Minerals Engineering 143 (2019) 105922

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Lime use and functionality in sulphide mineral flotation: A review T

a,b,⁎ c c
M. Zanin , H. Lambert , C.A. du Plessis
a
University of South Australia, Australia
b
MZ Minerals Pty Ltd, Australia
c
Lhoist, Belgium

ARTICLE INFO ABSTRACT

Keywords: Lime (calcium oxide or calcium hydroxide) is arguably the most common reagent used in the extractive minerals
Lime processing industry. As an effective and economic pH modifier, lime is widely used in the process of selective
Calcium oxide flotation of the major sulphide minerals. This paper reviews: lime preparation factors that influence the reagent
Calcium hydroxide performance properties; mechanisms of lime interaction with collector chemicals and mineral surfaces; its role in
Slaked lime
promoting selective separation between different sulphide minerals; and the effect on pulp and froth properties.
Milk of lime
Flotation
The practical aspects of lime dose locations and the most common sulphide flotation process applications are
Sulphide minerals also discussed.
Mineral processing
Extractive metallurgy

1. Introduction
Minerals flotation exploits the difference in mineral surface prop-
erties in order to separate them via physico-chemical processes. To
enhance such surface properties, different chemicals can be used that
can be broadly classified as either: collectors, modifiers, depressants, or
frothers. Lime (in the form of calcium oxide, CaO, or calcium hydro-
xide, Ca(OH)2) is a very common modifying reagent. Modifying re-
agents react either with the mineral surfaces or with collectors and
other ions in the flotation pulp, resulting in a modified and controlled
flotation response (Bulatovic, 2007a). More specifically, lime is cate-
gorized as an inorganic modifier, with its main role being modification
of the pulp pH. The flotation response of sulphide minerals and their
interactions with collectors (xanthates, dithiophosphates, thionocarba-
mates, and their derivates) is strongly pH dependent. Selective flota-
tion, of one mineral over another, can thereby be achieved by varying
the pulp pH. For example, chalcopyrite can be selectively floated from
iron sulphides (pyrite, pyrrhotite) in a highly alkaline environment
(pH > 11.5), while at lower pH values pyrite readily adsorbs collectors
and reports to the flotation concentrate (Wang and Forssberg, 1991).
Alkalinity in sulphide flotation is generally controlled by the addi-
tion of lime. Alternatives to lime for pH control include soda ash
(Na2CO3) and caustic soda (NaOH). Soda ash and caustic soda are,
however, more expensive than lime. The former is only used to control
the pH up to about 10.5, due to the highly buffered pH response of
carbonate, while the second is a strong base that can increase the pH to
14. But it is highly corrosive, which can raise safety concerns, and its
industrial use is mainly limited to the processing of non-metallic mi-
nerals (Wills and Napier-Munn, 2006; Bulatovic, 2007a).
Sulphide ores are the major source of valuable metals such as
copper, lead, zinc, and nickel, as well as gold, silver, and platinum
group metals (PGMs), and flotation is the dominant industrial process
to recover these metals via the production of a sulphide concentrate. Of
total world copper-mine production, almost 80% originates from flo-
tation of the copper (Cu) sulphides (Table 1). The ready availability and
relatively low cost of lime makes it the preferred pH modifier used in
the flotation of these ores. Dosage and addition points of lime in the
circuit require however careful consideration for a cost-effective use of
lime. This paper reviews the preparation of lime and its main me-
chanisms of action in the flotation of sulphide minerals, as well as the
major industrial applications.
2. Lime formulation, synthesis, and production
2.1. Calcination
Quicklime (CaO) is produced from the calcination of limestone
(CaCO3), a sedimentary rock of mainly marine sediments containing
calcium carbonates in a range of crystal forms. The chemistry and the
physical properties of the originating limestone significantly affect the

⁎
Corresponding author.
E-mail address: max.zanin@mzminerals.com (M. Zanin).

https://doi.org/10.1016/j.mineng.2019.105922
Received 30 March 2019; Received in revised form 13 July 2019; Accepted 11 August 2019
0892-6875/ © 2019 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/BY-NC-ND/4.0/).
M. Zanin, et al. Minerals Engineering 143 (2019) 105922

Table 1
Annual world mine production of copper by industrial process (2013 data from
Matos et al., 2015).
Mine Production (metric tons) Percentage (%)

Flotation 12,700,000 78.9

Leaching, electrowon 3,470,000 21.6
Total 16,100,000 100.4

calcination process and hence the final lime product qualities and
performance. During calcination calcium carbonate undergoes thermal
decomposition when heated at temperatures higher than 800 °C. The
products of this decomposition are calcium oxide (quicklime) and
carbon dioxide gas:

CaCO3 + heat = CaO + CO2

ΔH(900 °C) = 2953 kJ/kg CaO; ΔG(900 °C) = −35 kJ/kg CaO

The reaction is highly endothermic, thus requiring an energy fuel

source such as coal or gas (Herrier et al., 2010).
The decarbonation process of expelling CO2 from calcium carbonate
happens on a migrating front starting on the limestone surface within
the calcination kiln. The exterior of the stone decarbonates first, due to
the fact that limestone and lime are poor heat conductors. The heat then
penetrates deeper into the stone enabling further thermal decomposi-
tion (core-shell model). The purpose of decarbonation is to increase the
conversion extent of CaCO3 into CaO. The driving force of this process
is the equilibrium between the carbonate and the partial pressure of
carbon dioxide. At atmospheric pressure, the temperature must exceed
900 °C to drive the reaction towards CO2 evolution (Boynton, 1980).
The extent of conversion can be increased by calcination intensity
(temperature) or duration. However, the requirement to achieve a high
level of conversion is practically limited by the risk of over-burning
when calcination conditions are too severe. Over-burning reduces the
reactivity of lime when reacting in aqueous mineral slurries and
thereby the utilization efficiency of the reaction.
2.2. Quicklime porosity
The CO2 gas expelled from the limestone during calcination causes
porosity within the resulting quicklime CaO product. Theoretically, the
porosity could be as high as 54%. In practice, however, lower porosity
is observed due to sintering effects of CaO grains, as illustrated in Fig. 1.
Increased calcination temperatures increase this effect. The presence of
different impurities such as iron, sodium, potassium, phosphate,
chlorides, or sodium can also promote the formation of larger grains via
interstitial liquid phases (Boynton, 1980) even at lower temperatures.
Larger CaO grains will have an important effect on the quicklime
properties, with lower surface area (from larger grains) lowering the
reactivity of quicklime with water, thus affecting the resulting milk of
lime quality and utilization efficiency.
2.3. Calcination fuel source effects
The fuel source is an important driver of quicklime cost and quality.
Fuel cost generally represents approximately 50% of the final quicklime
production cost (Boynton, 1980). Fuel sources include coal, natural gas,
oil, plastic waste, or biomass (Oates, 1998). Two key fuel selection
criteria are cost-per-GJ and level of impurities. Impurity levels are
important because all non-carbon-based impurities will report to the
final quicklime product. Coke and heavy fuel oil, for example, contain
high levels of sulphur (Oates, 1998). High sulphur content in the cal-
cination fuel has a coarsening effect on Ca(OH)2 particles during the
slaking process that, in turn, could result in poor lime utilization effi-
ciencies during mineral processing (Ineich et al., 2017).
Fig. 1. SEM images and diagram of lime grain sintering as a function of the
temperature, internal Lhoist.
2.4. Quicklime slaking
Adding dry quicklime to plant circuits is not generally practiced,
because of problematic operating issues such as dusting, clogging and
poor dose controllability (National Lime Association, 1995). Instead,
quicklime is generally slaked before addition to the mineral processing
circuit as a slaked lime slurry, also known as milk of lime, composed of
suspended hydrated calcium hydroxide Ca(OH)2 at a solids concentra-
tions in the range 15–25% w/w. CaO particles exothermically react
with water to form Ca(OH)2.
CaO + H2O = Ca(OH)2 + Heat
ΔH(50 °C) = −1175 kJ/kg CaO; ΔG(50 °C) = −1020 kJ/kg CaO
These Ca(OH)2 particles are smaller in size than the CaO particles
because of capillary water penetration into the porous CaO and sub-
sequent decrepitation of the CaO upon hydration to form Ca(OH)2. The
extent of water penetration, lime hydration and subsequent decrepita-
tion is dependent upon the CaO porosity, which, in turn, is dependent
upon the calcination conditions as indicated earlier. A low porosity CaO
will result in coarser Ca(OH)2 particles, causing reduced lime utilization
efficiency.
2.5. Ca(OH)2 particle size effects
It is important to note that Ca(OH)2 particles generated in the
slaking process are only slightly soluble in water (about 1.4 g.l−1
CaOH2 at ambient temperature, (National Lime Association, 1995) and
that it is the soluble calcium (Ca2+) and hydroxyl ions (OH−), rather
than the solid Ca(OH)2, that participate in target reactions (Giles et al.,
1993). Dissolution of Ca2+ and OH− from the surface of solid Ca(OH)2
particles is the limiting step in the reaction. Finer Ca(OH)2 particles,
with a large surface area of dissolution, result in improved kinetics and
utilization efficiency, compared to larger Ca(OH)2 particles. The pre-
ferable Ca(OH)2 particle size distribution is a d50 lower than 15 µm.

2
M. Zanin, et al.
The particle size of the slaked Ca(OH)2 is therefore an important de-
termining factor influencing overall reagent utilization efficiency and
kinetics. Fine particle size is also important to avoid particle coating
effects and settling problems in lime distribution pipes (Hassibi and
Singh, 2012). Ca(OH)2 particle size is mainly determined by the fol-
lowing factors:
• Reactivity of the lime (influenced by the calcination process con-
ditions and fuel), with more reactive lime typically resulting in finer
Ca(OH)2 particles (National Lime Association, 1995).
• Soluble elements contained in the slaking water, e.g. high con-
centrations (> 500 mg/L) of sulphate in the water will coarsen the
milk of lime (Potgieter et al., 2003).
• Operating temperature of the slaker, i.e. higher slaking tempera-
tures (65–85 °C) generally result in finer Ca(OH)2 particles. (Zinck
et al., 2000) This phenomenon is particularly relevant for low re-
activity lime, but less relevant for higher reactivity lime. For a
continuous production process, the slaking temperature is primarily
controlled by the lime-to-water feed ratio of the slaker (typically at
mass ratio of 1:6 to 1:4) and the reactivity of the lime.
• Extent of mechanical abrasion or comminution during or after
slaking. Some slakers, for example, make use of comminution
methods (as in ball mill slakers) to reduce the particle size of the
slaked lime. This is particularly used in scenarios where other fac-
tors would otherwise result in coarse Ca(OH)2 (Gartner and Diaz
Chavez, 2015).
2.6. Grits management
During the slaking reaction the impurities and unburned carbonate
in the lime will not be slaked. Unreacted and inert particles that do no
convert to Ca(OH)2, known as grits, are, in some plants, rejected from
the slaked lime product prior to distribution into the plant circuit
(National Lime Association, 1995). Grits rejection is, however, not re-
quired for scenarios where grits particles are sufficiently small and their
introduction into the mineral processing circuit is negligible relative to
the ore feed.
2.7. Quicklime quality and reactivity metrics
Lime quality is commonly assessed by measuring the available CaO
content (EN 459-2 or ASTM C110). This metric, however, does not give
an indication of reaction kinetics with water and has been found to be
an insufficient predictor of utilization efficiency (Ineich et al., 2017).
Determining the kinetics of the slaking reaction consists of tracking the
temperature rise of water when quicklime is added to it, with a rapid
rise in temperature indicating high reactivity. A T60, (EN 459-2) cor-
responds to the time required for 600 g of water at 20 °C to reach 60 °C
after addition of 150 g of quicklime. T60 values typically range from 0.5
to 5 min. A T60 lower than one minute may present safety concerns due
to the risk of boiling, while a T60 > 5 min is an indicator of poor
slaking behavior, again increasing the potential for larger particles of
Ca(OH)2 in the final product and resulting in poor utilization efficiency
(Ineich et al., 2017).
2.8. Safety considerations
Lime is not classified as acutely toxic. Nonetheless, it is an irritant
for respiratory tracks (H335) and skin (H315), and it is corrosive for the
eyes (H318) (Lime SDS, 2019). Specific care and personal protective
equipment are required to avoid contact with skin and eyes as well as
inhalation and ingestion. This is particularly relevant due to the exo-
thermic reaction of lime with water from moist skin, eyes and internal
mucous membranes. Care should also be taken to prevent water ingress
into lime during transport and storage. In severe cases, the heat re-
leased from the hydration reaction may ignite plastic liners (big bags)
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Minerals Engineering 143 (2019) 105922
used during transport and storage. Appropriate firefighting measures,
using dry powder foam or CO2, are required for such scenarios as water
is not a suitable extinguishing media (Lime SDS, 2019).
3. Lime interactions with collectors and depressants
Flotation is an electrochemical process, in which mineral surfaces
react with reagents in solution to form hydrophobic complexes that
impart flotability to the mineral particles. In sulphide minerals flota-
tion, these reactions involve oxidation of some species and reduction of
others, resulting in selective adsorption of collector on the mineral
surfaces (Chander, 1988).
The collectors used in sulphide flotation are anionic collectors
(xanthates, dithiophosphates, thionocarbamates, etc.), characterized by
the presence in the molecule of either sulphydryl (SH) or thiol (C-SH or
R-SH) groups. Collector decomposition and the formation of species at
the mineral surface is a complex process that is both kinetically and
thermodynamically controlled (McFadzean et al., 2015). Different
theories were developed for the mechanisms of collector adsorption
(Gaudin, 1957; Fuerstenau et al., 1968; Allison et al., 1972; Wang and
Forssberg, 1990, 1991; Miller et al., 2002). It is now accepted that
flotation occurs due to the adsorption of either the negatively charged
thiol collector (with the formation of a hydrophobic metal-collector
species at the mineral surface) or of a neutral molecule or dimer of the
collector (Fairthorne et al., 1997a, 1997b; Fuerstenau, 2005) (Fig. 2).
Lime, mainly added as slaked Ca(OH)2 as a pH modifier, plays an
important role in the selective flotation and depression of sulphide
minerals. Sulphide flotation is generally conducted in alkaline condi-
tions, which is where the collectors are more stable. Early literature
suggested that in a mixed minerals/collector system there was an op-
timum pH range in which each mineral could be floated. Wark and Cox
(1934) showed that the flotability of each sulphide mineral was pro-
portional to the relative concentration of collector and hydroxyl ions
[DTP−]/[OH−] and calculated a critical pH value for flotation of
chalcopyrite, galena and pyrite with dithiophosphate (Fig. 3).
The pulp redox potential, which is correlated to pulp pH and dis-
solved oxygen by the relation:
Eh = 1.23 + 0.015 log PO2 0.059pH (1)
also plays a role in the oxidative reactions at the surface of minerals and
the complexation with collectors. Richardson and Walker (1985)
showed that the flotation of chalcocite, bornite, chalcopyrite and pyrite
with potassium ethyl xanthate is controlled by the conditioning redox
potential (Eh). The active surface entities were found to be metal
xanthates for chalcocite and bornite, dixanthogen for pyrite, metal
xanthate for initial flotation of chalcopyrite and dixanthogen for full
flotation. For pyrite, Fuerstenau et al. (1968) found a window for flo-
tation between pH 3 and pH 10 in the presence of ethyl xanthate. The
upper limit of pH 10 is actually explained as the limit for oxidation of
xanthate to dixanthogen on the surface of pyrite (+163 mV). Above pH
10, this oxidation does not occur.
The different pH/Eh ranges of thermodynamic stability of the metal-
collector species allows for the selective flotation of metal sulphides, by
conditioning both pH and redox potential. Lotter et al. (2016) over-
lapped the results of previous flotation studies on a number of sulphide
minerals with the Pourbaix stability diagrams of both xanthate and
dithiophosphate species in water solution, identifying regions in the
pH-Eh domain in which collector adsorption is more or less likely on
each mineral, and selective flotation can, in principle, be achieved
(Fig. 4). In a flotation plant, lime can be used to control the pulp pH and
NaSH/SO2 to regulate the Eh in the proper range for selective flotation
to occur. From a practical point of view, however, it is difficult to
maintain the pH/Eh at the specified range in flotation if air is used as
the carrier. Indeed the dissolved O2 will continuously shift the potential
towards higher values. In such conditions, improved Eh control may be
achieved by using N2 as carrier flotation gas, instead of air.
M. Zanin, et al. Minerals Engineering 143 (2019) 105922

Fig. 2. Mechanisms for sulphide mineral surface/collector interaction. Both oxydryl and sulphydryl ions interact with the mineral surface, and the two compete for
adsorption. Adapted from Fuerstenau (2005).

The mechanisms for collector adsorption in mixed sulphide mineral

systems are also influenced by electrochemical interactions between
minerals, and between minerals and grinding media. Sulphide minerals
are semiconductors with distinct rest potentials (Table 2), and when
two sulphide minerals come into contact there is a transfer of electrons
from the less cathodic to the more cathodic one (Yelloji Rao and

Table 2
Rest potential of selected sulphide minerals at pH 4 and 7. Adapted from Fallon
et al. (2017).
Mineral Formula Rest Potential at pH 4 (pH 7)

Pyrite FeS2 0.66 (0.45)

Marcasite FeS2 0.63
Chalcopyrite CuFeS2 0.56 (0.34)
Sphalerite (Zn,Fe)S 0.46
Covellite CuS2 0.42
Fig. 3. Relationship between concentration of sodium diethyldithiophosphate Bornite Cu5FeS4 0.40
and critical pH value for the flotation of chalcopyrite, pyrite and galena. Curves Galena PbS 0.28 (0.17)
at constant [DTP−]/[OH−]. Flotation occurs under conditions to the left of Argentite Ag2S 0.28
Stibnite Sb2S3 0.12
each curve but does not occur to the right of the curve. Adapted from Wark and
Molybdenite MoS2 0.11
Cox (1934).

Fig. 4. Empirically arranged flotation domains of chalcopyrite (Cpy), bornite (Bor), chalcocite (Cc), and Covellite (Cov) in terms of Eh and pH values, with Pourbaix
Diagram of butyl xanthate and ethyl dithiophosphate overlain. Adapted from Lotter et al. (2016).

4
M. Zanin, et al.
Fig. 5. Mechanisms of galvanic interactions between sulphide minerals in so-
lution. Adapted from Fallon et al. (2017).
Natarajan, 1989; Rao, 2004; Nava and Gonzalez, 2006; McFadzean
et al., 2015; Fallon et al., 2017).
In grinding mills, fresh and reactive mineral surfaces are con-
tinuously generated. Galvanic surface reactions between minerals and
grinding media can be intense (forged steel grinding media is reactive
in contact with the sulphides), causing either the formation of hydro-
phobic sulphur species upon oxidation, or dissolution of metal ions
(Cu2+, Pb2+) which can then activate other minerals (Ball and Rickard,
1976; Leppinen, 1990; Senior and Trahar, 1991; He et al., 2005;
Bruckard et al., 2011; Moslemi et al., 2012). As a consequence, mineral
surfaces are contaminated (i.e. activated), and contamination may
cause a shift in the pH-Eh flotation domain. For example, chalcopyrite
(CuFeS2) in an ore can release Cu and Fe ions in solution upon galvanic
contact with pyrite (Fig. 5).
Metal ions in solution may then precipitate in the form of hydro-
xide, but copper can also be adsorbed on the surface of pyrite, making
the mineral readily flotable (Fig. 6) with the usual thiol collectors
(Fornasiero and He, 2008). Lime can be added to depress pyrite, with
both the hydroxyl and calcium ions contributing to the formation of
Fig. 6. Proposed effect of copper activation on pyrite flotation.
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Minerals Engineering 143 (2019) 105922
Fig. 7. Relationship between concentration of sodium cyanide and critical pH
value for the flotation of different sulphide minerals (at 25 mg/L potassium
ethyl-xanthate). Flotation occurs under conditions to the left of each curve but
does not occur to the right of the curve. Adapted from Wark and Cox (1934).
hydrophilic precipitates on the pyrite surface, but higher flotation pH is
needed when pyrite is copper activated (pH > 11.5), thereby imposing
a high lime consumption. Every ore is, however, different and it is
difficult to determine a priori lime consumption for a specific ore. Also,
lime demand in the plant can change significantly over time due to feed
and process-water chemistry variability.
3.1. Interactions between lime and depressants
Lime in flotation, as a pH modifier, can also regulate not only col-
lector adsorption, but also the effect of other commonly-used de-
pressants such as sodium sulphide or sodium cyanide (Yoon, 1981;
Ghiani et al., 1984; Wang and Forssberg, 1996). Cyanide acts by dis-
solving copper from the surface of the activated sulphides, thus pre-
venting collector adsorption. Lime is used in combination with sodium
cyanide for selective flotation of multi-metallic ores, by regulating the
effective concentration of cyanide needed (Wark and Cox, 1934)
(Fig. 7). For example, this strategy can be applied to pyrite. According
to Fig. 7 pyrite could be separated from chalcopyrite at pH 7.5 in the
presence of NaCN (30 mg/L). Separation may also occur in the absence
of cyanide, but only in a narrow pH window between 10.5 and 11.
4. Calcium ion interactions with mineral surfaces
The role of lime in flotation is not limited to pH modifier, indeed the
hydroxyl ion (OH−) is not the only active component of lime. Calcium
ions, which are released in solution, can also interact with the mineral
surfaces, producing different effects in flotation, either favorable or
detrimental to the process.
Lime was found to be a preferred pyrite depressant over other pH
regulators such as sodium hydroxide or soda ash. Several studies
highlighted the specific role of calcium ions in the depression of pyrite.
Tsai et al., (1971) observed that the adsorption of Ca2+ ions increases
rapidly on pyrite as the alkalinity of solutions increases, and attributed
depression to the adsorption of Ca2+ ions associated with OH− ions. Hu
et al. (2000) attributed the depression of pyrite by lime to the surface
formation of Ca(OH)2, CaSO4 and Fe(OH)3, as determined by XPS
analysis (Fig. 8). Niu et al. (2018) also showed that the poor flotation
response of pyrite at high pH was due to the prevailing adsorption of
CaOH+ species on the surface, indicating a stronger affinity of the
hydrophilic calcium species towards pyrite with respect to the collector
(Fig. 9). Calcium clearly plays a specific role. All alkali do not exhibit
M. Zanin, et al.
Fig. 8. XPS spectrum for Ca on pyrite surface indicating the formation of Ca
(OH)2 and CaSO4. Adapted from Hu et al. (2000).
the same behavior during flotation of different sulphide minerals.
Studies by Hodgson and Agar (1989) and Malysiak et al. (2003)
correlated the adsorption of calcium ions to the poor flotation of pen-
tlandite and pyrrhotite in a Ni ore, which was attributed to the for-
mation of hydrophilic species on mineral surfaces. Gibson and Kelebek
(2014) conducted a study on two types of complex Ni-Cu sulphide ores
and found that when lime was replaced by soda ash (Na2CO3) as pH
modifier, the adverse effect of hydrophilic calcium species on pen-
tlandite was largely eliminated and the mineral’s flotability restored.
Chalcopyrite flotation recovery was less affected, due to higher natural
hydrophobicity, while pyrite was depressed to a similar extent by either
lime or soda ash. The use of soda ash in place of lime in plant practice is
however limited, mainly due to cost considerations, and confined to
specific situations in which calcium in process water can pose an issue.
Fig. 9. ToF-SIMS normalized intensities of DDTC adsorption (left) and Ca
species (right) on galena (Ga) and pyrite (Py) at pH 10.5 and 12.5. Adapted
from Niu et al. (2018).
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Minerals Engineering 143 (2019) 105922
4.1. Zeta potential and slimes
The adsorption of CaOH+ species on the surface of the sulphide
minerals is not the only effect of lime addition. Hydrophilic CaOH+
species and Ca2+, like other alkaline metal ions, adsorb onto the sur-
faces of both sulphide and non-sulphide gangue minerals causing a
reverse in zeta-potential (Rao and Finch, 1989). As a result, electro-
static attraction with the opposite charged sulphides may cause the
formation of slime coatings.
Metal sulphides are expected to have negative surface charge in
alkaline conditions, having generally an isoelectric point pHIEP < 3.5
(Bebie et al., 1998). In a flotation pulp, the sulphides pHIEP can shift to
much higher values due to oxidation and/or the adsorption of positive
metal ions (e.g., Cu2+) from solution (Multani et al., 2018). Upon ad-
sorption of collector, however, the surface charge of sulphides is gen-
erally restored to negative values as illustrated in Fig. 10.
Slime coatings can originate from gangue minerals that naturally
have positive z-potential in alkaline conditions, such as serpentine
(Fig. 11). However, slime coatings may also originate from the ad-
sorption of divalent Ca2+ ions on negatively-charged gangue particles
and the reversal of their zeta potential (Raghavan and Hsu, 1984; Uribe
et al., 2016). This phenomenon can be particularly problematic in the
flotation of clay-rich ores at high lime addition rates.
Clay particles in the pulp may exhibit either positive or negative
charges on the basal (planar) and edge surfaces depending on the pH
conditions (Gupta and Miller, 2010). Some clays can, however, easily
adsorb Ca2+ ions from solution, thereby becoming become positively
charged, and subsequently cover the surface of the negatively-charged
sulphide mineral particles. This will have two detrimental effects. The
first is that the covered sulphide minerals of interest will be depressed
by the slime coating and report to the tailings. The second is that the
sulphide minerals will also carry some attached slime material into the
concentrate, reducing its grade (Alvarez-Silva et al., 2016).
4.2. Viscosity
Pulp viscosity can also be affected by lime addition in clay-rich ores.
Depending on clay type and ore type, the adsorption of calcium ions can
either promote or adversely affect heterocoagulation of particles, re-
sulting in increased or decreased pulp viscosity. Cruz et al. (2015a)
showed reduced pulp viscosity when calcium ions were added to a Cu-
Au ore/bentonite mixture, while viscosity increased when kaolinite was
added instead of bentonite. In the case of bentonite, a high con-
centration of Ca2+ ions can displace Na+ ions in the interlayer space
Fig. 10. Zeta potential curves for pyrrhotite (10−3 mol/L KCl background
electrolyte): baseline (as is) and with 10−4 mol/L CuSO4, and PAX. Adapted
from Multani et al. (2018).
M. Zanin, et al.
Fig. 11. Zeta potential of pentlandite and serpentine versus pH in both KNO3
solution and calcium-rich supernatant. The z-potential of both minerals is ne-
gative at pH > 9 in KNO3 solution, while in supernatant water the adsorption
of calcium reverses the z-potential, causing electrostatic attraction and slime
coatings. Adapted from Alvarez-Silva et al. (2016).
and prevent hydration and swelling (Alther, 1986). In the case of
kaolinite, the increased viscosity is attributed to Ca2+ ions modifying
the electrical double layer on clay mineral surfaces and contributing to
the formation of network structures (Abdi and Wild, 1993; Wild et al.,
Fig. 12. Simplified diagram illustrating the typical lime dose locations in sulphide flotation plants.
7
Minerals Engineering 143 (2019) 105922
1993). The increased viscosity in flotation leads to more fine gangue
particles reporting to the concentrate by unselective water entrainment,
and diluting the concentrate grade. This was not observed when soda
ash was used instead of lime as the pH modifier (Cruz et al., 2015b).
The ability of lime to modify the pulp and froth viscosity is some-
thing that can also be used advantageously. In addition to pH control
reasons, lime is also frequently used to increase the settling rate and
improve the water recovery of tailings (Watson et al., 2010), or to in-
crease froth stability in poorly mineralized scavenger froths. Increased
froth stability at high solution ionic strength, and in particular when
lime (and Ca2+) is added, has been reported widely (Manono et al.,
2012, Corin et al., 2011). The phenomenon is explained by a reduction
of the zeta potential of bubbles and particles, hence reducing the re-
pulsive forces, resulting in increased solids and water recovery (Yoon
and Sabey, 1989; Paulson and Pugh, 1996). By adding lime, it is in
some scenarios possible to reduce frother consumption. Some con-
centrators do not employ frother due to the high salt content of their
plant water (Quinn et al., 2007).
5. Typical lime addition locations in flotation plant circuits
The layout of the flotation plants, the reagents used, and the se-
quence of unit operations may vary from ore to ore, and from mine to
mine. However, the general processing route always comprises: (i)
comminution (crushing and grinding), (ii) flotation, and (iii) dewa-
tering/thickening/tailings management. The typical lime dose locations
are indicated in Fig. 12. The typical rationales for lime dosing at these
locations are provided below:
1. Primary grinding – Lime is often added into the semi-autogenous
(SAG) mill together with the ore feed and process water. Sulfide
minerals are, by nature, acid to varying degrees causing the milled
pulp to have a pH ranging from 4 to 8 depending on the sulphide
and gangue mineral composition of the ore. In most circuits the bulk
of the lime addition occurs in this location. Lime is added to avoid
acid pH conditions that could lead to metal dissolution effects that
would impede flotation recovery, and has been found to reduce the
rate of ball wear during milling (Yelloji Rao and Natarajan, 1991).
Lime addition to the mill also provides for good mixing of lime with
the incoming ore.
2. Rougher flotation – Lime is added after primary (typically SAG) and
secondary (ball) milling, usually in a conditioning tank, to ensure
optimal pH control in the subsequent rougher flotation process.
3. Regrind – Lime is added to the concentrate regrinding feed to
M. Zanin, et al. Minerals Engineering 143 (2019) 105922

counter a pH drop during regrinding, due to fresh exposure of sul- may result in altered flotation response, with losses of value to tailings
phide surfaces. and diluted concentrate grade. Significant savings can, therefore, be
4. Cleaner flotation – Lime addition prior to cleaner flotation is parti- achieved by careful selection of lime and pH control in the process.
cularly important where this step is used for pyrite rejection, which Proper pH control results in higher product yield, at reduced reagent
often occurs at relatively high pH levels (up to pH 11.5 in some consumption and operating costs.
plants, as shown in Table 3). In plant practice the pH is controlled by regulating lime addition in
5. Tailings disposal – In locations where the tailings contain high the form of slaked lime Ca(OH)2. This is generally achieved by setting a
concentrations of rejected sulphides, particularly acid-generating target pH value in key locations within the circuit (e.g., mill discharge),
sulphides like pyrite (FeS2), precautions have to be taken to ensure by means of pH probes and dosing pumps connected to a ring main and
acid generation and associated acid mine drainage do not occur controlled by a feedback loop. The control of lime addition is, however,
(Qian et al., 2017). This is particularly relevant in high rainfall not trivial, to ensure efficient flotation and also to minimize the reagent
areas. consumption. Common problems involve pH probes not being properly
6. Final concentrate – Lime is added to concentrates in some locations calibrated and cleaned at the required time intervals, causing false
prior to filtration to ensure pH control of the final concentrate readings and excessive or insufficient lime addition. But even when the
product. This prevents odors arising from the decomposition of pH probes operate properly, the control strategy itself plays a role in the
collection chemicals during concentrate storage, handling and overall efficiency of its usage (Tammia, 2017).
transport (du Plessis and Senior, 2014). Moon and Vaughn (1972) patented a method of controlling lime
additions in sulphide flotation, which aims at maintaining a pre-
determined degree of alkalinity in the flotation pulp at or above a pH of
6. Lime dose and control about 9. The method comprises continuous sensing of the flotation
pulp’s electrical conductivity, and controlling lime additions to the
Lime is a relatively inexpensive reagent, making it the most fre- flotation circuit in accordance with deviations from the pre-set con-
quently used alkali in mineral processing. Based on indicative (2019) ductivity value. It is claimed that better control in flotation can be
bulk reagent prices (excluding logistics costs), the effective mol OH− achieved if alkalinity is targeted instead of pH only.
yield per US dollar of reagent is approximately 200 for CaO, compared In an operating plant there is no linear correlation between lime
to 150, 70 and 50 for MgO, N2CO3 and NaOH respectively. The total addition and the resulting pulp pH (and/or alkalinity), because changes
lime dose requirement in flotation operations (typically in the range of in feed ore throughput and composition continuously change the de-
0.4–2.5 kg per metric ton of ore feed), some treating up to 80 million mand for lime. Lime addition rate needs to be varied in real time in
metric tons of ore feed, can be significant. On average, it has been es- response to feed changes, and problems such as overshooting and slow
timated that the cost of lime in sulphide minerals flotation is approxi- system response are intrinsic in the control strategy. It has been sug-
mately double the cost of collectors (Fee and Klimpel, 1986), although gested that better control could be achieved if the pH probe reading/lime
it can vary significantly from operation to operation. Variation in the flowrate feedback loop also considered the incoming ore flow (Tammia,
slurry pH and pulp potential in both the milling and the flotation circuit 2017). In the proposed approach the error e = pHsp − pH is the ratio set
point. Multiplying the ratio set point with the incoming ore flow yields
Table 3 the amount of reagent needed to achieve the required pH level. To
Reagents scheme and operating pH in rougher and cleaner flotation in major improve the efficiency of lime addition, a new proposed control
North and South American porphyry copper plants. Adapted from Bulatovic strategy is based on a constant ratio between the added lime and the
(2007c) and Woodcock et al. (2007). incoming ore flow, while ensuring that the pH level is maintained
Plant Collectors Frothers pH within allowable limits (Tammia, 2017). The pH level is maintained
using upper and lower bound pH controllers that utilize the concept of
Ro Cl an equivalent control objective known as the strong acid equivalent
Canada (Wright and Kravaris, 1991).
Gibraltar Dithiophosphate, PAX MIBC 10.5 11.1 Conventional off-line sampling and analyses methods limit process
Island Copper SIBX Dow 1012 10.5 11.2 control options available to plant operators. Improvements in online
Highland valley PAX, fuel oil Dow 250/ 9.2 10.5 analytical technologies, such as Laser-inducted Breakdown
pine oil
Spectroscopy (LIBS) to determine mineral slurry elemental composition
USA every 15 minutes, in combination with smart software processing
Utah Copper Dithiophosphate, fuel oil Doz 250/ 8.5 9.5
strategies, are enabling new process control methods and philosophies.
MIBC
Sierrita SIPX, xanthic ester, fuel oil MIBC 11.0 11.5 Codelco, for example, uses this technology at its Ministro Hales copper
Morenci Thionocarbamate Dox 250/ 10.5 10.5 plant in Chile to continuously monitor the Fe level of the feed (mainly
MIBC influenced by the pyrite content) and concentrate, particularly in the
Pinto Valley NIBX, dithiophosphate MIBC 11.5 11.5 cleaners. Rather than dosing lime based on pH control set-points, lime is
Mineral Park Thionocarbamate, xanthic esther MIBC 11.5 11.5
Bagdad PAX, Fuel oil Pine oil/MIBC 11.5 11.5
dosed to reduce Fe level in the final concentrate based on analytical
San Manuel SIPX, mercaptobenzothiazole, MIBC/store 8.0 8.0 measurement and intelligent process control that directly monitors the
dithiophosphate oil Fe level in response to lime dose and finds an optimal dose level for the
Chile particular set of prevailing conditions (Tapia, 2019). Using this meth-
El Salvador PAX, thionocarbamate Teefroth TB/ 10.8 11.5 odology, copper concentrate grades were improved from 26.3 to 27.7%
pine oil while decreasing the iron content from 20.8 to 20.3%.
Escondida SIPX, mercaptan, xanthic ester MIBC/pine 10.5 10.8
oil/Dow 1020
Los Bronces Dithiophosphate Dow 250 10. 10.5 7. Common lime-consuming flotation circuits
El Teniente Xanthic ester, fuel oil Dow 250 11 11.5
Andina Thionocarbamate, fuel oil MIBC/Dow 9.0 9.5 7.1. Cu, Mo, and Au flotation in porphyry copper ores
250
Chaluahuasi SIPX, thionocarbamate Pine oil/MIBC 10.5 10.5
Porphyry copper ores are the most abundant source of copper
Chiuquicamata SIPX, dithiophosphate Dow 250/ 11.0 11.5
pine oil worldwide. Vast, disseminated deposits are spread all around the globe,
from North to South America, to East Europe, Africa and Australia. The

8
M. Zanin, et al.
geology of these deposits can vary significantly from region to region,
but the mineralization generally consists of copper sulphide (chalco-
pyrite, chalcocite) with low-to-moderate pyrite content (1–15% of the
total ore). These deposits may also contain molybdenite or gold in
economic concentrations, which are recovered as by-products. In the
flotation of these ores, pyrite is generally treated as gangue mineral and
it is therefore depressed or floated separately. Also, pyrite may contain
significant amounts of ‘penalty’ elements, such as As, and it is important
to remove such elements from the different sulphide concentrates be-
fore smelting.
Processing plants for porphyry copper ores are generally very large,
processing up to 200,000 tpd of ore (JX Nippon, 2018)), and emphasis
is put on throughput. Ores with low pyrite content (< 2%) are gen-
erally considered easier to process (and the reagents scheme only in-
cludes copper collectors, pH regulator, and frother). As pyrite content
increases the process becomes more complicated, due to the significant
effect of galvanic interactions in the pulp. The addition of lime to in-
crease pH in the range where pyrite is depressed is common practice.
Generally, pyrite is floated together with the copper sulphides in the
roughers, in moderately alkaline conditions, and depressed in cleaning
(after regrinding) at very high pulp pH values (pH > 11) (Table 3).
High lime consumption is recorded in some operations, up to 5 kg lime/
t ore (Wills and Napier-Munn, 2006), since pyrite, especially when
present in high ratio with the copper sulphides, can easily become
copper activated during grinding, and be more difficult to depress.
The presence of gold in porphyry copper ores may require specific
flotation strategies to ensure optimum recovery of both Au and Cu,
which may differ according to gold mineralogy. Native gold generally
floats well with the collectors used for the Cu sulphides (e.g., xanthates,
dithiophosphates). However, when Au is mineralogically associated
with the sulphides, or when high pyrite content in the ore poses a
problem, different processing routes are possible (e.g., bulk flotation of
Au and the sulphides, or sequential flotation). The use of lime for pH
control is critical to the process. At Newcrest Telfer Cu-Au mine
(Australia), sequential flotation is used, in which pyrite is depressed
first (by using lime and cyanide), and re-activated (with CuSO4) prior to
a second flotation stage (Benson et al., 2007). This is due to the unique
copper-gold orebody at Telfer, which requires recovering gold that is
mineralogically associated with pyrite.
A possible issue with the use of large quantities of lime to depress
pyrite in porphyry ores is the unwanted depression of value minerals
such as molybdenite. Zanin et al. (2009) reported that molybdenite can
be depressed at high lime addition, the mechanism being adsorption of
divalent calcium ions and heterocoagulation of molybdenite and quartz
particles (Raghavan and Hsu, 1984; Smit and Bhasina, 1985). The
formation of hydrophilic slime coatings on the surface of the mineral
prevents efficient bubble/particle attachment and reduces its flot-
ability. At Kennecott Utah Copper, the separate treatment of an ore type
containing problematic silicate minerals was necessary to ensure stable
molybdenite recovery, as well as the optimization of the frother to
collector ratio to ensure adequate froth stability (Triffett et al., 2008).
Although pH control and the use of lime at high concentration may:
(i) not always be sufficient to depress pyrite, and (ii) negatively affect
Cu and Mo recovery, adding lime is still the most common strategy
adopted in the industry, with only a few copper flotation plants
adopting other solutions (e.g. intense aeration, addition of diethylene-
triamine, DETA, and/or sodium sulphite/metabisulphite) (Grano et al.,
1997, Agorhom et al., 2014). Park and Jeon (2010) found that mo-
lybdenite flotation efficiency using sodium silicate was higher than
using lime in typical alkaline conditions (pH 9.5–11), and this was at-
tributed to the absence of heterocoagulation between molybdenite and
the fine gangue particles when lime was replaced by sodium silicate. It
was concluded that sodium silicate could be used not only as pH
modifier but also as depressant/dispersant of slimes.
9
Minerals Engineering 143 (2019) 105922
7.2. Sequential flotation in Cu-Zn, Pb-Zn and Cu-Pb-Zn sulphide ores
In the majority of zinc operations, sphalerite (the zinc sulphide) is
often associated with galena (PbS), as well as copper sulphides and iron
sulphides. Two methods are generally used to produce separate Cu, Pb
and Zn concentrates. The first method is a bulk Cu-Pb flotation followed
by the activation and flotation of the Zn sulphide (Liu et al., 2000). The
other common process to treat these ores is sequential flotation stages,
each of which is optimized for the selective recovery of one mineral
over the others. The order is generally Cu, followed by Pb and Zn sul-
phides, respectively. This is because there is a window of pH values at
which copper (pH 5–6), lead (pH 7–7.5) and zinc (pH > 10) can be
floated from each other (Fig. 13). Pyrite is depressed throughout the
three flotation cycles, and is rejected in the final tailings, together with
the non-sulphide gangue.
There is no general rule by which a treatment method (bulk Cu-Pb
over sequential flotation) is selected, and the reagents scheme using
either technique also varies depending on the ore mineralogy
(Bulatovic, 2007b). At Rosh Pinah lead-zinc concentrator in southern
Namibia (the major valuable minerals being chalcopyrite, galena and
sphalerite), sequential Cu-Pb-Zn flotation is used. However, with a new
ore type being recently mined (lower in Cu) the circuit struggles to meet
grade requirements. For treating such a new ore, bulk Cu-Pb flotation
followed by Zn flotation has been recommended (Sehlotho et al., 2018).
An example of a sequential Cu-Pb-Zn flowsheet is given in Fig. 14. A
first flotation stage is carried out at low pH (pH 6), in which the copper
sulphide is floated while both galena and sphalerite are depressed. As
shown in Fig. 13, at low pH both lead and zinc float poorly, while
copper can still be recovered at high values. In a second flotation stage,
galena is re-activated (usually by increasing the pH to about 7.5, with
lime), while sphalerite is still depressed. Last, sphalerite is floated after
increasing the pH further (generally at pH > 10.5). Copper sulphate is
also added for improved sphalerite activation.
In the process of sequential flotation, the use of depressants (e.g., Na
cyanide, Zn sulphate, sodium sulphite, sodium metabisulphite) and
activators (e.g. CuSO4) at each stage is combined to carefully control pH
to achieve optimum separation. Lime (or soda ash) is added to the
different flotation stages to the required concentration. Black Mountain
mine (South Africa), operated separation of Cu from Pb/Zn by con-
ditioning the pulp with SO2 (800 g/t), to a pH between 4.5 and 6
(Bulatovic, 2007b). The dosage of alkali (lime) was shown to be critical
to ensure low Pb concentration in the Cu concentrate.
Several strategies aiming at replacing the toxic inorganic de-
pressants (e.g., cyanide, sodium dichromate) with more eco-friendly,
Fig. 13. Recovery of the different sulphide minerals versus pulp pH in the se-
quential flotation of Cu, Pb and Zn. Adapted from 911metallurgist.com.
M. Zanin, et al.
Fig. 14. Example of a sequential Cu-Pb-Zn flotation flowsheet. Copper is concentrated first, at lower pH, followed by lead and, finally Zn. Adapted from Bulatovic
(2007b).
organic, substances in the flotation of Cu-Pb-Zn ores also include lime
and pH control to the addition of the alternative substances. At Silver
Queen mine (Canada) a combined lime-starch-SO2 conditioning scheme
is used for copper flotation from the Pb/Zn sulphides (Bulatovic,
2007b). In the process, lime (1200 g/t) and starch (200 g/t) are used
first, at pH 10.5–11.2, after which the pH is reduced to 5.5 with SO2
(200 g/t) and the copper sulphide floated.
Liu and Laskowski (1989) obtained selective flotation of chalco-
pyrite from galena using lime and dextrin (a water-soluble carbohy-
drate with chemical formula (C6H10O5)n) as depressants, at pH 11 to
12. Liu et al. (2000) explained the adsorption of the polysaccharides by
bonding to the surface metal hydroxyl species, the formation of which
on the surface of the different sulphides is pH dependent, as discussed
elsewhere in this paper. The authors also observed, however, that the
Ca2+ ions released by lime adversely affect selectivity in Cu-Pb se-
paration using dextrin. Selectivity was restored when a complexing
agent, like citric acid, was used to remove the metal ions from the
surface of minerals. Similarly, in the lime-dextrin-SO2 method, selective
depression of Pb and Zn was enhanced by using ammonium persulphate
as the complexing agent for metal ions (Bulatovic, 1989; Bulatovic
et al., 1991).
7.3. Ni and Ni-Cu sulphide ores
Nickel-copper sulphide ores can differ significantly in the miner-
alogy of both the sulphide and the gangue minerals. Pentlandite is the
major source of nickel, and often carries with it cobalt or precious
group elements in economic concentration. Vast pentlandite deposits
are processed in Canada, Australia, and South Africa. The processing
routes and reagents used vary in these processes. Typical flotation
flowsheets involve either sequential flotation of Cu (first) and Ni
(second) from the ore (e.g., Strathcona and Kevitsa mines), or bulk
flotation of the sulphides and subsequent Cu-Ni separation (e.g.,
Thompson, Clarabelle, Jinchuan and Norilsk).
The preferred collectors for Cu-Ni flotation are high molecular
weight xanthates (e.g. potassium amyl xanthate, PAX or sodium iso-
propyl xanthate, SIPX), with strong hydrophobic behavior, although
thionocarbamates are sometimes used as secondary collectors, parti-
cularly in ores containing Pt and Co as secondary elements, since they
reportedly provide better Pt and Co recovery. Also, thionocarbamates
are more selective against pyrrhotite (Fairthorne et al., 1997a, 1997b).
As for many other mixed sulphide ores, selective flotation is
achieved by varying the pulp pH for which lime is most often utilized.
Bulk flotation is generally performed at around pH 9, while Cu-Ni se-
paration is performed at higher pH, around 11. In some cases, flotation
is operated at saturated lime pH condition (i.e. pH > 12) to strip the
10
Minerals Engineering 143 (2019) 105922
collector from the surface of pentlandite. Cyanide or dextrin can also be
used to help depress pentlandite (Lawson et al., 2014). The choice of
lime versus soda ash is dictated by the gangue minerals in the ore. As
discussed elsewhere in this paper, calcium ions can activate some clay-
type gangue minerals, or talc, contaminating the concentrate. In these
situations, soda ash is generally preferred to lime. On the other hand,
lime provides better depression of pentlandite in Cu-Ni separation. At
Vale's Thompson Mill (Canada) the predominant nickel and copper
minerals are pentlandite and chalcopyrite, respectively. Following bulk
sulphide flotation, where soda ash is added as the pH modifier, sodium
amyl xanthate as the collector and MIBC as the frother, slaked lime is
added to depress the pentlandite and effect Cu-Ni separation (Farr,
1992).
Selective flotation of pentlandite from the iron sulphides (mainly
pyrrhotite) is also an issue. Pyrrhotite, if not depressed, can con-
taminate copper and nickel concentrates. Magnetic separation is often
employed to separate pyrrhotite from the other sulphides, either before
flotation or during refining of Cu and Ni concentrates. In flotation,
pyrrothite is also depressed by means of pH control (lime or soda ash), a
combination of soda ash-organic depressant (Dong and Xu, 2016), or by
using dyethilenetriamine (DETA) as a chelating agent for metal ions
and sodium sulphite to complex with surface sulphur and the adsorbed
collector (Kelebek and Tukel, 2018). The DETA/Na2SO3 strategy has
been successfully implemented at Clarabelle concentrator (Canada)
since 1998 (Doucet et al., 2010).
7.4. Arsenic containing sulphides
Arsenopyrite (FeAsS) is generally considered a gangue mineral in
base metal flotation. The associated arsenic content (average stoichio-
metric content is 46% As) reduces the concentrate’s value and attracts
smelting and refining penalties due to the higher processing and dis-
posal costs (Wilson and Chanroux, 1993). Therefore, in most instances
arsenopyrite is depressed during the flotation of the other sulphides. An
exception is auriferous arsenopyrite (arsenopyrite associated with
gold), which is floated because of its Au content (Chen et al., 2010;
Subramanian et al., 2005).
Arsenopyrite can be floated with xanthate collectors (López
Valdivieso et al., 2006). Similarly to pyrite, oxidation of xanthate ions
(X–) to dixanthogen (X2) is attributed as the mechanism through which
the collector adsorbs (Allison et al., 1972). The pulp pH, and therefore
lime dosage, is critical in the flotation of arsenopyrite. Best recovery is
achieved in the pH range 4–7, and Eh potential in the range
100–500 mV SHE (Sirkeci, 2000; Peres et al., 1993), in which dixhan-
togen is more stable. As in the case of pyrite, depression of arsenopyrite
is achieved at high pH, by the formation of a layer of oxidation products
M. Zanin, et al.
(ferric hydroxide and arsenate) on the surface (Beattie and Poling,
1987). When floated in copper ores, copper ions may activate arseno-
pyrite, and poor depression is obtained. Copper activation is due to the
formation of copper arsenosulphide (CuAsS) at low pH and copper ar-
senate (Cu3(AsO4)2) or arsenite (Cu3(AsO3)2) at high pH (Wang et al.,
1989). The collector would then adsorb on these species rendering the
arsenopyrite surface hydrophobic (López Valdivieso et al., 2006).
At the Tampakan Cu-Au deposit in the Philippines (operated by
Sagittarius Mines, 2940 Mt resources graded at an average 0.6%
copper, 0.2 g/t gold, and 70 ppm molybdenum), the beneficiation of
copper from the ore requires rejection of arsenic that occurs in sig-
nificant levels in the deposit (Senior et al., 2006). Enargite
(3Cu2S·As2S5) is the major arsenic-bearing mineral. Separating enargite
from the other, non-arsenic copper sulphides reporting to the Cu con-
centrate is necessary. Depressing the arsenic-bearing sulphides is diffi-
cult, since the latter respond to the same collectors as the other sul-
phides and are also resistant to oxidation (high rest potential: pyrite
(FeS2) ≥ arsenopyrite (FeAsS) > chalcopyrite (CuFeS2)). Selectivity is
not possible based on pH, alone, while differential flotation is obtained
by pulp potential control (Smith et al., 2012). A sequential flotation
process was proposed to separate arsenic-bearing minerals from copper
concentrates (Fig. 15), in which a bulk Cu-As concentrate is produced
first, and subsequent flotation stages at pH 11 and varying redox po-
tential, from reducing to oxidizing conditions, are implemented
(Tayebi-Khorami et al., 2017).
Removal of arsenic (mainly as gersdorffite, NiAsS) from the Cu-Ni
bulk concentrate at Clarabelle (Canada) was also implemented as a
strategy to improve the smelter’s operation. Selective flotation was
achieved by combining high pH, oxidizing conditions, and a set of
chemical depressants. The arsenic recovery to the final Cu-Ni bulk
concentrate was reduced from 73% in baseline test to less than 30%
(Dai et al., 2005).
8. Impact of hypersaline- and seawater
Flotation in seawater is increasing in popularity within the industry.
Especially in geographical settings in which fresh water scarcity is an
issue, such as many South American massive porphyry Co/Mo deposits,
flotation in seawater is often the only sustainable solution (Castro and
Laskowski, 2011). Most Western Australian nickel operations also em-
ploy hypersaline bore water in flotation, with even high concentrations
of dissolved salts exceeding that of seawater (i.e. g > 6000 mg/l
SO42−, > 35,000 mg/l Na, > 65,000 mg/l Cl and > 1500 mg/l Mg in
Western Australian bore water).
The high salinity and ionic strength of seawater have an impact on
Fig. 15. Sequential flotation of different As bearing minerals in Tampakan ore
as proposed by Tayebi-Khorami et al. (2017).
11
Minerals Engineering 143 (2019) 105922
the response of mineral surfaces to both reagents and the flotation
environment, which have to be accounted for. Flotation at high ionic
strength has been reported to enhance the flotation of the inherent
hydrophobic minerals (Haga et al., 2014), since the electrical double
layer is compressed and attachment to the air bubbles enhanced (Lucay
et al., 2015), and also finer bubbles are produced (Jeldres et al., 2016).
Also, the flotation froth is more persistent and stable in the presence of
dissolved salts. This is because bubble coalescence is reduced (Castro
and Laskowski, 2011), and bubble/particle aggregates survive longer in
the froth before bursting. For these reasons, several operations world-
wide are able to successfully carry out flotation of sulphide minerals in
saline and seawater, e.g., Esperanza, Las Luces, Michilla, Sierra Gorda
and Centinela copper mines (Chile), Raglan Cu-Ni ore (Canada), and Mt
Keith Ni ore (Western Australia), (Drelich and Miller, 2012; Senior and
Thomas, 2005; George, 1996). In most cases, a reduction in the re-
quired reagents dosage (in particular frother) is also reported. However,
the increased froth persistency may cause other problems, such as high
entrainment of hydrophilic gangue diluting the concentrate and causing
difficulties in pumping and transporting the froth to subsequent process
stages (Ramos et al., 2013; Jeldres et al., 2016).
In seawater, pyrite depressing occurs at somewhat lower pH than in
fresh water (Castro and Laskowski, 2011). Lime consumption is, how-
ever, much higher when seawater is used in the process, due to the
buffering properties of saline water (Jeldres et al., 2015). Magnesium is
the main buffering element in seawater with a concentration of ap-
proximately 1.3 g/L, imposing a stoichiometric Ca(OH)2 consumption
of approximately 4 g/L to precipitate magnesium from solution as Mg
(OH)2. In scenarios where seawater is used without pre-processing, i.e.
raw seawater, lime consumption increases dramatically (Martín et al.,
2018) when the pH target is above the buffering effect of magnesium
(i.e. above 10). Nevertheless, in porphyry copper mines lime is the
preferred reagent for pyrite depression, and, more generally, for pH
control. This implies high reagent consumption and has other proces-
sing consequences. Lime in seawater can complicate the recovery of
other valuable sulphides. It has been shown that molybdenite flotation
tends to be depressed in seawater, due to the very high lime additions
required and the precipitation of magnesium hydroxide on its surface
(Martín et al., 2018). Also, the divalent calcium ions can adsorb onto
the hydrophilic molybdenite edges and promote the formation of slime
coatings that, in turn, reduce the flotability of the mineral (Zanin et al.,
2009; Hirajima et al., 2016). For these reasons, when molybdenite is
present, pyrite depression strategies other than high lime addition
would be preferable, such as operating at lower pH while using che-
mical depressants such as dyethylenetriamine (DETA) and/or sodium
sulphide (Zanin and Farrokhpay, 2011). Bio-depression of pyrite with
bacteria such as At. ferrooxidans in natural seawater pH (7.8–8.2) has
also been suggested to reduce the use of lime in the process (Martín
et al., 2018) but has not found industrial application.
9. Conclusions
Lime is the most common reagent used in sulphide minerals flota-
tion, and its use in the flotation of the most common ore systems was
reviewed in this paper. Lime plays a critical role by influencing col-
lector adsorption on the different minerals, while also controlling dis-
persion of clays, pulp rheology, settling of particles in the thickeners,
and froth stability.
Generally, the pulp pH regulates oxidation and adsorption of col-
lector, and, ultimately, minerals’ flotability. The pH can be manipulated
to promote the desired flotation conditions for the specific minerals of
interest. A variety of ores and commodities exists, and the flotation
flowsheet and operating conditions vary significantly between ore
systems, but every process relies on pH control, of which lime is the
most economical and commonly used reagent.
In flotation plants, lime additions are common in different points of
the circuit, such as comminution (crushing and grinding), flotation, and
M. Zanin, et al.
dewatering/thickening. All of these contribute to the overall lime
consumption. The cost of lime can be significant. Consequently, opti-
mizing and controlling lime dosage is crucial. Process control strategies
involving continuous sensing of the electrical conductivity of the flo-
tation pulp, and controlling lime additions also with respect to the feed
ore flowrate, have been proven to provide tangible advantages in terms
of both pH control and reduced lime consumption.
Control of pH, by means of lime addition, is also the most commonly
used strategy, to achieve selective flotation of minerals in sulphide ores.
Lime consumption can, however, be very high, especially for ores with
high pyrite content, and/or when flotation is carried out in seawater.
For some South American copper ores, pH values as high as 11.5 are
needed to depress pyrite, and lime consumption up to 5 kg/t of ore is
reported. In some cases, such talc- and clay-rich Cu-Ni ores for example,
other pH modifiers, such as soda ash are preferred. Other pyrite de-
pression strategies are emerging, including the use of DETA or Na2SO3,
which allow a good pyrite/chalcopyrite separation, but their use is still
very limited.
Overall for the next decade, lime as a cost effective and proven pH
modifier is likely to remain the most common reagent in sulphide mi-
nerals processing.
Acknowledgements
The authors thank Penelope Fabre for the adaptation of the figures
and Robert Gaertner for his useful inputs about milk of lime production.
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