Hydrometallurgy 146 (2014) 96110

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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Review

Chalcopyrite hydrometallurgy at atmospheric pressure: 2. Review of

acidic chloride process options
H.R. Watling
CSIRO Minerals Down Under, CSIRO Process Science and Engineering, P.O. Box 7229, Karawara, W.A. 6152, Australia

a r t i c l e i n f o a b s t r a c t

Article history: Hydrometallurgical process developments for the extraction of copper from chalcopyrite tend to target complex
Received 30 August 2013 concentrates, dirty concentrates that would incur penalties if smelted or low-grade ores that are thus far an un-
Received in revised form 24 February 2014 economic source of copper. Perceived advantages of chloride systems are the higher solubilities of copper and
Accepted 5 March 2014
iron, the ease of ferrous ion oxidation and faster leaching kinetics of chalcopyrite compared with ferric sulfate
Available online 29 March 2014
systems, and the generation of sulfur rather than sulfate as the product of sulde oxidation. Process develop-
Keywords:
ments for concentrates employ acidic, oxidising leach media containing sodium or other chloride salts and tem-
Chalcopyrite dissolution peratures up to the boiling points of the high-concentration solutions. In those processes, chloride ion is thought
Chloride lixiviant to be an active agent in the dissolution mechanism. Leaching conditions fall into two groups, those targeting
Seawater Cu(II) and those targeting Cu(I) in pregnant leach solutions. For low grade ores, usually processed in heaps,
Heap leaching the use of seawater or other naturally saline water in leaching operations may be an economic choice to over-
Bioleaching come the scarcity and/or cost of freshwater. Few studies have been published describing the advantages and dis-
advantages of seawater substitution for freshwater in leaching processes but, from the sparse information
available, seawater appears to be as efcient a solvent and carrier of acid and oxidant as freshwater. The recent
descriptions of some iron(II)- and sulfur-oxidising, salt-tolerant acidophilic microorganisms indicate that a
diverse group of microorganisms that could function in sulde heaps irrigated with seawater await discovery.
With regard to processing using seawater instead of freshwater, the salt content in seawater would impact
directly on solution transport costs to and round a mine (through increased solution viscosity and specic
gravity) and could adversely affect product and by-product purity.
2014 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
1.1. Sulfate systems reprised . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
1.2. Scope of this review . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
2. Benets and disadvantages of chloride leaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
3. Acidic chloride systems for chalcopyrite concentrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
3.1. Comparison of studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
3.2. Ferric chloride as oxidant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
3.3. Cupric chloride as oxidant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
3.4. Mixed ferric chloridecupric chloride oxidants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
4. Hybrid chloridesulfate systems applied to concentrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
4.1. Oxygen as oxidant in hybrid chloridesulfate system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
4.2. Ferric ion as oxidant in hybrid chloridesulfate system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
4.3. Chlorate as oxidant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
5. Other oxidants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
5.1. Cl2Br2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
5.2. High MgCl2low HClFeCl3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
5.3. Gaseous Cl2aqueous Cl2HClO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104

Corresponding author.
E-mail address: Helen.Watling@csiro.au.

http://dx.doi.org/10.1016/j.hydromet.2014.03.013
0304-386X/ 2014 Elsevier B.V. All rights reserved.
 H.R. Watling / Hydrometallurgy 146 (2014) 96110 97

5.4. HClO4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104

6. Acidic chloride systems for chalcopyrite ores in heaps or dumps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
6.1. Solution chemistry and secondary reaction products . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
6.2. Bioleaching in chloride heaps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
6.3. Use of saline water or seawater in heaps or dumps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
7. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108

1. Introduction (e.g., Dreisinger, 2009). Fundamental studies on the mechanisms of

The need to process low-grade and/or complex chalcopyrite-
containing ores (see Table 1 for minerals referred to in the text
and their ideal formulae) that cannot be concentrated has been the
main driver for the development of hydrometallurgical processes.
Other drivers are the current imbalance between copper supply and
demand, the overall decline in ore grades and the extensive exploita-
tion of low-grade oxide and secondary sulde ores that may eventu-
ally leave large quantities of low-grade chalcopyrite ores as a major
but, thus far, uneconomic source of copper. Typically, for large
near-surface deposits, average copper cut-off grade for conventional
processing is approximately 0.4% Cu (British Geological Survey,
2007), from which it may be deduced that the term low grade re-
fers to ores with b 0.4% Cu.
This review comprises the second part of an update on the status
of copper extraction from chalcopyrite under atmospheric conditions,
either in concentrated form or in low-grade ores. In the rst part,
sulfate-based systems operated at atmospheric pressure were described
and compared (Watling, 2013 and references therein), with the aim of
informing researchers, metallurgists and plant operators of the wide va-
riety of chemical systems that might be applied in the future. This sec-
ond part of the review is focused on the use of chloride systems for
the extraction of copper from chalcopyrite. Developments using chlo-
ride fall into two groups, (i) those employing acidic, oxidising leach
media containing sodium or other chloride salts up to concentrations
encountered in brines, at temperatures up to the boiling points of the
selected solution compositions (e.g., Hyvrinen and Hmlinen,
2005) and (ii) those in which naturally saline water is substituted for
freshwater water in leaching operations where freshwater is scarce
chloride leaching have been a common feature of process development
among the rst group of processes but are largely absent from the few
processes involving the substitution of saline water for freshwater.
1.1. Sulfate systems reprised
The rst part of the review covered the extraction of copper from
chalcopyrite using sulfate, sulfatechloride or sulfatenitrate leach
media (Watling, 2013). In summary, many studies generated
data consistent with leaching rates being largely independent of acid
concentration beyond that required to solubilise a sufcient concentra-
tion of ferric ions to react with available chalcopyrite surfaces, but de-
pendent on sulfate concentration and solution oxidation reduction
potential (ORP), the optimum ORP being dependent on ferrous
ion and cupric ion concentrations. Topics concerning the inuence of
chalcopyrite crystallographic structure and the formation of secondary
overlayers on chalcopyrite surfaces were also discussed. Copper extrac-
tion rates were enhanced by increased temperature, the presence of
some microorganisms or by the addition of a chloride salt. However, sul-
fate processes with the addition of nitric acid or a nitrate salt were less
well developed and the potential benets remain poorly dened at this
time. The efciencies of sulfate leaching systems with superior-strength
oxidants (compared with ferric ions) were discussed. For the most part,
these were studied at laboratory scale but are yet to be exploited at
commercial scale. The selected alternative oxidants were more costly
than ferric ions, but some offered advantages in terms of extraction
efciency and kinetics, and further studies are warranted.
1.2. Scope of this review

Table 1 In this second part of the review on chalcopyrite hydrometallurgy at

Minerals and their ideal formulae. atmospheric pressure, chloride-based leaching systems are described
Copper minerals Ideal formula
and compared. The majority of those processes targeted the processing
of copper concentrates and were operated at atmospheric pressure and
Bornite Cu5FeS4
at temperatures approaching the boiling point of ferric chloride solu-
Chalcocite Cu2S
Chalcopyrite CuFeS2 tions (Table 2). A few higher-temperature processes conducted in pres-
Covellite CuS sure vessels have also been described by McDonald and Muir (2007a, b)
Other minerals and the effects of adding sodium chloride to them investigated. These
Albite NaAlSi3O8 pressure oxidation processes are not considered further in this review.
Alunitea KAl3(SO4)2(OH)6
Ferrihydrite 5Fe2O3.9H2O
No account is taken of the possible economics of processing, but rather
Goethite FeOOH the aim is to inform researchers, metallurgists and plant operators about
Gypsum CaSO4.2H2O the wide variety of chemical systems that might be applied in the future
Hematite Fe2O3 when copper demand is higher, ore grades are lower and new technol-
Jarositea KFe3(SO4)2(OH)6
ogies, particularly for reagent recovery and recycle, have been devel-
Magnetite Fe3O4
Marcasite FeS2 oped. While the advantages or disadvantages of current technologies
Muscovite KAl2(Si3Al)O10(OH, F)2 may be referred to in the context of reported results or applications of
Phlogopite KMg3(Si3Al)O10(OH, F)2 specic systems, detailed accounts of the engineering of such technolo-
Pyrite FeS2 gies, their management and/or control are outside the scope of the
Pyrrhotite Fe1 xS (x = 02)
Schwertmannite Fe8O8(OH)6(SO4)nH2O
review.
Silicab SiO2
Vermiculite (Mg,Fe,Al)3(Al,Si)4O10(OH)24H2O 2. Benets and disadvantages of chloride leaching
Zeolite (natrolite) Na2Al2Si3O10.2H2O
a
Potassium or other monovalent cations. The strong interest in chloride systems resides in: (i) the increased
b
Silica varieties include amorphous, colloidal and gel. solubilities of iron and other metals; (ii) enhanced redox properties
98 H.R. Watling / Hydrometallurgy 146 (2014) 96110

Table 2
Some acidic chloride-based processes operated at atmospheric pressure for the extraction of copper from CuFeS2 or other copper sulde concentrates indicating the variety of lixiviants/
oxidants employed.

Process Leach reagents and initial concentrations T Size Scale

(C) (m)

1 U.S. Bureau of Mines (Haver and Wong, 1971) 4 M FeCl3; 0.24 M HCl; possible CaCl2 addition to control sulfate. 106 44 P
2 UBC-Cominco (Milner et al., 1974; Muir and Dixon, 2002) 13.6 M FeCl3; possible CaO or CaCl2 addition to control sulfate. 95100 44 L
3 CYMET (Atwood and Curtis, 1974, 1975) 1.8 M FeCl31.1 M CuCl23.94 M NaCl. 9598 n.s. P
4 Minemet Recherche (Demarthe et al., 1976; Guy and 0.4 M CuCl20.1 M HCl4.3 M NaCl. 107 n.s. P
Broadbent, 1983; Guy et al., 1983)
5 Duval CLEAR process (Dutrizac, 1992; Hoffmann, 1991; Two stage leach, 0.15 M CuCl20.02 MFeCl3 as oxidants in mixed 1.4 M NaCl + 0.6 M 104 n.s. C
Schweitzer and Livingston, 1982) KCl brine; residual CuFeS2 pressure leached with O2 (dissolution with iron rejection).
6 Elkem process (Andersen and Boe, 1985) FeCl3 in brine under controlled redox (430460 mV vs Pt/calomel electrode) such that 105115 n.s. P
all copper remains in solution as Cu(I).
7 Cuprex (Dalton et al., 1987, 1991; Muir and Dixon, 2002) Excess FeCl3 in two-stage counter-current leach; soluble copper as Cu(II). 95 n.s. P
8 Neo-ferric technologies high concentration chloride leach MgCl2 (2.94.3 M)HCl brine; secondary leach contains FeCl3 derived from primary 105116 150 P
(Harris and White, 2008; Harris et al., 2007) leach dissolution of CuFeS2.
9 Intec process (Intec Ltd., 2008; Moyes and Houllis, 2002; P. Solution of 0.47 M Cu(II), 4.9 M NaCl and 0.27 M NaBr has ORP 9501000 mV vs 85 n.s. D
Everett, 1996; P.K. Everett, 1996; Taylor and Jansen, 1999) Ag/AgCl due to formation of BrCl 2 (Halex
TM
)
10 Outotec hydrocopper process (Hyvrinen, and Hmlinen, 0.3 M CuCl2 in 4.8 M NaCl at pH 2 (HCl); 8595 100 D
1999, 2005; Lundstrm et al., 2009)
11 Falconbridge process(es) (Liddicoat and Dreisinger, 2007; FeCl3 (~0.5 M Fe for goethite process and ~1.5 M Fe for hematite process)CuCl2 95 41 L
Lu and Dreisinger, 2013a, 2013b) (~0.8 M Cu) in 0.08 M free HCl (pH 0 or lower) with CaCl2 (2.75 M Ca); (total Cl N5 M).
12 Sumitomo (Imamura et al., 2006; Makino et al., 1996) A two stage process: (i) Cu(II) and Fe(III) in solution reduced by reaction with CuFeS2; 110 44 C
N5.7 M total chloride; (ii) partially leached CuFeS2 reacted with Cl2 gas.

C, commercial; D, demonstration; P, pilot; L, laboratory; n.s., not specied; , ORP control by ne grinding (increased surface area).
Note: Flowsheets for processes are depicted in cited references as well as some reviews, e.g., Muir and Dixon (2002).

because cupric and cuprous ions were stabilised as chloride complexes
and the Cu(I)/Cu(II) redox couple could contribute to sulde oxidation
reactions; (iii) the faster leaching kinetics of chalcopyrite compared
with sulfate systems; (iv) the generation of elemental sulfur rather
than sulfate; and (v) low pyrite reactivity in chloride systems
(Demarthe and Georgeaux, 1978; Dutrizac, 1990; Lu and Dreisinger,
2013a; Muir and Dixon, 2002; Senanayake and Muir, 2003).
The production of elemental sulfur rather than sulfate during the
processing of metal sulde minerals is advantageous because sulfur is
inert and can be stored until market conditions are favourable for its fur-
ther processing and use. In a hydrometallurgical process, less energy is
used if the sulde oxidation stops at sulfur rather than progressing to
sulfate production. The adoption of hydrometallurgy rather than pyro-
metallurgy eliminates the environmental problem of SO2 production
(Spink, 1977). In addition, the production of less sulfuric acid is bene-
cial to downstream processing of pregnant leach solution (PLS) that
requires less neutralising agents and therefore the generation of lower
volumes of waste materials (e.g. gypsum).
Perceived disadvantages are: (i) the corrosive action of chloride,
thus necessitating the use of more expensive materials of construction
for reactors; (ii) the need for ne grinding for processes operated at at-
mospheric pressure; (iii) the co-leaching of multiple elements that re-
quire additional treatments and (iv) the difculty of electrowinning
high-grade copper from chloride solutions. Nevertheless, in respect of
the last point, there are four processes in which copper is recovered
from chloride solutions (Lu and Dreisinger, 2013b). Hein and Joly
(2011) surveyed 25 solvent extraction plants and reported that 18 of
them were operated with PLS containing high sulfate, chloride and cat-
ion concentrations, four of them with chloride concentrations N35 g L1
(1 M).
In the Copper Technology Roadmap of 2004 (AMIRA International,
2004), more efcient use of water in the unit processes associated
with extraction, comminution and separation was given top priority.
Among proposed strategies for improvements in water efciencies in-
cluded in the Roadmap were the use of saline water and recycled
water in processing. The use of seawater, brackish and hypersaline
water and recycled process water have been variously trialled and/or
implemented at mining operations over many years, mainly in
respect of substituting seawater for freshwater in otation circuits
(e.g., Moreno et al., 2011). There are few reports of leaching with seawa-
ter in the public domain (Table 3).
It was noted in the Copper Technology Roadmap that adaptation of
existing processes to different water sources requires better under-
standing of the impact of water quality on processing operations and
on materials of construction. Some of these have been reviewed by
Philippe et al. (2010). In respect of processing chemistry, they include
viscosity and specic gravity (increased water transport costs), chemi-
cal buffering effects (inuencing leach chemistry), product and by-
product contamination (clean water required for washing), evaporation
(and therefore water make-up) and capillary forces, and scaling
(secondary precipitation). In addition, Philippe et al. (2010) stated
that the use of sea water in the bioleaching of low-grade sulde ores
would inhibit benecial bacterial activity.
3. Acidic chloride systems for chalcopyrite concentrate
The leaching of chalcopyrite in acidic chloride media was studied
extensively in the 1980s and 1990s resulting in a number of proposed
processes accompanied by suggested owsheets. Winand (1991) and
Senanayake and Muir (2003) reviewed some important fundamentals
of chloride leaching systems and noted that, in multi-component sys-
tems such as those discussed in this review, solubilities, complexation
reactions and electrochemical reactions are important and possibly lim-
iting factors in the development of processes. In addition Winand
(1991), and also Hoffmann (1991), Dutrizac (1992) and Muir and
Dixon (2002) reviewed individual process developments with brief
descriptions, critical assessments and/or reasons why processes have
not seen long-term commercial success.
In each section that follows, the chemistry of the system is discussed,
based on fundamental laboratory studies. Then example processes that
utilise the chemistry are described briey.
3.1. Comparison of studies
While the main focus of this section is on acidic chloride processes
for concentrates, the rare examples of the application of such processes
to ores are included. Two main difculties arise when comparing the re-
sults of independent studies, temperature and chalcopyrite surface area.
As is the case for sulfate leaching systems, copper extraction rates
increase as the temperature is increased (Fig. 1), a characteristic of
chalcopyrite dissolution that has been exploited in many processes at
atmospheric (Table 2) and higher pressures. Thus, where possible,
 H.R. Watling / Hydrometallurgy 146 (2014) 96110 99

Table 3
Saline water use at mining operations.

Project Mining company Water source Unit processes References

Zaldivar, Chile Cu Placer Dome Brackish Leaching Weston et al. (1995)

Michilla, Chile Cu Antofagasta Minerals Seawater Agglomeration, heap leaching Aroca (1999); Wiertz (2009)
Esperanza, Chile Cu, Au, Mo Antofagasta Minerals Seawater Concentrate production Chadwick (2009); Parraguez et al. (2009)
Boleo, Baja California Zn, Co, Mn Baja Mining Corporation Seawater Tank leaching Dreisinger et al. (2005); Dreisinger (2009).

inter-study comparisons should be made between studies conducted at
similar temperatures.
The second variable is chalcopyrite particle or grain size used in dif-
ferent studies. Dutrizac (1981) leached various chalcopyrite sized frac-
tions in 0.2 M FeCl3 and 0.3 M HCl solutions, calculated initial rate
constants from the initial slopes and, by plotting the rate constants
against 1/r, where r was the mean particle size in microns, showed
that rates were directly proportional to the surface area of chalcopyrite
being leached. That result was consistent with data obtained for chalco-
pyrite leached in ferric sulfatesulfuric acid medium, though rates in
chloride medium were higher than in sulfate medium. The result was
also consistent with the demonstrated advantage of ne grinding in
some process developments conducted at above atmospheric pressure
(e.g., Activox process, chalcopyrite particles 510 m; Dreisinger,
2006). While a brief account of chalcopyrite preparation and measures
of particle size was provided in many of the studies reviewed in this
work, the relevant surface areas were not reported, making it impossi-
ble to normalise the data and so make convincing comparisons. Never-
theless, some data obtained at 8595 C for the leaching of chalcopyrite
in acidied chloride or hybrid sulfatechloride media are compared in
Fig. 2 and data obtained at 2355 C for the leaching of chalcopyrite in
chloridechlorine media are compared in Fig. 3.
3.2. Ferric chloride as oxidant
The oxidation of chalcopyrite in ferric chloride media, while faster
than oxidation in ferric sulfate media, was still generally slow for a metal-
lurgical process, thus driving the assessment of many multi-component
systems. The examples summarised below are for laboratory-scale tests
conducted at atmospheric pressure and temperatures up to approximate-
ly 100 C. Most of these processes were developed for the extraction of
copper from chalcopyrite concentrates.
medium was independent of temperature in the range of 45100 C, es-
sentially independent of acid concentration, but directly proportional to
chalcopyrite surface area.
0
CuFeS2 4FeCl3 CuCl2 5FeCl2 2S 1
The study by O'Malley and Liddell (1987) was focused on the forma-
tion of copper(I) species during the ferric chloride leaching of a ground,
natural chalcopyrite sample. Under test conditions in which ferric ion
concentrations were limiting, they showed that the extent of copper
extraction depended on the initial ferric chloride concentration and
that the total chloride concentration controlled the extent to which
copper(II) was reduced to copper(I) at the chalcopyrite surface (reac-
tion (2)). Wang (2005) also proposed that Cu(I) species had a role in
ferric chloride leaching of chalcopyrite and suggested that reactions (1)
and (3) were both principal reactions in the ferric chloride system.
CuFeS2 3CuCl2 4CuCl FeCl2 2S
0
2
CuFeS2 3FeCl3 CuCl 4FeCl2 2S
0
3
The rate of dissolution of monosized chalcopyrite in ferric chloride
sodium chloride media acidied with hydrochloric acid was studied to
establish the mechanism of leaching (Palmer et al., 1981). The linear
kinetics were consistent with the rate being controlled by surface
phenomena and being dependent on both chloride and ferric ion con-
centrations. Yoo et al. (2010) also focused on leaching mechanisms
when they investigated the leaching of chalcopyrite in FeCl3HCl and
FeCl3H2SO4 media, and mixtures of the two. In rank order, copper
extraction was Cl N ClSO4 SO4 medium. The authors cited the data
of Lin et al. (1991), who noted that copper existed as cupric ions in
solutions with low chloride concentration but that, at high chloride con-
centrations, cuprous ion species such as CuCl, CuCl 2
2 , CuCl3 and CuCl4
3

Dutrizac (1981) examined chalcopyrite dissolution in solutions were formed and that the standard potential between cuprous and cu-
containing 0.3 M HCl and 0.2 M FeCl3 at b100 C (reaction (1)) and pric ions increased. The results were consistent with those of O'Malley
summarised the results as follows: (i) leaching rates were higher in and Liddell (1987). After conducting a thermodynamic study of copper
chloride media than in sulfate media at temperatures N50 C, with a species in chloride solutions, Yoo et al. (2010) concluded that the
three-fold increase in leaching rate for equivalent-sized chalcopyrite
particles; (ii) the rate of chalcopyrite dissolution in ferric chloride 100
(5)
20
80
T C
Cu extraction [%]

(3)
80
15 60
Cu extraction [%]

(4)

70 40
10
(2)
60
20
(1)
5 50
40 0
0 1 2 3
20
Time [hours]
0
0 1 2 3 4
Fig. 2. Copper extraction from chalcopyrite leached in chloride media at 8590 C. Data
Time [hours] from: (1) Al-Harahsheh et al. (2008), 0.5 M FeCl3, 90 C; (2) Al-Harahsheh et al. (2008),
0.5 M FeCl30.025 M CuCl2, 90 C; (3) Bonan et al. (1981), 0.5 MCuCl20.1 M HCl4 M
Fig. 1. Effect of temperature on copper extraction from ground chalcopyrite in 1 M FeCl3 NaCl, 95 C; (4) Ruiz et al.(2011), 0.2 M H2SO40.6 M NaClO2 (gas sparge), 90 C; and
0.2 M HCl medium (redrawn from Havlik and Kammel, 1995). (5) Xian et al. (2012), 0.5 M NaClO31 M HCl, 85 C.
100 H.R. Watling / Hydrometallurgy 146 (2014) 96110
100 (1)
(2)
(3)
80
Cu extraction [%]
60
40
20
(4)
0 tration. Thus the leach chemistry of the UBC-Cominco process was
(5)
0 2 4 6 8 10
Time [hours]
Fig. 3. Copper extraction from chalcopyrite leached in chloride/chlorine media at
2355 C. Data from: (1) Brocchi and Jena (1992), slurry chlorination, 30 C; (2) Cho
(1987), 0.228 M HClO, pH 3.64.4, 23 C; (3) olak et al. (1987), water saturated with
Cl2, 33 C; (4) Dutrizac (1982), 0.1 M FeCl30.3 M HCl, 55 C; (5) Velsquez-Yvenes
et al. (2010b), 0.008 M Cu2+0.2 M HCl0.34 M NaCl, ORP 550620, 35 C.
increase in the critical potential caused by cuprous ion species in a chlo-
ride solution was a key parameter in the faster chalcopyrite leaching
rate.
Elemental sulfur is the major sulfur-reaction product when chalco-
pyrite is oxidised in ferric chloride media (reactions (1)(3)). Dutrizac
(1990) reported that more than 95% of the sulde moiety of chalcopy-
rite was oxidised to elemental sulfur in medium containing 02 M
FeCl3 and 03 M HCl at 95 C, with only 5% of the sulde being oxidised
to sulfate, independent of leaching time (090 h). Dutrizac (1990)
noted that small chalcopyrite grains rapidly became enveloped in ele-
mental sulfur and that the sulfur morphology was independent of either
ferric chloride or hydrochloric acid concentrations. In a similar investi-
gation, Rath et al. (1988) conducted dissolution tests at temperatures
up to 100 C and concluded that the chalcopyrite oxidation rate was di-
rectly proportional to the square root of the ferric chloride concentra-
tion and inversely proportional to particle diameter. In other studies,
different sulfur morphologies were described (Hirato et al., 1986; Lu
et al., 2000; Majima et al., 1985) but relationships between them and
leaching conditions, particle sizes or retention times are yet to be
elucidated.
Saxena and Mandre (1992) studied the ferric chloride leaching (0.2
M FeCl3) of chalcopyrite in an ore containing 0.75% Cu. Agitated batch
leaching tests of up to 6 h duration were conducted in the temperature
range of 3090 C using the 104 + 74 m size fraction of the ore. In
those tests, the solution and ore were both pre-heated before being
contacted. The results indicated that the process was controlled initially
by chemical reaction between ferric chloride and chalcopyrite but that,
subsequently, the rate was controlled by diffusion through the sulfur
product layer.
Example processes utilising ferric chloride as oxidant include the
USBM process (Haver and Wong, 1971; Haver et al., 1975) and the
UBC-Cominco Process (Milner et al., 1974; Muir and Dixon, 2002).
The purpose of the USBM investigation (Haver and Wong, 1971) was
to develop an alternative method of obtaining copper from chalcopyrite
without the evolution of SO2. Ferric chloride was chosen as the oxidant
because it had the correct oxidation potential to convert sulde to ele-
mental sulfur (reaction (3)). Conditions were: 4 M FeCl3, with a ratio
of 2.7:1 FeCl3:CuFeS2; 106 C and 2 hour leach duration. The small
amount of sulfur that was oxidised to sulfate could be precipitated as
gypsum with the addition of CaCl2 to the solution. The leachate
contained 1 M Cu (60:40 Cu(I):Cu(II)), 4 M Fe and only 0.03 M SO2 4 leach solution pH, elemental sulfur formed mainly as isolated globules
and the residue contained 16 wt.% Fe, 72 wt.% S (approximately 50% of
which was elemental sulfur) and 0.024 wt.% CaO. The original
owsheet, utilising solvent extraction to remove the sulfur, cementa-
tion to recover copper from solution and chlorination to regenerate
the ferric chloride, was estimated to be too expensive for commercial
acceptance (Haver et al., 1975). Subsequent cost-reducing modica-
tions to the process were the extraction of sulfur from residues using
aqueous ammonium sulde, direct electrowinning of copper in a dia-
phragm cell and regeneration of ferric ions by aeration.
Milner et al. (1974) described a closed-cycle hydrometallurgical pro-
cess in which the high-quality products metallic copper, metallic iron
and elemental sulfur were produced. A solution containing 13.6 M Fe
as FeCl3 was used to leach chalcopyrite (912 h at 95100 C) (reac-
tion (3)) and CaCl2 or CaO addition was used to control sulfate concen-
almost identical to that of the USBM process, yielding solutions with a
1:1 ratio Cu(I):Cu(II) (Muir and Dixon, 2002). In the UBC-Cominco pro-
cess, the hot ltered solution was treated with copper metal to reduce
Cu(II) to Cu(I) and insoluble CuCl, crystallised from the cooled solution,
was converted to high purity copper powder by hydrogen reduction.
3.3. Cupric chloride as oxidant
In the previous section, the results discussed were obtained from
studies in which the starting acidic solutions contained ferric chloride.
The distinction is made in this section, that the studies were initiated
in acidic solutions containing cupric chloride. Clearly, once chalcopyrite
dissolution had commenced (e.g., reactions (2), (4) and (5)), ferrous
ions would be released to solution during chalcopyrite oxidation, poten-
tially become oxidised to ferric ions and increase the contribution of re-
actions such as (1) and (3) to chalcopyrite dissolution.
CuFeS2 H2 SO4 CuS FeSO4 H2 S 4
3 1 0
CuFeS2 CuCl2 =4 O2 2CuCl =2 Fe2 O3 2S 5
Nicol and co workers (Miki and Nicol, 2011; Nicol et al., 2010;
Velsquez-Yvenes et al., 2010a, 2010b) conducted a wide ranging
study of the dissolution of chalcopyrite in chloride solutions containing
cupric ions and dissolved oxygen. Initially, it was shown that the rate of
chalcopyrite dissolution was enhanced when leaching was conducted in
an ORP range of 550620 versus SHE at 35 C in a solution containing:
0.2 M HCl, 0.008 M Cu2 + (simulating rafnate) and 515 mg L 1
dissolved O2 (Velsquez-Yvenes et al., 2010a). Leaching at ORP
b540 mV caused reduced rates of chalcopyrite dissolution and covellite
or chalcocite formed on some chalcopyrite surfaces.
In the extension of their work, Velsquez-Yvenes et al. (2010b) fo-
cused on the kinetics of chalcopyrite dissolution under conditions that
might be expected in a heap leach operation. Experiments were con-
ducted at 35 C with controlled ORP and initial test solutions were 0.2
M HCl with 0.008 M Cu2 +. However, the addition of ferrous ions or
the conduct of tests at low pH caused difculties in controlling the
ORP. The presence of a small concentration of cupric ions was essential
but increased copper concentrations did not result in enhanced chalco-
pyrite dissolution rates. Dissolution rates were not greatly affected by
changes in the total chloride concentration, which was varied by adding
sodium chloride. The strong dependences of dissolution rates on both
temperature and particle size (surface area) were consistent with
many other literature data (e.g., Ikiz et al., 2006; Naderi et al., 2011;
Skrobian et al., 2005; Xian et al., 2012).
The goal of the third part of the study (Nicol et al., 2010) was to de-
scribe a reaction mechanism consistent with the newly acquired data
and their previous results. In ancillary experiments it was shown that:
(i) the chalcopyrite surface was converted to a covellite-like phase dur-
ing leaching at potentials below the potential window; (ii) at normal
and seldom on the chalcopyrite surface, suggesting that an aqueous
 H.R. Watling / Hydrometallurgy 146 (2014) 96110
intermediate sulfur species existed; and (iii) nely ground pyrite
catalysed the reaction and became covered in layers of sulfur. Nicol
et al. (2010) proposed a reaction model in which, within the potential
window, chalcopyrite dissolved partially to form H2S and a covellite-
like surface species (reaction (4)) and that the H2S was oxidised by ox-
ygen in a reaction catalysed by cupric ions in two stages (reactions (6)
and (7)). The authors noted that in the proposed reactions, the species
represented as Cu2 + and Cu+ included both aquo-ions and chloro-
complexes that varied according to solution composition. Nicol et al.
(2010) supported the hypothetical reaction model with a detailed
study of the kinetics of copper-catalysed oxidation of H2S. Subsequently,
in the fourth part of their study, Miki and Nicol (2011) modied their
proposed mechanism to account for a newly-detected, intermediate
peroxide species (reaction (7) replaced by reactions (8), (9) and (10)).
2 0
H2 S 2Cu 2Cu S 2H rapid 6 leach fresh concentrate. Copper was partially extracted from the other
2
4Cu O2 4H 4Cu 2H2 Oslow 7 residue was treated in a second dissolution stage under the same condi-
Cu O2 Cu O2 8
2 product, in accord with reactions (2) and (11) (Demarthe et al., 1977).
Cu O2 Cu H 2Cu HO2 9
2 2Fe
2Cu H2 O2 2H 2Cu 2H2 O 10
In a recent mechanistic study Cai et al. (2012) showed that, when
treated in sealed vessels for a month with hydrochloric acid (with and
without cupric ions) at temperatures up to 100 C, chalcopyrite was
transformed into chloride-rich covellite-like phases of different stoichi-
ometries (e.g., CuS10.5xClx; CuS0.5Cl0.5; reaction (4)) and that some of
the iron leached from the chalcopyrite was precipitated as an iron
oxide thought to be hematite (Fe2O3; e.g., reaction (5)).
Key conditions used for the study by Bonan et al. (1981) were as
follows: ground chalcopyrite particles (sized fractions in the range of
2590 m, 5 g) were suspended in 500 mL of 0.10.5 M Cu(I)Cu(II)
chloride solution with 0.1 M HCl and 2.54 M NaCl in a reactor from
which oxygen was largely eliminated by sparging with nitrogen gas
(see also a similar study by Tchoumou and Roynette, 2007). Removal
of oxygen was necessary to prevent reaction (7) from proceeding, as
this reaction would cause an increase in ORP during the experiment.
Strong chloride solutions were chosen to promote reaction (2) and sta-
bilise the cuprous chloride complexes, mainly CuCl 2 and CuCl3
2
(Lin
et al., 1991); the Cu(II)/Cu(I) ratio was varied in the range of 0.57.
Initial ORP values for each solution composition were not reported but
for selected tests, were in the range of 555585 mV (versus SHE). The
results showed that chalcopyrite leached faster in solutions of higher
Cu(II)/Cu(I) ratio and as the chloride concentration and/or temperature
was increased. Leaching rates were primarily dependent on ORP regard-
less of the Cu(II)/Cu(I) ratio and chloride concentration that created the
condition. In all tests, sulde was converted to elemental sulfur with
almost no sulfate formation.
Padilla et al. (1997) gave a good account of the chemistry of the
CuCl2NaClO2 system for chalcopyrite leaching. They studied oxygen-
ated brine solutions containing up to 5 M chloride ions in tests conducted
at atmospheric pressure and temperatures up to 105 C and reported that
high copper extraction could only be achieved at temperatures near the
boiling points of the solutions. In separate but similar studies Skrobian
et al. (2005) and Turkmen et al. (2012) examined the leaching of chalco-
pyrite concentrate in CuCl2NaClHCl. The results of both studies indicat-
ed that the addition of cupric ions strongly enhanced copper extraction
but that the addition of sodium chloride enhanced copper extraction to
a lesser extent. The nature of the elemental sulfur formed during
CuCl2HCl leaching of chalcopyrite was not investigated in either study.
Skrobian et al. (2005) noted that it is commonly accepted that sulfur pre-
cipitated on chalcopyrite surfaces can slow the rate of extraction, report-
ed that sulfur was partially oxidised to sulfuric acid by cupric chloride,
and concluded that the formation of a compact layer that would slow
101
extraction if it were to form on chalcopyrite surfaces was not observed.
Turkmen et al. (2012) analysed leaching kinetics using the shrinking
core model, but failed to report whether the elemental sulfur had formed
on chalcopyrite surfaces, which is a basic assumption of that model.
Example processes utilising cupric chloride as the initial oxidant in-
clude the Minemet Recherche Process (Demarthe et al., 1976, 1977; Guy
and Broadbent, 1983; Guy et al., 1983) and the HydroCopperTM Process
(Hyvrinen and Hmlinen, 1999, 2005; Lundstrm et al., 2005, 2009).
The Minemet Recherche process was developed for the extraction of
Cu, Pb and Zn from complex sulde concentrates (Demarthe et al.,
1977). The sulde concentrate was leached in 0.4 M CuCl20.1 M HCl
4.3 M NaCl solution (pH 1) at temperature 107 C for 3 h. This reaction
mixture was ltered and separated into two parts. One part of the solu-
tion was subjected to air oxidation (pH 13, temperature N90 C);
precipitated goethite was removed before the solution was recycled to
portion of the solution using an organic extractant. The partially leached
tions as the rst. Advantages of the two stage dissolution process were
iron removal and elemental sulfur as the main sulfur-containing reaction
2 2
4Cu 1:5O2 H2 O2FeOOH 4Cu 11
Some of the above cited laboratory studies may have contributed to
the development of the HydroCopperTM process, a CuCl2NaCl system
operated at pH 1.52.5 and close to 100 C (Hmlinen, 2005;
Hyvrinen and Hmlinen, 2005; Lundstrm et al., 2005). Chalcopyrite
is leached by the strong CuCl2 (0.3 M)NaCl (4.8 M) solution sparged
with oxygen or air to oxidise the product ferrous ions and therefore
facilitate iron(III) rejection as goethite (reaction (11)) or hematite (re-
action (5)). The copper is precipitated as cuprous oxide and then con-
verted to metal by hydrogen reduction. A standard chloralkali cell is
used to regenerate the reagents chlorine, caustic and hydrogen.
Hyvrinen and Hmlinen (2005) make a number of claims in respect
of the process: (i) capital costs mid way between heap leaching and
pressure leaching, depending on ore mineralogy and some external
factors; (ii) suited to smaller operations, e.g., 20150 thousand tonnes
per annum capacity; (iii) applicable to low quality concentrates; and
(iv) operating costs approximately US 2030 cents per kilogram
depending on feed mineralogy and energy costs. These attributes, togeth-
er with efcient extraction of copper and precious metals, iron(III) (and
arsenic) rejection, various process routes for solution purication and
reagent generation, make this a promising technology but the absence
of independent assessments in the public domain and/or commercial de-
velopment thus far may be indicative of unresolved operational issues.
3.4. Mixed ferric chloridecupric chloride oxidants
According to Parker et al. (1981), a mixed oxidant of ferric and cupric
ions in chloride medium was an effective oxidant for chalcopyrite
because the reduction of copper(II) to copper(I) occurred faster than
the reduction of iron(III) to iron(II) at the chalcopyrite surface (reac-
tions (2) and (3)). Iron(III) or oxygen subsequently oxidised the
cuprous ions formed in the surface reaction to regenerate the cupric
ion oxidant. In addition to faster reaction kinetics with added chloride,
sulfur crystallinity was increased and there was minimal oxidation of
sulde or sulfur to sulfate (Senanayake and Muir, 2003). Al-Harahsheh
et al. (2008) examined the catalytic effect of cupric ions on the oxidation
of chalcopyrite in ferric chloride medium, especially noting the effect
of agitation. They explained the observed reduction in chalcopyrite
oxidation rates in agitated systems, compared with stagnant systems,
as being due to the removal of cupric chloride complexes formed at
the interface between chalcopyrite surfaces and ferric ions and pro-
posed that cupric ion was acting as a secondary oxidant in the dissolu-
tion reaction. These authors also noted that chalcopyrite oxidation
102 H.R. Watling / Hydrometallurgy 146 (2014) 96110
was faster in a closed vessel (without agitation) than in an open vessel
but could not provide an explanation for this phenomenon.
The chemical system cupric chlorideferric chloridehalide (single
or mixed salts) was a key component of the Cymet process (Allen
et al, 1973; Atwood and Curtis, 1975; Kruesi, 1972; Paynter, 1973),
the Duval CLEAR process (Schweitzer and Livingston, 1982) and the
Falconbridge process (Liddicoat and Dreisinger, 2007).
In the CYMET process, described as a hydrometallurgical process for
pollution-free recovery of metallic copper from chalcopyrite (Atwood
and Curtis, 1974), copper suldes were almost completely dissolved
(107 C) in two stages (oxidation and reduction) with the production
of elemental sulfur (reaction (3)) and concomitant cupric chloride reduc-
tion to cuprous chloride. The process required a molar ratio of at least 4:1
FeCl3:CuFeS2. The cuprous chloride was prevented from precipitating in
the strong chloride solution or, in a later process modication (Atwood
and Curtis, 1975), a mixed NaClKCl solution, the KCl assisting the rejec-
tion of iron and sulfate as K-jarosite (reaction (12)). In a subsequent iron
and sulfate control stage, iron(II) was re-oxidised to iron(III) and excess
amounts precipitated with sulfate ions. The CYMET process was operated
for a period of about 10 years but shut down in 1982, ostensibly because
of a slump in the copper industry (Hoffmann, 1991).
3 2
3Fe 2SO4 6H2 O M MFe3 SO4 2 OH6 6H 12 surface.
where M = K+, Na+, NH+ 4 or H3O
+
The Duval Clear (Copper Leach, Electrolysis and Regeneration)
process (Schweitzer and Livingston, 1982) applied similar chemistry
for the initial partial leaching of chalcopyrite using Fe(III) and Cu(II) as
oxidants in a mixed NaClKCl brine at 104 C (e.g., reactions (1)(3)).
In the second stage, the nal chalcopyrite leaching and oxy-hydrolysis
of iron were combined in a pressure leach at 150 C. Part of the iron
was precipitated as K-jarosite (reaction (12)). A commercial plant was
operated in Arizona in the early 1980s for a period of 6 years, producing
approximately 80 tonnes copper per day, but the purity of the copper
was not high enough to justify the cost (Ayres et al., 2002). Muir
and Dixon (2002) briey described some of the technical problems en-
countered with the CLEAR process. The recently-described, two-stage
counter-current chloride leach developed for Falconbridge (Liddicoat
and Dreisinger, 2007) also applied similar chemistry at temperatures
near the boiling point of the lixiviant. The feed solution contained high
concentrations of ferric chloride (~0.5 M Fe for the proposed goethite
process and ~1.5 M Fe for the hematite process), ~0.8 M Cu as cupric
chloride, 2.75 M Ca as calcium chloride with 0.08 M free HCl
(pH 0); the total chloride concentration was N5 M.
4. Hybrid chloridesulfate systems applied to concentrates
4.1. Oxygen as oxidant in hybrid chloridesulfate system
The advantage of using sulfuric acid and sodium chloride to create a
chloride lixiviant is that those reagents are cheaper than ferric chloride
or cupric chloride. Nevertheless, an oxidant is still required, in this case
oxygen (reaction (13)). There should be no need to add ferric ions to the
system initially; ferrous ions produced during chalcopyrite leaching
would be oxidised to ferric ions and subsequently contribute to overall
copper extraction (reactions (1) and (3)). With careful selection of
leaching conditions, most of the iron and some sulfate can be precipitat-
ed as sodium jarosite (reaction (12)).
2 2 0 chloride to the reduction of ferric iron concentration (jarosite precipita-
CuFeS2 O2 4H Cu Fe 2S 2H2 O 13
Li et al. (2010) examined the extraction of copper from a chalcopy-
rite concentrate (size fraction 3875 m) for a suite of leach systems.
In tests conducted at 75 C, they measured faster kinetics for the NaCl
(0.25 M)H2SO4 system at pH 2 (97% copper extraction in 170 h) than
at pH 1 (58% copper extraction in 170 h). This difference was attributed
to the increased solubility of iron-containing secondary minerals due to
the formation of FeCl2+ solution species and the consequent lower fer-
ric ion activities in the presence of chloride. Ruiz et al. (2011) reported
that leaching of chalcopyrite concentrate with average particle size of
12 m in sulfatechloride solutions was rapid, 90% of the copper being
extracted in 180 min at 100 C. The presence of 0.5 M chloride ions
(29 g L1 NaCl) enhanced the leaching rate signicantly but the addi-
tion of 3 g L1 Fe3+ caused the ORP to increase and the leaching rate
to slow.
Lu et al. (2000) dissolved nely-ground chalcopyrite concentrate
in solutions of pH b 0.8 (0.8 M H2SO4) containing 1 M NaCl at temper-
atures in the range of 6095 C. They achieved up to 97% copper
extraction in 9-hour tests. Based on their results showing that
chloride concentrations N0.5 M did not enhance the leaching rate
of chalcopyrite (consistent with the results of Palmer et al., 1981),
Lu et al. (2000) concluded that it was important only that there
were sufcient chloride ions present rather than an excess. This nd-
ing has commercial implications for geographical areas lacking in
freshwater but able to use saline bore water or seawater; seawater
contains approximately 0.5 M chloride ions. Examination of the
residues showed that the sulfur reaction product obtained in the
presence of 1 M NaCl was crystalline and porous, allowing reactants
to diffuse through the surface product layer to the unreacted mineral
An application of this leach chemistry is described in a patented
process (Sawyer and Shaw, 1983) for the recovery of copper from a
copperlead matte using oxygenated acidic sulfatechloride solutions.
According to Lu et al. (2000), that was possibly the only low-pressure
sulde leach process to have been commercialised. O'Brien et al.
(1999) piloted a similar process that involved oxygen sparging of an
agitated leach at 8095 C and atmospheric pressure. A size fraction
100 + 75 m of the ground chalcopyritepyrite ore (4% Cu) was
used for the tests of duration less than 24 h. The pyrite in the ore
promoted chalcopyrite oxidation via galvanic interaction and up to
95% of the chalcopyrite was oxidised compared with only 17% of the
marcasites/pyrite content.
4.2. Ferric ion as oxidant in hybrid chloridesulfate system
Dutrizac (1981) undertook a critical survey on the ferric ion
leaching of chalcopyrite and augmented the reported data to resolve
some inconsistencies. Using lithium chloride as the additive, Dutrizac
(1981) reported that increased chloride ion concentration in a ferric
sulfatesulfuric acid leach system resulted in progressively accelerated
copper extractions from chalcopyrite concentrate ( 20 + 14 m
particle size) at temperatures higher than 50 C, specically 2.5 times
at 34 M chloride ion, 0.3 M H2SO4 (~ pH 0.2), 0.1 M Fe2(SO4)3 and
90 C. The addition of lithium chloride was a means of increasing the
chloride concentration without promoting the formation of jarosite-
like compounds, as would happen if sodium or potassium chlorides
were added. More recently, the inuence of sodium chloride on ferric
sulfate oxidation of chalcopyrite was studied at 95 C using a nely-
ground chalcopyrite concentrate (5% solids loading; d50 = 5.5 m)
in 0.9 M Fe2(SO4)3 solution acidied with H2SO4 to pH 0.15 and sparged
with O2 (Carneiro and Leo, 2007). Up to 90% of the copper was extract-
ed with 1 M sodium chloride (58 g L 1), compared with 45% of the
copper in the absence of sodium chloride. Carneiro and Leo (2007)
attributed the enhanced copper extraction in the presence of sodium
tion; reaction (12)), the formation of cuprous chloride complex ions
and the participation of the Cu(I)/Cu(II) redox couple in oxidation,
and a chloride-induced increase in the surface area and porosity of
the sulfur reaction product. Not specically mentioned by Carneiro
and Leo (2007) but probably also contributing to enhanced copper ex-
traction would be the acid generated during jarosite precipitation
(reaction (12)).
 H.R. Watling / Hydrometallurgy 146 (2014) 96110
In a 20-day study at 87 C (Kinnunen and Puhakka, 2004), a much
lower addition of sodium chloride (5 g L 1; 0.09 M) resulted in en-
hanced copper extraction in ferric sulfate media initially 0.38 M Fe(III)
and pH 1. Copper extractions of approximately 100% and 80% were
achieved with and without added sodium chloride, respectively. In
that study, ferric ions were regenerated in a secondary bioreactor con-
taining a chloride-tolerant culture of iron(II)-oxidising microorganisms.
In the tests with added sodium chloride, solutions were pH b1, com-
pared with pH 1.21.3 in the absence of sodium chloride; the increased
acidity in the chloride-amended test would have contributed to en-
hanced copper extraction.
4.3. Chlorate as oxidant
Kariuki et al. (2009) studied chalcopyrite leaching in sealed vessels.
They mixed 2 g chalcopyrite concentrate with up to 3 g sodium chlorate
and then added 30 mL of 10 g L1 H2SO4 (solution composition 0.9 M
NaClO3, 0.1 M H2SO4; ~ pH 0.7). The results showed that chalcopyrite
oxidation (reaction (14)) increased with increased temperature in the
range of 45100 C. Assuming a stoichiometric reaction, the end result
would be a solution containing 0.9 M Cl, sufcient to contribute to en-
hanced copper extraction through the stabilisation of iron and copper
complex ions but at higher pH than the conditions of Carneiro and
Leo (2007).
6CuFeS2 17NaClO3 3H2 SO4 3Fe2 SO4 3 6CuSO4 17NaCl 3H2 O
14
Sodium chlorate also enhanced the dissolution of a chalcopyrite
concentrate in hydrochloric acid solutions (Xian et al., 2012). At 45 C,
copper extractions after 5 h in solutions 0.5 M and 1 M NaClO3 in 1 M
HCl were 45% and 65% respectively (Xian et al., 2012). The leaching
rate accelerated with increased hydrochloric acid up to 1.5 M. In addi-
tion to chlorate ion, the reaction products ferric chloride and gaseous
chlorine (detected by odour during leaching; reaction (15)) could
also have oxidised chalcopyrite but the stoichiometry of the reaction
products indicated that the gaseous chlorine was more likely to
have been volatilised. Surface area (grain size) was an important pa-
rameter in the study by Xian et al. (2012), consistent with published
data (e.g., Ikiz et al., 2006; Lottering et al., 2008; Naderi et al., 2011;
Watling et al., 2009).
NaClO3 6HCl3Cl2 NaCl 3H2 O 15
5. Other oxidants
5.1. Cl2Br2
The halide complex BrCl 2 is described as having a number of
advantages when applied to mineral leaching. It is known to store
anodic energy in a soluble form, which should therefore not contam-
inate the metal product of electrolysis, and the resulting high oxida-
tion potential of the anolyte promotes the leaching of specic metals
such as precious metals (P. Everett, 1996). In the INTEC process, the
lixiviant (0.47 M Cu(II), 4.9 M NaCl and 0.27 M NaBr) is generated
at the anode of the electrowinning cell. The complex anion BrCl 2 rately predicted solidliquid and liquidvapour equilibria as well as lin-
(HalexTM) with Cu(II) and O2 are the oxidants during the leaching
of copper concentrate at atmospheric pressure, 8085 C and ORP
9501000 mV vs Ag/AgCl (reactions (16)(19)) (Intec Ltd., 2008).
The solution is maintained at pH 23 during the leach to avoid HCl
or Cl2 volatilisation and to promote goethite precipitation in the
rst stage of leaching. In the third stage, the Eh is enhanced by the
BrCl2 complex ion, allowing free gold to dissolve and stabilise as
103
the AuBr
4 complex once all the copper has been leached (Muir and
Dixon, 2002).
0
4CuFeS2 5O2 20HCl4CuCl2 4FeCl3 8S 10H2 O 16
0
2CuFeS2 5NaBrCl2 2CuCl2 2FeCl3 4S 5NaBr 17
4CuCl O2 4HCl4CuCl2 2H2 O 18
CuFeS2 4CuCl2 5CuCl FeCl3 2S
0
19
The technical advantages of the Intec process were marketed as
(i) not requiring an autoclave and the use of inexpensive materials of
construction such as bre glass and polypropylene (temperature
below solution boiling point), (ii) high intensity electrowinning from
Cu(I) solution (not requiring solvent extraction) to yield high purity
granular copper (meeting LME A grade specication), (iii) ability to
treat low-grade and contaminated concentrates and (iv) lixiviant re-
generation (Moyes and Houllis, 2002; P. Everett, 1996; P.K. Everett,
1996). However, according to Muir and Dixon (2002), while the Intec
process showed promise, several issues remained. Gold was encapsulat-
ed in sulfur or pyrite, requiring separate treatment for gold recovery,
sulfur and pyrite reported to the leached residue, presenting an envi-
ronmental issue for residue-disposal, and the amalgamation of silver re-
quired strict control with respect to copper product contamination
and the environment. Operating costs were relatively low, but copper
extraction was also low (94%) (Lu and Dreisinger, 2013a).
5.2. High MgCl2low HClFeCl3
Harris et al. (2006a, 2006b, 2007, 2008); Harris and White, 2006,
2008) described a method for the leaching of sulde minerals at atmo-
spheric pressure in a temperature range of 75115 C using high chlo-
ride salt/low hydrochloric acid concentrations with an oxidant. The
solution, initially 2.94.3 M MgCl2 was acidied with HCl to pH ~1. Sub-
sequently, the solution also contained ferric chloride after reaction with
the ore, and was controlled at solution pH ~1 and ORP 200600 mV ver-
sus SHE. The leaching conditions were chosen to promote the formation
of hydrogen sulde from the base metal sulde (example reactions (20)
and (21) for chalcopyrite). The hydrogen sulde was stripped from the
solution, reducing the amount of sulfate generated in the leach to very
low levels.
2CuFeS2 6HCl Cl2 4H2 S 2CuCl2 2FeCl3 20
4CuFeS2 20HCl O2 8H2 S 4CuCl2 4FeCl3 2H2 O 21
This process was developed for the Ferguson Lake Project in Canada
(Harris et al., 2006a, 2006b, 2008), where the massive sulde ore body
containing base and precious metals was not amenable to concentration
by otation or other physical separation. In this process, the ore was
treated directly in the highly-concentrated chloride brine with its high
proton activity. Reagent recycle was one of the keys to the economics
of the process. Knigsberger et al. (2008a) developed a Pitzer model
with which the thermodynamic properties of MgCl2HCl aqueous solu-
tions up to 350 g L1 (10 M) chloride in the temperature range of
25120 C could be predicted. The authors noted that the model accu-
ear trends indicating nearly ideal mixing behaviour in MgCl2HCl
solutions. In a further study, Knigsberger et al. (2008b) showed that
the solubilities of metal(II) chlorides, the solubility constants of iron(III)
oxides and hydroxides, and the redox potentials of Fe(III)/Fe(II)
depended on the MgCl2 concentration in a near-linear relationship. The
authors concluded that these results could be used to predict process pa-
rameters for improving yields or controlling iron and other impurities.
104 H.R. Watling / Hydrometallurgy 146 (2014) 96110
5.3. Gaseous Cl2aqueous Cl2HClO
Brocchi and Jena (1992) and Jena and Brocchi (1992) examined slur-
ry chlorination of a chalcopyrite concentrate (~35 wt.% Cu, 75 m par-
ticle size) at 30 C. An aqueous slurry of the concentrate was prepared
and chlorine gas bubbled through it for the selected time period. The
pH of the slurry before and during chlorination was not reported. It
was found that the rapid reaction was dependent on solids loading.
With a 5% w/v solids loading, 100% copper extraction was possible in
5 min; with a 10% solids loading, the time required for 100% extraction
was 30 min; but with a 15% solids the maximum extraction was 85% Cu.
The possible process was described as attractive because of the high
yield, ease of operation, small capital investment, low energy consump-
tion and relatively easy scale-up for commercialisation.
In chlorination tests at 23 C and solutions of pH 3.64.4, conditions
under which hypochlorous acid was the dominant chlorine solution
species (Fig. 4) and cupric ions would remain in solution, Cho (1987)
found that up to 92% Cu was extracted in 1 h from a chalcopyrite
concentrate in a 0.228 M HClO solution. The reaction was pH-
independent within the chosen pH range (reaction (22)). olak et al.
(1987) studied the dissolution kinetics of chalcopyrite in water saturat-
ed with chlorine and represented the overall reaction (23) as the net re-
sult of a series of intermediate reactions between Cu2S, CuS, FeS, S, FeCl2
or S2Cl2 with chlorine. Dissolution rates decreased with increased tem-
perature in the range of 1033 C, the decrease being attributed to the
lower concentration of dissolved chlorine at higher temperature. Up to
95% Cu was extracted at 10 C in 80 min. Solution pH values before and
after leaching were not reported but were presumably mildly acidic.
While the proposed overall reaction (23) does not contain any insoluble
compounds, olak et al. (1987) noted that the dissolution rate was con-
trolled by diffusion through a product layer on the unreacted chalcopyrite
surface containing sulfur and an undened ash layer of insoluble gangue
minerals. The work by Jackson and Strickland (1958) was carried out
using dilute aqueous chlorine solutions at pH 1. The title of their report
is misleading in that the study was made using individual mineral speci-
mens, not ore as suggested. The authors reported that a layer of elemental
sulfur or sulfur monochloride formed on chalcopyrite surfaces.
2 2 0
2CuFeS2 11HClO2Cu Fe2 O3 2SO4 2S 11Cl 11H 22
2CuFeS2 17Cl2 16H2 O2CuCl2 2FeCl3 4H2 SO4 24HCl 23
In the study described by Ikiz et al. (2006), the active agent
was hypochlorous acid prepared by acidifying commercial grade hypo-
chlorite solution with hydrochloric acid. The optimum pH for copper
extraction from an ore was pH 5 but the pH decreased during the disso-
lution, consistent with reaction (22). Using a 0.2 M HClO concentration
1 perchloric acid were examined. The rst was a mechanistic study
0.8 chlorine aq
hypochlorous
0.6 acid
mol
chloride
0.4
hypochlorite
chlorine vap
0.2
0
0 2 4 6 8 10
pH
Fig. 4. Chlorine speciation as a function of solution pH for a 0.2 M solution of sodium
hypochlorite acidied with hydrochloric acid (OLI Analyzer Studio Version 3.2).
and a 4 g L1 solids loading, Ikiz et al. (2006) measured copper extrac-
tions of 4080% in 115 min. They compared copper extraction from
153 m to 212 + 150 m size fractions and showed that extraction
rates decreased with increased particle size. The results highlight the
importance of chalcopyrite liberation and available sulde surface area
for larger particles.
Processes employing chlorine or hypochlorous acid to oxidise
chalcopyrite are not new. For example, Slater (1922) described a two-
stage process in which a copper ore was (i) subjected to a sulfuric acid
leach to remove copper oxides and, after separating the leached ore
from solution and (ii) the residue was reacted with a relatively concen-
trated oxidizing agent, either sodium hypochlorite or calcium hypo-
chlorite in slightly acidic condition. Slater (1922) presented case
studies on several ores which yielded high extractions. The inventor
failed to note the ore crush size, but as liberation was not reported
to be an issue, presumably the ores were milled or pulverised for
the test work. Kissock (1940) employed hypochlorous acid (chlorine
monoxide) for the dissolution of mineral suldes and extracted nickel
and cobalt. The mechanism was described as the oxidation of the metal
suldes through the release of nascent oxygen which attacked non-iron
containing compounds preferentially. More recently, Welham et al.
(2012) proposed the use of an aqueous solution of chlorine-based
oxidising species to oxidise ore or concentrate containing sulde miner-
al phases. The leach process steps were (i) exposure of ore or concen-
trate to 10 mol% HClO (acidic) and (ii) allowing or facilitating the
oxidation of sulde phases, in the process decreasing the pH so that
the predominant oxidising species was Cl2.
In the Sumitomo Process, based on the earlier MCLE Process for
leaching nickel matte, copper is leached from chalcopyrite concentrate
using chlorine gas at atmospheric pressure (Imamura et al., 2006). A
two-stage leach is employed. In the rst stage, the introduction of chal-
copyrite concentrate to a solution containing cupric and ferric chlorides
causes their reduction to cuprous and ferrous ions, respectively,
with chalcopyrite dissolution (reactions (2) and (3)). The almost 6 M
background concentration of chloride prevents the precipitation of
cuprous chloride (CuCl). In the second stage, conducted at 500520 mV
vs Ag/AgCl, the partially leached chalcopyrite is reacted with chlorine
gas (reactions (24)(26)) to effect the complete extraction of copper.
CuFeS2 1:5Cl2g CuCl FeCl2 S2 24
2 3
2Fe Cl2g 2Fe 2Cl 25
2
2Cu Cl2g 2Cu 2Cl 26
5.4. HClO4
Two studies were found in which the reactions of chalcopyrite with
(Harmer et al., 2006). In that study, perchloric acid was chosen because,
at the concentrations used, it would not act as an oxidising agent, the
perchlorate anion would not complex other solution species, and its
use would facilitate the monitoring of soluble sulfur species arising
from chalcopyrite dissolution. An extensive study of the reaction prod-
ucts was undertaken and a reaction pathway, generally consistent
with that of Hiroyoshi et al. (2000) for ferrous-promoted chalcopyrite
dissolution, was proposed.
In the second study (Li et al., 2010) on chalcopyrite dissolution
rates at a temperature of 75 C and pH 1 and 2 in different acids, includ-
ing perchloric acid, the conditions employed were closer to those
applied in extraction studies. Nevertheless, this study also focused on
mechanisms, rather than copper extraction and, with specic excep-
tions, was most like an acid leaching (ferric ion-decient) system,
that progressed according to reaction (4) rather than reaction (1). An
interesting result was that perchloric acid was the most effective copper
extractant at pH 1 but the least effective at pH 2. In contrast, the
 H.R. Watling / Hydrometallurgy 146 (2014) 96110 105

hydrochloric acid-sodium chloride system was the most effective ex-
tractant at pH 2 but very poor at pH 1.
6. Acidic chloride systems for chalcopyrite ores in heaps or dumps
Heap leaching is a technology developed for the extraction of metals
from whole ores crushed to particle sizes appropriate for the required
extraction, acid consumption and heap permeability. It is a renement
of the less-closely controlled in situ, in stope and run-of-mine dump
leaching options, and has been practised for many years as a means of
recovering metal values from ores that are not economic to concentrate
(Domic, 2007; Watling, 2006; and references therein).
There are a number of challenges associated with whole ore leaching
in heaps or other types of reactor, which must be addressed during pro-
cess development. Those discussed in this review are restricted to dif-
ferences that might be encountered when saline water is substituted
for freshwater in the leaching process, not including engineering issues
such as those described by Philippe et al. (2010). It should be noted that
Philippe et al. (2010) also concluded that the construction of a desalina-
tion plant could be an economic alternative to the delivery and use of
seawater at a mine site, and this conclusion was supported by a recent
report (Nueva Minera y Energa, 2013) in which it was indicated that
the use of desalinated water by the Chilean mining industry was likely
to increase eight-fold by 2022, with 16 ofcial projects in the pipeline.
6.1. Solution chemistry and secondary reaction products
The solution chemistry of seawater, its composition, complexes
(inorganic and organic) and ion associations, has been investigated for
many years and comprehensive data are available concerning the prop-
erties of seawater (e.g., Millero et al., 2008; Safarov et al., 2012; Turner
and Whiteld, 1987; Turner et al., 1981, and references therein). Not
surprisingly, acidication [from approximately pH 8.2 to pH 7.6] affects
copper, iron and other element speciation in seawater (Breitbarth et al.,
2009; Byrne, 2002; Byrne et al., 1988; Millero et al., 2009; Richards et al.,
2011). Acidication of seawater in mineral leaching is extreme in
comparison and has a major impact on solution speciation. However,
the predicted copper speciation in seawater at pH 6 is essentially the
same as that for pH 12, the range commonly employed in heap
leaching (Table 4, models of the inorganic components of a seawater
composition based on Turner et al. (1981), pH adjusted with H2SO4).
Simulated iron speciation evolves over a wider pH range, where the
predicted number of supersaturated solution species diminishes from
30 at pH 8 to eight at pH 6, two at pH 4 and zero species at pH 12. In
Table 4
Predicted copper and iron speciation in simulated seawater in the range pH 8 (natural) to
pH 1 (metal extraction).
Speciesa Distribution (%) of total for element
respect of acid consumption, the simulation predicted that 10% and 4%
less acid (H2SO4) would be required to achieve pH 1.5 or pH 2.0 set
points, respectively, in seawater in the absence of ore compared with
a freshwater system.
A number of coincident reactions take place when an ore is
contacted with a lixiviant, in this case acid solution, depending on ore
mineralogy. These include acid consumption as a result of the adsorp-
tion of protons on gangue mineral surfaces and congruent dissolution
(e.g., muscovite, reaction (27)) or incongruent dissolution of gangue
minerals (e.g., phlogopite alteration to vermiculite, reaction (28))
(Dreier, 1999; Jansen and Taylor, 2003). In combination, the reactions
result in increased element concentrations in solution and/or the
precipitation from solution of a potentially large number of phases
that may become supersaturated (Dreier, 1999; Jansen and Taylor,
2003).
3
KAl2 AlSi3 O10 OH2 10H K 3Al 3SiOH4 27
2KMg3 AlSi3 O10 OH2 10H Mg2 Al2 Si3 O10 OH2 3SiOH4
2
4Mg 2K 28
Two published studies were found in which copper extraction
in freshwater was compared with seawater and more concentrated
process solutions. Torres et al. (2013) identied the main secondary
reaction product in the leached residues as gypsum with, in addition,
up to 8% of poorly-crystalline material typically comprising a mixture
of iron(III)- and Si-rich compounds (unpublished data). Watling et al.
(2014) showed that the amounts of poorly-crystalline iron(III)- and
silica-rich phases formed during leaching increased with increased sa-
linity. In general, the dissolution of silicate minerals with the formation
of amorphous silica (SiO2) or silica gel (e.g., Halinen et al., 2009) or dis-
ordered aluminium silicates comprises an important but possibly detri-
mental suite of reactions. Secondary reaction products like these could
reduce the permeability of the heap bed, and increase the viscosity of
the solutions being recycled around the heap operation. A simulation
of muscovite dissolution in acidied freshwater, seawater and double-
strength seawater indicated that the number of supersaturated
compounds increased with increased salinity and with increased pH
(Fig. 5). At pH 1.5, it was predicted that silica and, in double strength
seawater, gypsum were supersaturated but that iron(III) compounds
were undersaturated; at pH 2, iron (III) oxides, iron(III) hydroxyoxide
and jarosite were supersaturated, together with alunite, albite, gypsum
and silica, depending on the salinity.
A reaction that would impact directly on copper extraction is the
precipitation of ferric ions as insoluble iron(III) compounds such as
ferrihydrite, schwertmannite, goethite, iron(III) hydroxide or one of
several jarosite compounds (reaction (12)), possibly leaving a limiting

pH 8 pH 6 pH 4 pH 2 pH 1 8
pH 1.5
CuBr+
number of supersaturated

Copper(II) monobromide ion (+1) b0.1 0.1 0.1 7

Copper(II) chloride CuCl2 1 3 3 pH 2
Copper(II) monochloride ion (+1) CuCl+ 8 31 31
6
compounds

Copper(II) dicarbonate ion (2) Cu(CO3)2

2 3 5
Copper(II) carbonate CuCO3 70 1
Copper(II) ion (+2) Cu2+ 17 64 65 4
Copper(II) monohydroxide ion Cu(OH)+ 1
(+1)
3
Iron(III) dichloride ion (+1) FeCl+
2 0.4 0.4 0.4 2
Iron(III) monochloride (+2) FeCl2+ 0.4 0.4 0.4
3+
Iron(III) ion (+3) Fe 18 94 98 1
Iron(III) dihydroxide ion (+1) Fe(OH)+2 18 5
Iron(III) hydroxide Fe(OH)3 93 79 0
Fresh Sea 2 X Sea
Iron(III) tetrahydroxide ion (1) Fe(OH)4 7
Iron(III) monohydroxide ion (+2) FeOH2+ 3 76 4
Iron(III) sulfate ion (+1) FeSO4+
0.1 1 1 Fig. 5. The predicted number of supersaturated species in a simulation of muscovite disso-
lution (representing low-grade ore) in acidied freshwater, seawater and double-strength
a
Calculated using a seawater composition based on Turner et al. (1981) but omitting seawater at pH 1.5 (representing heap feed solution) and pH 2 (representing heap
organic components, acidied with H2SO4 (OLI Analyzer Studio 3.2 software). discharge solution) (OLI Analyzer Studio version 3.2).
106 H.R. Watling / Hydrometallurgy 146 (2014) 96110

concentration of the ferric ion oxidant for sulde dissolution. A greater
extent of precipitation of iron(III) compounds from seawater leachates,
together with their known ability to sequester trace metals (Burgos
et al., 2012; Scott, 1987) may cause copper hold-up in the heap, in addi-
tion to loss of permeability in the heap bed. An increased proportion
of jarosite compounds precipitated, relative to iron (III) oxides and
hydroxides, as a consequence of the high concentration of monovalent
cations in seawater (this laboratory, unpublished data), is consistent
with the predicted supersaturated compounds and with the results of
Carneiro and Leo (2007).
6.2. Bioleaching in chloride heaps
Historically, it has been believed that the presence of chloride at the
concentrations found in seawater (approximately 0.5 M NaCl) would
preclude the bioleaching of sulde ores, based on published laboratory
studies about the limited salt tolerance of iron- and sulfur-oxidising
bacterial cultures of species known to colonise sulde heaps (Zammit
et al., 2012 and references therein). Known halophiles, such as
Halothiobacillus spp. (Kelly and Wood, 2000), were not acid-tolerant
and did not oxidise iron(II), a key reaction in the dissolution of sulde
minerals. A strategy commonly used to overcome the inhibitory chlo-
ride effect was to dilute saline water with freshwater. For example,
for the column bioleaching tests that formed part of the development
of heap leaching at Ivan Mine, Chile, underground saline water was
diluted to approximately 0.14 M chloride, so as to permit bacterial
iron- and sulfur-oxidation (Leong et al., 1993).
A second strategy was to adapt microbial cultures to the presence
of chloride. Weston et al. (1995) adapted bacterial cultures to water
containing ~0.08 M chloride, because that was the anticipated chloride
content in the water supply for Zaldivar Mine, Chile. At Pacic Ore Tech-
nologies, sulfur-oxidising microbial cultures were developed and
adapted to different levels of salinity up to eight-times that of seawater
for application in a process that was not reliant on iron(II) oxidation
(Williams, 2006); one of those cultures was applied to the bioleaching
of ore from Sherlock Bay (Western Australia) as a process option for
the nickelcopper sulde deposit near which the underground water
supply had a salinity similar to that of seawater.
In the mean time, the application of molecular microbiological
techniques to mining and acid mine drainage systems is revealing an
increasing number of acidophiles that are halotolerant and possess
the ability to oxidise iron(II) and/or reduced inorganic sulfur com-
pounds (Table 5). For example, a mixed culture, NiS-J069B, has been
developed, capable of functioning at pH 3.5 and 5060 C in saline
solution of up to 1.4 M chloride, and applied to the leaching of a nickel
sulde ore, arsenic-rich sulde tailings and a chalcopyrite concentrate
(McCreddan and Seet, 2013). In respect of chalcopyrite concentrate,
the results reported were unimpressive (91% copper extraction
in 118 days), but the low ORP values recorded during leaching indicated
that this mixed culture did not oxidise iron(II) efciently. The main inter-
est lies in the putative identication of the species in the culture (Table 5)
because that shows that some well-known genera of bioleaching micro-
organisms can function in high-chloride environments.
It must be concluded that, far from being inhospitable environments
to microorganisms, chloride heaps host diverse and active iron(II)- and
sulfur-oxidising microbial populations that will be isolated and de-
scribed in the future. Their expected importance to the mining industry
is reected by their inclusion in recent patent applications related to
mineral leaching (e.g., Davis-Belmar et al., 2010; Dew and du Plessis,
2002; Ohtsuka and Mitarai, 2007; Rautenbach et al., 2011).
6.3. Use of saline water or seawater in heaps or dumps
Dutrizac and MacDonald (1971) investigated copper extraction
from chalcopyrite ore (3% Cu) under simulated dump leaching condi-
tions. For column tests, the ore was crushed to 0.63 mm and 3 kg
portions loaded into 5 mm internal diameter columns to give a 1 m
bed depth. When the ore was leached with solution containing 0.1 M
Fe(III) and 0.1 M H2SO4 with/without approximately 0.1 M NaCl,
copper extractions ranged from 1 to 8% in tests conducted in the
range of 2540 C but, more importantly for that evaluation, the
presence of sodium chloride suppressed copper extraction. However

Table 5
Halotolerant acidophiles capable of oxidising iron(II) and/or reduced inorganic sulfur compounds.

Microorganism/culture NaCl (g L1) pH Fe(II) OX S OX Reference

range [optimum] range [optimum]

Leptospirillum ferriphilum-like strain YSK 07 1.6 Wang et al. (2012)

[0]
Leptospirillum sp.-Cl 530 13 a Rautenbach et al. (2011)
Sulfobacillus sp. TPY 030 [2] Qi et al. (2009); Wang et al. (2012)
[10]
Thiobacillus prosperusb strains 060 14.5 Huber and Stetter (1989)
[0] [2]
Thiobacillus prosperus Milos culture 2550 1.7 c Norris et al. (2010)
[30]
Thiobacillus-like strain KU2-11 1030 23 Kamimura et al. (2001)
[20] [2]
Acidihalobacter aerolicus strain V6 ~847 1.8 Nicolle et al. (2009); Kelly et al. (2005)
[0]
Acidihalobacter ferrooxidans (V8) 60 2 Norris and Simmons (2004); Kelly et al. (2005)
Alicyclobacillus-like strains 550 1.64.5 Holden et al. (2001); Rodgers et al. (2002)
[5]
Acidithiobacillus-like strain TTH19A 030 14 Ohtsuka and Mitarai (2007)
[10]
Acidithiobacillus thiooxidans-like strain SH 1045 15 Kamimura et al. (2003, 2005)
[20] [4]
NiS-J069B mixed cultured 80 3.5 McCreddan and Seet (2013)
a
Growth with halophilic sulfur oxidising species.
b
Closest relatives now known to be Acidihalobacter spp. with which it is likely to be reclassied as Acidihalobacter prosperus.
c
Tetrathionate 1 mM and CO2 enriched air stimulated iron(II) oxidation.
d
Putatively identied genera were Acidimicrobium, Acidiphilium, Acidithiobacillus, Acidobacterium, Acidocella, Acidisphaera, Alicyclobacillus, Sulfobacillus and a dominant but unidentied
microorganism.
 H.R. Watling / Hydrometallurgy 146 (2014) 96110
at 60 C, copper extractions were approximately 17% and 10% after
55 days leaching with/without added chloride, respectively. Having
conrmed the greater than 50 C temperature requirement for en-
hanced extraction using a second ore, together with ancillary laboratory
tests, Dutrizac and MacDonald (1971) concluded that large chloride ad-
ditions would not benet copper extraction in a dump-leach, as temper-
atures were generally below 50 C. In contrast, Muoz-Ribadeneira and
Gomberg (1970, 1971) reported that the addition of as little as 0.1 M
HCl to a sulfuric acid leach of chalcopyrite resulted in increased copper
extraction.
The earliest reference to seawater use in heap leaching found so far
is one by Domic (2007) in which it was noted that in 1991, the rst
commercial leachingsolvent extractionelectrowinning plant using
Pudahuel's thin layer leaching technology and license using seawater
for leaching started at Lince (now Mina Michilla). With more than
20 years experience, it can be assumed that seawater is as good a
solvent and carrier as freshwater, of acid, ferric ions and possibly salt-
tolerant microorganisms to the ore and the soluble metals to the next
stage of a heap leach process.
The chloride heap leaching process invented by Muller et al. (2011),
underpinned by the body of work described by Nicol and co-researchers
(Miki and Nicol, 2011; Nicol et al., 2010; Velsquez-Yvenes et al.,
2010a, 2010b), was not per se a seawater heap-leach process, although
the range of chloride (Cl) concentrations proposed for the method's
greatest efciency did encompass that of seawater. The strategy
was to control ORP in an acidic mixed sulfatechloride solution to main-
tain the chalcopyrite surface potential in the range of 550600 mV ver-
sus SHE. The chloride concentration in the proposed process was
between 5 and 100 g L 1 (0.142.8 M Cl) and the presence of at
least 1 mg L1 (ppm) oxygen was required. Muller et al. (2011) pro-
posed that, in the presence of chloride in the suggested concentration
range, (i) the type, morphology and distribution of elemental sulfur
was such that it formed away from a chalcopyrite surface, (ii) Cu(I) spe-
cies were stabilised allowing the Cu(II)/Cu(I) couple to control ORP,
(iii) the thermodynamics and possibly the rate of the non-oxidative re-
action was enhanced (reaction (29) or (4)) and (iv) the formal potential
of the Cu(II)/Cu(I) couple was increased. They also proposed that chlo-
ride affected (v) the rate of oxidation of Cu(I) to Cu(II) and the dissolved
O2 concentration, and (vi) resulted in a reduction in the required acid to
achieve the desired pH. The inventors noted that iron had no direct role
in the leaching mechanism, provision of acid drove the non-oxidative
reaction and that ORP determined the mixed potential at the mineral
surface and controlled the mechanism of chalcopyrite dissolution. It
was further suggested that a number of insoluble materials such as
pyrite, magnetite, hematite, activated carbon of coal, zeolites and several
elements (Ag, Bi, Cd or Hg) might enhance the kinetics of H2S oxidation
(see reaction (30)), thus increasing the rate of chalcopyrite dissolution.
2
CuFeS2 4H 2SO4 CuSO4 FeSO4 2H2 Saq 29
0
H2 Saq O2 2S 2H2 OcopperII catalysed reaction 30 cupric ions are the predominant copper species in solution. There is a
The CuproChlor process (Aroca et al., 2012; Espejo et al., 2001; Rauld
Faine et al., 2005) was developed to extract copper from copper oxide
and mixed copper oxidesecondary sulde ores containing chalcocite,
bornite and covellite (Herreros et al., 2006). It is a chloride heap leach
with two main differences; rst, ne copper-rich ore or concentrate
particles were bound by salt bridges (gypsum) to host rocks during ag-
glomeration in a process akin to the Geocoat technology (Kohr et al.,
2004) and second, the chloride concentration in solution was more
than three times that of seawater. It was proposed that the chloride
(i) stabilised Cu(I) formed during leaching with the result that the
Cu(II)/Cu(I) couple could contribute to sulde oxidation, (ii) enhanced
sulde oxidation by ferric ions and (iii) inuenced the morphology of
elemental sulfur, facilitating the movement of ferric and ferrous ions
to and from chalcopyrite surfaces. At the Michilla mine, Chile, 65%
107
of the contained copper was extracted in 50 days of leaching and
90% in 110 days; the CuproChlor process was considered to be compet-
itive with bioleaching (Herreros et al., 2006). A modication of the
CuproChlor process incorporated the calcium chloride agglomeration
strategy to facilitate the leaching of copper sulde concentrates (includ-
ing chalcopyrite) in heaps (Rauld Faine et al., 2005), by which it was
differentiated from other processes for the leaching of concentrates in
heaps, such as the GEOCOAT process described in numerous patents
(e.g., Kohr et al., 2004).
7. Summary
Hydrometallurgical process developments for the extraction of
copper from chalcopyrite, an abundant but refractory mineral with
respect to its dissolution, tend to be targeted at complex or dirty con-
centrates that would incur penalties were they to be smelted or low-
grade ores that are a major but, thus far, uneconomic source of copper.
The copper values in concentrates permit a degree of exibility in pro-
cess development but the lower values in low-grade ores demand that
new technologies be low cost. Perceived advantages of chloride sys-
tems, such as the high solubility of copper and ferric iron, the ease of fer-
rous ion oxidation, faster leaching kinetics of chalcopyrite compared
with ferric sulfate systems, and generation of sulfur rather than sulfate
as the primary product of sulde oxidation, have driven research and
development over many years. Perceived disadvantages were the corro-
sive action of chloride, thus necessitating the use of more expensive
materials of construction for reactors, the need for ne grinding for pro-
cesses operated at atmospheric pressure, and the difculty of electro-
winning high-grade copper from chloride solutions.
Process developments for concentrates employ acidic, oxidising
leach media containing sodium or other chloride salts up to concentra-
tions encountered in brines, at temperatures up to the boiling points of
the selected solution compositions. In these processes, chloride ion is
proposed to be an active agent in the dissolution, which may occur by
different mechanisms depending upon the solution composition. Inno-
vative reactors and ow sheets, the need for process controls and addi-
tional reagent costs, are offset by the copper values in concentrates
which, for a number of reasons including undesirable impurities, may
make them unsuitable for smelting. Reagent recovery and recycle is in-
corporated into some owsheets, for example the High Concentration
Chloride Leach, the Intec Process and Hydrocopper Process, contributing
to their potential economic and environmental sustainability.
For low grade ores, usually processed in heaps, the use of seawater
or other naturally saline water in leaching operations is an economic
choice to overcome the scarcity and/or cost of freshwater. Few studies
have been published describing the advantages and disadvantages of
seawater substitution for freshwater in leaching processes but, from
the sparse information available, seawater appears to be as efcient a
solvent and carrier of acid and oxidant as freshwater. In seawater solu-
tions the chloride concentration is too low to stabilise cuprous ions and
view that seawater use for sulde ore heaps would prohibit the bene-
cial catalytic action of acidophilic microorganisms. However, the recent
description of some iron(II)- and sulfur-oxidising, salt-tolerant acido-
philes suggests that there is a diverse group of still-to-be-described
microorganisms that could function in sulde heaps irrigated with
seawater. With regard to processing, the salt content in seawater
would impact directly on solution transport costs to and around a
mine (through increased solution viscosity and specic gravity) and
could impact on product and by-product contamination (requiring
clean water and additional unit process).
Common to high- and low-chloride processes, accessibility of
chalcopyrite grains to the lixiviant and chalcopyrite grain size are key
parameters in the success of a technology and increased temperature
and stronger oxidants than cupric and ferric ions can be employed to in-
crease reaction kinetics.
108 H.R. Watling / Hydrometallurgy 146 (2014) 96110
Acknowledgements
Dr. R. McDonald is thanked for a careful and critical review of the
typescript. The nancial support of the Australian Government through
the CSIRO Minerals Down Under Flagship is gratefully acknowledged.
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