulphide, respectively). Mineralogically, the ore contained 80% of the
minerals atacamite and paracamite. The ore sample was ground to 97%, passing 150 μm,
and all flotation experiments were performed at pH 8.7. A mixture of potassium octyl
hydroxamate (0.2 kg/t) and potassium amyl xanthate (0.4 kg/t) was added as the collector
and conditioned for 20 min. After the addition of pine oil and methyl iso butyl Carbinol
mixture in a 1:1 ratio (as a frother), a copper concentrate of 83.6% recovery with a copper
Minerals 2022, 12, 545 22 of 42

grade of 6.88% (6.52% copper oxide and 0.36% copper sulphide) was obtained [105]. How‐
ever, the kinetics data of each type of mineral were not evaluated, which is critical in de‐
signing the reagent suite, along with the conditions needed for better collector adsorption.
Additionally, the liberation and particle size distribution of each type of minerals are crit‐
ical in analyzing the floatability aspects.
The copper oxide deposit of Dali in Yunnan, China, contained 0.69% Cu (0.46% and
0.23% in the form of sulphide and oxide minerals of copper, respectively) and 11.24 g/t
silver. The ore was upgraded by the sulphidization process, followed by xanthate collector
flotation. Sodium sulphide as a sulphidization agent (100 g/t) and butyl xanthate and am‐
monium dibutyl dithiophosphate as a combined collector were used during the experi‐
ments. Applying closed‐circuit tests, a copper concentrate with 18.34% copper grade and
70.13% copper recovery was obtained [106]. A mineralogical study also revealed the pres‐
ence of chalcopyrite, malachite and chyrosocolla as major copper minerals with minor
amounts of chalcosine, bornite and covellite in the beneficiation of copper oxide ore from
Yunnan [106]. The best test conditions were determined as 1000 g/t, 1000 g/t, 150 g/t and
30 g/t of lime, sodium sulphide, sodium n‐butyl xanthate and terpenic oil, respectively.
Even though it was a mixed ore, the focus was on the flotation of sulphide minerals. Fi‐
nally, after closed‐circuit tests of two roughing, two cleanings and one scavenging, a con‐
centrate containing 20.20% Cu with 68.11% recovery was obtained [106].
The recovery of copper from the Abu‐Swayel ore deposit by reverse flotation was
attempted by Abdel‐Hady and his co‐researchers [107]. The deposit contained mainly
copper oxide minerals, i.e., malachite, calcanthite and brochiantite, which show a poor
response towards flotation. The other minor associated minerals were chalcopyrite, bra‐
voite, violarite, hematite, goethite and ilmenite. The reverse flotation tests were carried
out using oleic acid as the collector and pine oil as the frother to retain copper oxide min‐
erals in the pulp. The results showed that about 90% copper recovery with 10% copper
grade could be achieved by using a 1.5 kg/t oleic acid collector at pH = 10, 7 dm3/min air
flow rate and 5 min flotation time. The copper mineral lost in the froth product may be
recovered by cleaning of the concentrate under the same flotation conditions [107].
A flotation study was carried out on a low‐grade complex copper ore sample by
Singh and his co‐researcher [108]. The sample was of low grade, with a copper content of
0.95% and silica and alumina as the major impurities. The primary copper‐bearing min‐
eral was chalcopyrite, followed by bornite and covellite, with tetrahedrite, malachite and
azurite. The flotation tests were carried out using sodium iso propyl xanthate (SIPX) as
the collector for the sulphide mineral, methyl isobutyl carbinol (MIBC) as the frother, so‐
dium hydroxide as the pH regulator and sodium sulphide as the sulphidizing agent. The
presence of oxidized copper minerals and slimes considerably affected the flotation per‐
formance. However, the use of sulphidizing agent helped to enhance the copper recovery
by converting the surface of oxide minerals into sulphide and providing it as suitable for
flotation using xanthate. The use of sodium silicate as a depressant for siliceous gangue
can also improve the copper grade. After rougher flotation followed by two cleaning
stages, a copper concentrate with 29.25% Cu at 81.7% recovery was obtained.
A patentable work was done on a Chilean copper oxide sample, which had a grade
of 2.6% copper oxide and 0.28% copper sulphur. The sample was ground to 60%, passing
75 μm. The reagents used in the tests were potassium amyl xanthate (PAX), pine oil, so‐
dium sulphide, 5‐methyl benzotriazole, light oil and mobile oil no. 20. Finally, a flotation
concentrate with 27.8% Cu grade and 71.2% recovery was obtained [109].
A synthetic mixed copper sample was studied by blending 70% sulphide copper and
30% oxide copper from Sherwood Copper’s Minto Mine Yukon in Canada with a grade
of 3.6% Cu. Potassium amyl xanthate (PAX) and potassium n‐octyl hydroxamate (AM28)
were also used as the collectors. The sulphidization reagent, i.e., sodium hydrogen sul‐
phide (NaHS), was used to modify the oxide surface. The dosages of AM28 and MIBC
were maintained at 1200 g/t and 50 g/t, respectively. In the cleaning stages, an extra 100
g/t of AM28 and 50 g/t of MIBC were added. This process yielded a concentrate assaying
Minerals 2022, 12, 545 23 of 42

33.9% copper with 78.5% recovery. It was concluded that AM28 successfully beneficiated
malachite and minor azurite in Minto’s oxide ore [71,81].
To develop a flotation procedure for an oxide copper ore, samples from a region of
Central Africa were subjected to flotation tests [110]. The feed grade of 4.5% Cu was con‐
tributed by 88% copper oxide minerals and 12% sulphide minerals. A concentrate of 18%
Cu grade was obtained with potassium amyl xanthate as the sulphide collector; n‐octyl
hydroxamate, Oleofloat 6540, rinka lore, diesel, sodium carbonate and tall oil as the oxide
collectors; sodium hydrogen sulphide (NaHS) as the sulphidizer and Dowfroth 200 as the
frother. The recoveries achieved from the experiments were less than 50%, despite trials
with varying reagent combinations and conditions. The poor recoveries were attributed
to copper silicates around 70% by mass, which made it too complex to be floated by the
conventional method. The sulphidization procedure at a high flotation temperature and
extended flotation residence time could give the best results [110]. Similarly, an experi‐
mental research work was reported on an oxide copper ore from Guizhou, China. The ore
contained 1.15% Cu with chalcopyrite, chalcocite, covellite and bornite as the sulphide
minerals and malachite and chrysocolla as the oxide minerals, whereas quartz, dolomite
and mica were the main gangue minerals. Using a new collector, in a closed‐circuit flota‐
tion, a concentrate of 22.1% Cu grade with 88.52% recovery was reported [110].
Due to the presence of higher oxidized and carbonaceous mud, traditional flotation
resulted in the poor recovery of copper from copper–cobalt sulphide–oxide mixed ores
[111]. Before the direct flotation of these types of ores, desliming and decarbonization
were suggested via the flotation process, using alcohol pine oil, alcohol butyl ether and an
oil combined with a frother The used frother showed a significant result in terms of de‐
sliming and selective copper flotation. After that, the sample was subjected to copper ox‐
ide activation, using both sodium sulphide (Na2S) and sodium hydroxide sulphide
(NaHS). Amyl xanthate was used as a collector at rougher, cleaner and the scavenging
stages. A concentrate with 21.2% copper grade was obtained with 88.55% copper recovery
from the sample, containing 2.63% Cu and 0.04% Co [111].
The copper oxide ore of the Yangla Mine in Yunnan, China, with 1.02% copper was
subjected to flotation with a mixture of potassium amyl xanthate (PAX) and hydroxamate
AM28 as the collector. A rougher concentrate was reported with a 3.19% Cu grade and
38.4% recovery [112]. Another flotation study was carried out on copper oxide ore from
Yunnan, China, containing covellite, malachite and bornite as copper minerals and
quartzite, dolomite, plagioclase, chlorite, calcite, hematite and pyrite as major gangue
minerals. With a reagent combination of butyl xanthate as the collector, pine oil as the
frother, sodium sulphide as the sulphidizing agent and lime as the pH regulator, after
three stages of cleaning, a concentrate with 18.06% copper and 80.81% recovery was re‐
ported [77].
Ausmelt developed an important hydroxamate, i.e., AM28 (potassium n‐octyl hy‐
droxamate). It has been implemented in flotation and has been found as an effective col‐
lector for oxide copper minerals and native copper over a wide pH range. It is also con‐
firmed as an efficient collector for chrysocolla in an alkaline pH range, i.e., pH 7–10 [113].
Mexican mixed‐type copper ore contained ramsbeckite and malachite as the copper oxide
minerals and chalcopyrite as the copper sulphide mineral, with SiO2 as the main gangue
mineral. The total copper assay was 1.19%—out of which, oxide copper was 0.84% and
sulphide copper was 0.35%. The combination of flotation and leaching were studied. Us‐
ing sodium sulphide and butyl xanthate, a concentrate with 19.01% copper grade and
35.02% recovery was obtained. Around 83.33% oxide copper was recovered from the tail‐
ing via the leaching method under suitable conditions stirring for 1 h at 25 °C with a mix‐
ing speed of 500 rpm, 1 M H2SO4 and mass ratio (slurry/liquid) of 3. A final yield of 89.18%
was obtained after the completion of flotation and leaching, which was better than the
single leaching or flotation technique. It was concluded that a combination of flotation
and leaching was convenient for the beneficiation of Mexican mixed copper ore. Hence,
Minerals 2022, 12, 545 24 of 42

the “flotation‐agitation‐leaching‐solvent extraction‐electro‐winning” process route was

able to produce a pure copper of 99.9% [114].
A bench‐scale test on the beneficiation of mixed oxide–sulphide ore of copper from
the Malanjkhand deposit was studied. The effect of sodium isopropyl xanthate (SIPX) and
sodium diethyl dithiocarbamate (DTC) as collectors; sodium silicate, guar gum, Mang‐
nafloc‐140 and Mangnafloc‐351 as depressants and pine oil as the frother were systemati‐
cally studied and optimized. The improved result was obtained with SIPX and sodium
silicate at pH 9. The results obtained from dithiocarbamate were quite good compared to
SIPX, but it has not been reported in the literature about their industrial‐scale application
[115]. For better understanding the reagent suite to float the mixed ore, a detailed list of
used reagents, along with the case details, is summarized in Table 9. From Table 9, it can
be found that Potassium octyl hydroxamate (POH), Potassium Amyl Xathate (PAX) and
Sodium Iso‐propyl Xanthate (SIPX) have been used at different proportions to float the
copper minerals effectively from the mixed ore. The commonly used frother is MIBC or a
mixture of IMPC and pine oil. Additionally, surface modifiers in the form of sulphidizers
such as Na2S and (NaSH) have been used to enhance the flotation selectivity. There is
enough scope to study the reagent chemistry and their synergistic effects on the mixed
ore’s floatability.

Table 9. Reagents for the mixed copper ore (sulphide and oxide).
Deposit
Ore Collector Frother Modifier Remark Reference
/Country
Patentable work for the ef‐
Atacamite + para‐ Hanna Mining Potassium octyl hydroxamate Pine Oil:
fective flotation of mixed cu
camite + chalcopy‐ Company, (POH): Potassium Amyl Xathate MIBC: ‐ [104]
ore using hydroxamate col‐
rite Ohio. (PAX): 1:2 1:1
lector
NaOH (Ph), Single Rougher step fol‐
Chalcopyrite ([ma‐ Sodium Iso Propyl Xanthate (SIPX) Na2S (Sul‐ lowed by three stage clean‐
Indian copper
jor) + Malachite, Potassium Octyl hydroxamate MIBC phidizer) and ing yield final concentrate [109]
mine
Azurite (traces) (POH) Na2SiO3 (De‐ of 31.77% cu from 0.95% Cu
pressant) feed
Sulphide (Bornite + AM28 recovered copper ox‐
Sherwood Cop‐ Potassium Amyl Xanthate (PAX) +
Chalcopyrite) and Sulphidizer ide mineral without affect‐
per’s Minto Potassium n‐octyl hydroxamate MIBC [116]
Oxide (Malachite + (NaHS) ing recovery of sulphide
mines, Canada (AM28)
Azurite) minerals
Potassium amyl Xanthate (PAX)‐
(Cu Oxide (88%) + Sulphide collector Sulphidizer
Central Africa Dowfroth 200 Mixed natural ore [116]
Cu Sulphide (12%)) N‐Octyl hydroxamate and (NaHS)
Oleofloat 6540‐Oxide collector
Copper Mixed ore Malanjkhand Sodium Iso‐propyl Xanthate (SIPX) Only copper sulphide re‐
(Chalcopyrite + copper mine, Sodium Diethyldithiocarbamate Pine Oil Sodium Silicate covery is focused even after [115]
Malachite) India (SDTC) its mixed type

6.4. Effect of Mineralogy on Copper Mineral Zeta Potential

In colloidal chemistry, the zeta potential is used to study the characteristics of min‐
erals in a liquid dispersive system. Thus, it plays an important role in the physicochemical
separation processes, i.e., flotation and flocculation. The relation between mineral electro‐
chemistry and the practice of flotation has been extensively discussed for decades [117–
120]. The zeta potential value remains positive for pH lower than the IEP and vice versa.
IEP is defined as the pH, where the net charge on the mineral surface is zero. According
to Ottewill, the aggregation tendency of mineral particles is dominant within −30 mV to
+30 mV zeta potential [121], which was later confirmed by Mokone et al. [122] and also
ascribed that copper sulphide mineral in suspension was found to be stable at a more
negative zeta potential. It was also explained that, at the IEP, the colloidal system is least
stable (i.e., aggregation of the copper mineral particle is confirmed and, hence, affects the
Minerals 2022, 12, 545 25 of 42

flotation process). Mineralogical association of an ore mainly controls the colloidal sys‐
tem’s pH, adsorption of the reagent on the mineral surface and, ultimately, zeta potential,
which is responsible for effective flotation.
From the literature, it was found that Malanjkhand chalcopyrite has a positive zeta
potential up to its isoelectric point, which was found to be <3 pH [123]. The same IEP of
chalcopyrite was previously reported by many researchers [43,124,125]. The IEP of pure
chalcopyrite was reported around a pH of 5.7 [68,78]. The shifting of IEP towards a lower
pH was due to the presence of a higher amount of quartz in Malanjkhand copper, whose
IEP was at a pH of 2, as per the previous literature [126]. Copper sulphide minerals are
oxidized easily due to their surface reactive nature, and their order of oxidation is given
as follows [127]: Chalcocite > Tennantite > Enargite > Bornite > Covellite > Chalcopyrite.
The IEP of high‐purity malachite was reported at a pH of 8.4 [128], which was nearer to
the IEP value reported by Liu et al. [129,130]. Li et al. [130] studied the adsorption mech‐
anism of the chelating reagent on the surface of the malachite mineral from the Lupe Mine
in Mexico. During this investigation, the IEP of the malachite ore (in the absence of the
reagent) was found at a pH of 9.1, which corroborates with the findings of Liu et al. [129]
(i.e., at a pH of 8.7). The slight change in the IEP (from pH 8.7 to 9.1) may be due to pseudo
malachite in the Lupe Mine deposit. Many other authors have outlined that chrysocolla
has no IEP [131,132], whereas a researcher informed the IEP of chrysocolla at pH 2 and
pH 6.5 [133]. The varying IEP values of chrysocolla may be reflected due to the variability
in its mineralogical composition. Based on the above literature, the optimum pH ranges
reported as the IEP for different copper minerals are listed in Table 10. It is concluded that
the oxidation of copper sulphide minerals is confirmed by the zeta potential analysis. Its
variation (zeta potential value) with respect to the pH reveals the extensive presence of a
copper hydroxide layer covering the sulphur‐rich surface, which is responsible for esca‐
lating the oxidation environment. From Table 10, it is also found that chalcopyrite can be
present at a lower IEP, which may be due to the presence of silicate gangue minerals,
along with the ore. Similarly, the malachite is present at a higher range of IEP (8.4–9.1). In
this direction, detailed studies are necessary to analyze the surface charge of the mixed
ores, as well as their surface oxidation.

Table 10. Iso Electric Points (IEP) of different copper minerals.

Mineral Ore Deposit IEP (at pH) Remark Reference

Malanjkhand Copper Lower IEP is due to the presence of
Chalcopyrite 2.9–3.3 [43,124,125]
Mine, India abundant silicate gangue
Guangxi Province, China 8.4–8.7 High purity mineral [128–130]
Malachite
Lupe Mine, Mexico 9.1 Presence of Pseudo malachite (5%) [134]
Dongchuan, Yunnan
Not found Pure Mineral with 40% SiO2 [131]
Chrysocolla Province, China
Exotica Mine, Chile Not found Purest Lump with 43% SiO2 [132]

6.5. Bio‐Collector for the Flotation of Copper

Thiol collectors (e.g., xanthate, thionocarbamate and dithiophosphate) are exten‐
sively used as reagents for the flotation of copper minerals. These “sulphur”‐based collec‐
tors are costly and can produce toxicity with an abhorrent odor [69,78]. The use of xanthate
can cause a detrimental effect on health and the environment, as it is highly inflammable
and emits virulent carbon disulphide (CS2) gas during its production [135,136]. Moreover,
in 1998, Boening also stated that xanthates are dangerous for aquatic habitats [137]. These
drawbacks lead to the emergence of alternative flotation reagents to xanthate for copper
sulphide minerals with a higher selectivity and eco‐friendly nature. Bauer et al. [138] and
Green et al. [139] had patented the recovery of chalcopyrite from a feed containing 0.58%
Cu, using different oils as a collector, in a replacement for the thiol collector (thio phos‐
phate). The flotation result produced a concentrate of grade 8.43% Cu with 82% recovery.
Minerals 2022, 12, 545 26 of 42

Owusu and his co‐researcher studied the selective flotation of chalcopyrite from pyrite
using fatty acid‐based oils such as canola oil and palm oil instead of sodium isopropyl
xanthate [140]. The flotation results showed an improved Cu recovery and grade when
200 g/t canola oil was used (Figure 17). Thiol based collectors are widely used in copper
mineral flotation, mainly due to their high potential towards selective flotation, lower
prices and easy availability. However, many researchers have shifted their focus towards
bio‐collector flotation, where fatty acid‐based oils (canola oil/palm oil) are used as a sub‐
stitute to the conventional sulphydryl collector for the recovery of sulphide copper min‐
erals. Bio‐collectors have yet to prove their applicability with the ore variations. Addition‐
ally, there is not much literature on the variations in the temperature of the slurry, which
is very critical in plant operations.

Figure 17. Chalcopyrite and pyrite recoveries, as well as chalcopyrite grade data, as a function of
canola oil dosage for a 50:50 chalcopyrite–pyrite mixture [140].

6.6. Effect of Water Quality on Copper Flotation

Many researchers have investigated the water quality in copper flotation [141–144].
According to Alvarez and Castro, pure chalcopyrite’s flotation performance is affected by
using sea water [141]. Castro also reconfirmed this observation; the deleterious effect was
observed in chalcocite flotation [141,142]. Bakalarz et al. studied the effect of varying qual‐
ity water (i.e., natural saline water, saline + tap water, saline +NaCl and tap water) on
copper flotation [145]. They concluded that the dilution of tap water with saline water in
a ratio of 70:30 produced a better copper flotation response as compared to the other water
samples (Figure 18). Smith and Heyes investigated chalcopyrite‐bornite ore’s flotation and
reported that chalcopyrite recovery is not enhanced by using seawater, while the flotation
kinetics moderately improve. On the other hand, bornite recovery was diminished due to
the entrainment [143].
Minerals 2022, 12, 545 27 of 42

Figure 18. Result of the copper ore flotation response in different water types [145].

7. Problems Associated with Copper Tailings

Currently, the mining sector has encountered problems related to off‐grade copper
deposits, while their demand in the global market has hiked [146]. Hence, tailing dams
are considered as a potential secondary source to meet the requirements. Falagan et al.
[147] stated that the past beneficiation techniques are less efficient in processing tailing.
Since 1960, the copper grade of tailing dams has decreased from 0.74 to 0.14% [148], and
the past tailing ponds consist of a higher grade compared to the current deposits. There‐
fore, their reprocessing is profitable to the industry in various ways. The processing of
tailings is not only cost‐effective; it also reduces the environmental pollution [18,149–151].
A number of studies were focused on the recovery of copper from its flotation tailings
[18,22,152]. Ramakokovhu et al. [22] investigated the beneficiation of copper tailings from
the Konkola Copper mine in Nchanga, Zambia. They studied the leaching characteristics
of copper tailing before and after upgrading by using a Knelson gravity concentrator. The
raw tailing contained 0.61% Cu, which was upgraded to 1.2% Cu after physical treatment
with Knelson (Table 11).

Table 11. Elemental composition of the raw tailing feed and upgraded feed [22].

Element (Wt.%)
Stream
Cu Fe Al Mg O
Raw tailing feed 0.61 2.44 9.17 3.42 50.16
Upgraded feed 1.02 1.64 6.54 1.52 54.97

Katwika et al. reprocessed copper–cobalt tailing from the New Concentrator of

Kipushi using a Knelson gravity separator. Due to the copper–cobalt fine dissemination
in the gangue matrix, a traditional gravity unit may not be effective. The copper tailing
was upgraded to 31.57% cu and 7.44% Co, with recoveries around 65% Cu and 67% Co,
respectively (Figure 19) [20]. Continuous depletion of high‐grade copper ore deposit has
constrained us to utilize the old tailings as a secondary resource. Numerous copper tailing
beneficiation studies have been reported in the literature using a Knelson gravity separa‐
tion as a preconcentration due to the liberation of copper mineral at a very finer‐sized
fraction where studies with a falcon gravity separator are limited. Apart from these meth‐
ods, selective reagent combinations may be practiced in floc‐flotation methods for the re‐
covery of finely disseminated copper sulphide minerals.
Minerals 2022, 12, 545 28 of 42

Figure 19. Schematic for the separate treatment of tailings (PFF: Pre‐floated feed, PFT: Pre‐float tails,
CT: cleaning tails, ST: scavenger tails and FT: final tails) [20].

8. Different Aspects of Copper Plant Flowsheet/Practice

8.1. Dexing Copper Plant, China
A refractory copper porphyry ore was investigated through both bench‐scale and
industrial‐scale flotation experiments to concentrate copper minerals at the Dexing Cop‐
per Mine of Jiangxi Province in China by using N‐propyl‐N‐ethoxycarbonyl thiourea
(PECTU) and sodium butyl xanthate (SBX) as the collectors (Figure 20). They observed
that PECTU has a strong collecting power for copper sulphide minerals and enhanced
selectivity against iron sulphide minerals under moderately alkaline conditions. A com‐
bination of PECTU and SBX resulted in an increase in the Cu grade (from 0.44 to 23.16%),
with 75.6% copper recovery in the final concentrate, whereas single SBX produced a final
concentrate with a 22.23% cu assay and 74.57% copper recovery. It also provided a better
flotation separation of Cu/Fe sulphide minerals at a pH of 10.5 with comparatively less
lime addition. The reasons for the better flotation performance of PECTU have been ex‐
plained, as it had a moderate electron‐donating power, and, also, the covalent bond’s en‐
ergy between PECTU and iron sulphide minerals may be low enough to improve its non‐
selectivity for iron sulphide minerals [71].

Figure 20. The flow sheet of bulk flotation by separation in the Dexing Copper Mine [71].
Minerals 2022, 12, 545 29 of 42

8.2. Sungun Copper Plant, Iran

The combined effect of four flotation reagents, i.e., Z11 (sodium iso‐propyl xanthate)
and AP407 (combination of mercapto benzothiazole and dithiophosphate) as the collec‐
tors and AF56 (ether polyglycol) and AF70 (Methyl Isobutyl Carbionl) as the frothers were
evaluated by Vazifeh et al. [153] using a statistical technique in the rougher concentrate
plant of Sungun Copper in Iran (Figure 21). The feed contains mainly chalcopyrite, chal‐
cocite and covellite with 0.61% Cu. Two levels of a four‐factorial design were used for the
modeling and optimization of these flotation reagents. The high correlation coefficients of
the model equations for the grade (R2 = 0.89) and recovery (R2 = 0.96) indicated that the
predicted values were in good coordination with the observed values. With using the op‐
timum dosage of reagents, it was possible to produce a concentrate of maximum copper
recovery and grade [153].

Figure 21. Flow sheet of the Sungun Copper Flotation plant [153].

8.3. Telfer Copper Processing Plant, Western Australia

Seaman et al. studied the upgrade of the Telfer copper processing plant in Western
Australia by adding new cleaning and regrinding circuits [153]. Previously, the copper
minerals were initially recovered, followed by pyrite (Figure 22). After reopening in 2004,
it has faced many challenges, as a low‐grade copper concentrate was produced due to the
uncontrolled entrainment of non‐sulphide gangue. Thus, they have modified the existing
circuit by installing two ISAMill for ultrafine grinding (for the copper and pyrite flotation
circuit), two Jameson cells for enhancement of the fine gangue rejection and a bank of five
Outotec flotation cells for the recovery of copper and gold from the pyrite reground
stream (Figure 23) [154].
Minerals 2022, 12, 545 30 of 42

Figure 22. Pre‐configuration plant flow sheet of Telfer [154].

Figure 23. Post‐configuration plant flow sheet of Telfer [155].

8.4. Mosabani and Malanjkhand Copper Plant, India

Sastri et al. explained the copper plant flow sheet of the Mosabani and Malanjkhand
copper mines, India [156]. The ROM grade of the Mosabani copper plant (Figure 24) is
around 1.5% Cu and crushed in a close circuit (by two parallel jaw crushers, screening and
then the screen’s overflow was further crushed in a cone crusher). The products were sub‐
jected to ball mill operation in a closed circuit with the spiral classifier. The classifier’s
overflow was fed into the flotation circuits, with SIPX as the collector, pine oil as the
frother and soda ash as the pH regulator. The final concentrate obtained from flotation
cells with a higher grade (25% Cu) were filtered in a vacuum disc filter. The final tailings
Minerals 2022, 12, 545 31 of 42

with 0.05% Cu were dumped in the tailings dam. The ROM of the Malanjkhand copper
plant (1.2% Cu) (Figure 25) was the feed for the closed‐circuit crushing unit (gyratory
crusher‐screen‐secondary crusher‐screen‐tertiary crusher), and the products were trans‐
ferred into the ball milling unit in the closed circuit with hydrocyclone. The overflow of
hydrocyclone was sent to the flotation circuit units. A vacuum disc filter sorted the final
concentrate obtained from the second stage cleaner with a high‐grade copper content (25%
Cu). Similarly, the final tailings of 0.08% Cu were discarded into the tailing dam.

Figure 24. Mosabani copper concentrator plant flow sheet (India) [156].

Figure 25. Malanjkhand copper concentrator plant flow sheet (India) [156].
Minerals 2022, 12, 545 32 of 42

8.5. Cerro de Maimón Copper Plant, Dominican Republic

The Cerro de Maimón deposit’s mineralogical analysis confirms the presence of chal‐
copyrite, pyrite and sphalerite as the major minerals, along with covellite, bornite and
chalcocite. There are two different plants, a sulphide plant (recovery of copper and zinc)
and oxide plant (recovery of gold and silver) [157]. In the sulphide plant (Figure 26), the
feed content was 2.7% Cu. The feed ROM was subjected to primary grinding followed by
rougher flotation. The concentrate obtained was sent to the regrinding circuit, followed
by cleaner flotation. The tailings, i.e., rougher flotation and cleaner flotation, were taken
into another flotation circuit to recover zinc as a coproduct. The final cleaner stage pro‐
duced a concentrate with 28% Cu at 83.3% recovery (Table 12).

Figure 26. Flow sheet of the Cerro de Maimón copper plant (Dominican Republic) [157].

Table 12. Summary of the copper plant flow sheets.

Sl. Place and CuFG CCG; CuCR CuTG Beneficiation

Mineralogy Reagents References
No. Country (%) (%) (%) Units
Dexing cop‐ Classification
Cpy, cc, dg, bor, 23.16. SBX: PECTU as collector,
1 per Mine, 0.443 0.11 and Flotation [71]
mal, cup, cv, qtz 75.6 Lime pH modifier
China (3‐stage)
SIPX and AP407 as collector;
Cpy, Sungun Cop‐ Classification
2 0.61% 3.78; 87.03 0.09 Ether Polyglycol and MIBC as [153]
cc, cv, py per, Iran and Flotation
frother.
Mosabani
copper Classification SIPX as collector, Pine oil as
Cpy, py, 25.
3 mines, 1.5% 0.05 and Flotation frother, soda ash as pH modi‐ [156]
po, asp, qtz 96.86
Singhbhum, (2‐stage) fier
India
Cpy, cv, dg, py, Malanjkhand Classification
SIPX as collector, Pine oil as
4 mal, azu, qtz, copper 1.2% 25; 83.6 0.08 and Flotation [156]
frother, Lime as pH modifier
kfs mines, (3‐stage)
Minerals 2022, 12, 545 33 of 42

Balaghat, In‐
dia
Cerro de Grinding,
Maimón cop‐ rougher flota‐ Aero 9810 as collector, MIBC
Cpy, sph, cv,
5 per mine,Do‐ 2.7 28; 83.3 0.49 tion, regrind‐ as frother, Lime as pH modi‐ [157]
bor
minican Re‐ ing, and cleaner fier
public flotation
cpy—halcopyrite, cc—chalcocite, dg—digenite, bor—bornite, cv—covellite, mal—malachite, cup—
cuprite, azu—azurite; po—pyrrhotite, asp—arsenopyrite, py—pyrite, qtz—quartz, kfs—k‐feldspar,
sph—sphalerite, CuFG—feed copper grade, CuCG—concentrate copper grade, CuTG—tailing copper
grade and CuCR—recovery of copper.

9. Future Prospect of Pretreatment Methods for Copper Minerals

From the point of view of copper’s utilization in the future as a renewable and sus‐
tainable resource, we must adapt and develop an advanced process route to use all the
low‐grade copper deposits, tailing dams and overburden to meet the global supply–de‐
mand chain requirements.

9.1. Microwave Pretreatment

The microwave pretreatment method has been studied in the copper mineral to in‐
vestigate its effect on the comminution characteristics [158–160]. The sieving breakage test
outcome revealed a better efficiency of size reduction (increase up to 50%) for both
porphyry and vein types of ores because of macro‐fracture formations during the micro‐
wave treatment at their respective threshold temperatures. The bond grind ability of the
porphyry type and vein type was increased up to 7% and 13%, respectively, at higher
temperatures (i.e., above 400 °C) [158].
The effect of the microwave treatment on the chalcopyrite surface properties such as
surface roughness and wettability has been studied [159]. It has been reported that the
chalcopyrite surface’s roughness reduces after exposure to microwave radiation (using
AFM data), as shown in Figure 27. The iron oxide formation might ascribe it, along with
surface oxidation. In comparison, the wettability of the chalcopyrite surface was increased
with increasing the radiation period, which might be due to the reduced surface rough‐
ness [159].

Figure 27. Three‐dimensional AFM microphotograph images of a chalcopyrite surface (a) before
and (b) after microwave radiation [159].
Minerals 2022, 12, 545 34 of 42

The impact of the microwave treatment on the liberation size and flotation operation
for a copper sulphide ore has been also studied [160]. The results have confirmed that both
treated coarser and finer particle materials have relatively higher degrees of liberation
than untreated particles. It was observed that the microwave‐treated coarse size particles
(P80 = 238 μm) produce around an equal percentage of liberation compared to the un‐
treated finer‐sized particles (P80 = 182 μm) (Figure 28). Its selective breakage attributed to
the increase in the percentage of liberation for copper sulphide at the grain boundaries.
Due to the increasing liberation, the copper recovery through flotation slightly increased
for the treated particles (Figure 29). The above literature concluded that microwave pre‐
treatment enhanced the grinding ability of the copper sulphide mineral (chalcopyrite rich)
up to 50%, with a reduction in the surface roughness, which intensified the wettability of
chalcopyrite and, hence, yielded a better flotation performance of the coarser size fraction
at the laboratory/batch scale. However, their effect in large‐scale flotation operations
should be checked in the future with different types of copper sulphide minerals.

Figure 28. (a) Cumulative copper sulphide liberation by composition profiles, and (b) copper sul‐
phide liberation versus grind size [160].

Figure 29. Copper‐grade recovery curves for (a) fine‐grained and (b) coarse grained materials under
untreated and microwave‐treated condition [160].
Minerals 2022, 12, 545 35 of 42

9.2. High‐Voltage Pulse Treatment

The effect of a high‐voltage pulse to improve the copper ore flotation has been re‐
cently studied [161,162]. This technique involves grain‐induced preferential breakage un‐
der a controlled supply of pulse and size‐wise separation of the feed material into body
breakage and surface breakage products by ore grade splitting. It has been reported that,
with increasing the voltage load, the copper grade increases due to the preferential break‐
age (Figure 30) [161]. More research should be carried out in this aspect for its applicability
benefit in the mineral industry, especially in the comminution sector. More research
should be carried out in this aspect for its applicability benefit in the mineral industry,
especially in the comminution sector, which assist the methods of downstream pro‐
cess/beneficiation, i.e., size‐based separation and breakage mode—multi‐mineral separa‐
tion. Research should be focused on liberation improvement, along with changes in the
surface properties due to the pretreatment.

Figure 30. Proposed electrical pulse preconcentration characteristics curves [161].

9.3. Ultrasonic Pretreatment

Taheri and Lotfalian studied the effect of ultrasonic pretreatment on chalcopyrite flo‐
tation against pyrite [163]. The results of micro‐flotation revealed that the selective flota‐
tion of chalcopyrite is possible by ultrasonic pretreatment and aeration. The ultrasonic
pretreatment caused the desorption of precipitate metal hydroxide from the chalcopyrite
surface and enhanced the chalcopyrite selective flotation from pyrite (Figure 31) [163]. The
existing literature revealed that the selective separation of copper sulphide minerals
Minerals 2022, 12, 545 36 of 42

(mainly chalcopyrite) requires the selective depression of pyrite by flotation, which is dif‐
ficult to achieve due to their (chalcopyrite and pyrite) galvanic interaction and involuntary
activation of pyrite by the copper ion. However, the ultrasonic pretreatment method prior
to flotation stated that the successful removal of metal hydroxide was possible from the
chalcopyrite surface (caused by the galvanic interaction). It allowed the sulphide collector
to adsorb preferentially on the chalcopyrite surface and resulted in enhanced chalcopyrite
flotation as compared to pyrite. However, the effect of the ultrasonic pretreatment method
may be applied in other copper sulphide minerals to compare its wider applicability.

Figure 31. Chalcopyrite (Cp) and pyrite (Py) recoveries as a function of the pH at different concen‐
trations of KEX (a) before and (b) after ultrasonic treatment [163].

10. Summary
The current global economy demand for copper has been increased sharply because
of its multiple applications in almost the whole sector, along with its never‐ending reusa‐
bility property throughout its life cycle assessment. From this review, it is clearly under‐
stood that copper flotation is the most extensively practiced beneficiation process. Primar‐
ily, the flotation of copper sulphide minerals was rigorously practiced using a thiol group
collector, and the best results were achieved with xanthate. Due to the depletion of a high‐
grade sulphide deposit, many researchers’ foci have shifted to the flotation of copper ox‐
ide minerals as a secondary resource. Traditional thiol collectors failed to float oxide cop‐
per in the concentrate. In comparison, the hydroxamate (chelating) group collector suc‐
ceeded in copper oxide flotation. In the mixed ore (both copper sulphide and oxide), flo‐
tation was successfully performed using the concept of a mixed collector, i.e., mixing thiol
and hydroxamate in a definite proportion. A bio‐collector, i.e., canola oil, was also used
for the selective flotation of chalcopyrite against pyrite.
Apart from physicochemical separation, the gravity concentration technique was
also adopted, only if a significant difference in their specific gravity was observed between
copper and the gangue mineral. Most of the time, gravity separation is used as a pre‐
concentration step before the flotation process. In the case of ultrafine particles, flotation
became inefficient, and hence, many researchers have tried the flocculation of copper min‐
erals using classical flocculants and bioflocculent. Due to its smaller capacity, its applica‐
bility has been limited to the dewatering unit. Copper tailing is also considered a potential
source of copper. Many researchers have successfully recovered copper from processed
tailings, for example, by using a Knelson separator. Advanced pretreatment technologies
such as microwave pretreatment, high‐voltage pulse treatment and ultrasonic pretreat‐
ment were also investigated for processing copper ore to ease the downstream process.
The copper minerals subjected to microwave treatment resulted in a better efficiency dur‐
ing the comminution process, which may be due to the formation of macro‐fractures, and
Minerals 2022, 12, 545 37 of 42

resulted in a higher degree of liberation, along with a decrease in the mineral surface
roughness. Similarly, the high‐voltage pulse treatment was practiced on rejected copper
lumps for preferential breakage. The ultrasonic treatment enhanced the selective flotation
recovery of chalcopyrite against pyrite due to the desorption of metal hydroxide precipi‐
tate from its surface. The visualization analysis showed the recent trends followed for
copper ore processing and found that flotation is the leading research area.

Author Contributions: Conceptualization, S.S.J.; methodology, R.V. and S.K.T.; Software, S.K.T.;
validation, S.S.J. and S.K.T.; formal analysis, S.S.J.; investigation S.S.J. and S.K.T.; resources, S.S.J.
and S.K.T.; writing‐original draft preparation, S.S.J., writing‐review and editing S.K.T., R.V. and
S.S.J.; visualization, S.K.T. and S.F.; Supervision, R.V., S.K.T., S.F. and N.R.M.; project administra‐
tion, R.V. and N.R.M. All authors have read and agreed to the published version of the manuscript.
Funding: This research did not receive any specific grant from any funding agencies in the public,
commercial or not‐for‐profit sectors.
Acknowledgments: The first author is thankful to Deepak Singh Panwar and Aryasuta Nayak for
their writing assistance and support during this period.
Conflicts of Interest: The authors declare no conflicts of interest.

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