Accepted Manuscript

Challenges with elemental sulfur removal during the leaching of

copper and zinc sulfides, and from the residues; a review

Esmaeil Jorjani, Ahmad Ghahreman

PII: S0304-386X(17)30125-1
DOI: doi: 10.1016/j.hydromet.2017.06.011
Reference: HYDROM 4603
To appear in: Hydrometallurgy
Received date: 25 February 2017
Revised date: 6 May 2017
Accepted date: 6 June 2017

Please cite this article as: Esmaeil Jorjani, Ahmad Ghahreman , Challenges with elemental
sulfur removal during the leaching of copper and zinc sulfides, and from the residues; a
review, Hydrometallurgy (2017), doi: 10.1016/j.hydromet.2017.06.011

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 ACCEPTED MANUSCRIPT

Challenges with elemental sulfur removal during the leaching of

copper and zinc sulfides, and from the residues; a review

Esmaeil Jorjani*, Ahmad Ghahreman

The Robert M. Buchan Department of Mining, Queen's University, Goodwin Hall, 25 Union St., Kingston,
ON K7L 3N6, Canada

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Abstract

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The hydrometallurgical recovery of metal values from sulfide concentrates, such as
chalcopyrite, enargite, and sphalerite, typically generates elemental sulfur in the oxidative

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leaching processes. The main disadvantage of the generation of sulfur is that it retards or
hampers the efficiency of the leaching process. The oxidative leaching of sulfide mineral
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concentrates at temperatures above 180 C and at high pressures, known as total pressure
oxidation (TPOX), completely converts the sulfide minerals to sulfate ions and sulfuric acid.
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However, the TPOX process has several negative aspects that increase costs, including the
capital cost of the TPOX operations, the high oxygen demand to convert sulfide to sulfate, and
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the lime that is required to neutralize the excess acid in the autoclave discharge. Alternative
processes that can reduce the capital and operating costs associated with the treatment of
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sulfidic concentrates include the medium temperature pressure oxidation (MT-POX) processes
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that operate below 150 C, such as the Cominco Engineering Services Ltd. (CESL) process, and
atmospheric leaching (ATL) processes, such as the Albion and Galvanox processes. In the MT-
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POX and ATL processes, a proportion of the sulfides from the sulfide concentrates are oxidized
to elemental sulfur, reducing the generation of acid and the oxygen demand of the oxidative
leaching processes. Despite the lower operating and capital costs of the MT-POX and ATL
processes, elemental sulfur may cause environmental problems such as acid mine drainage, or
downstream process operation problems such as low solid/liquid separation efficiency or
leaching efficiency. Thus, it is important to remove the elemental sulfur effectively during the
leach process or from the residues after the leach process. In this paper, we present a summary
of the research that has been conducted to decrease the passivating effect of molten sulfur

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during the leaching of copper sulfide and zinc sulfide, and the approaches to remove the
elemental sulfur from the leach residues. Also, the paper reviews the most important
approaches that have been developed to address the elemental sulfur issue, including the
application of polytetrafluoroethylene (C2F4)n, carbon tetrachloride (CCl4), ozone, nanosilica,
sulfur-oxidizing bacteria, thermophilic iron-oxidizing archaea, sulfur-reducing bacteria (SRB),
calcium lignosulfonate, quebracho, tetrachloroethylene (C2Cl4), Na2S leachingCO2

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precipitating, and vacuum and atmospheric distillation.

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Keywords: sulfur removal, leaching residue, copper sulfide, zinc sulfide

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Corresponding author: Email address: esmaeil.jorjani@dheminerals.com

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1. Introduction
Sulfur is a yellow, crystalline solid with melting points of 112.8 and 119.5 C for the rhombic and
monoclinic structures, respectively. The boiling point of elemental sulfur is 444.6 C. Relatively
strong oxidizing agents can oxidize sulfur to sulfate in aqueous media. Examples of such
oxidizing agents are nitric acid, aqueous chlorine, basic solutions, concentrated sulfuric acid,
and, to a limited extent, highly-oxygenated water (Habashi, 1999). Elemental sulfur mainly

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occurs in hydrothermal vents, but it also is present in the base metal sulfide resources of

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copper, zinc, lead, and iron. This review is focused on the two most important commodities,

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i.e., copper and zinc.

Copper in the Earths crust can occur as native copper, but most often it is contained in various

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minerals, such as copper sulfides, copper carbonates, and copper oxides. The most important
commercial copper minerals are copper sulfides, which include chalcopyrite (CuFeS2), bornite
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(Cu5FeS4), chalcocite (Cu2S), covellite (CuS), and enargite (Cu3AsS4) (Hammond, 2004).
Chalcopyrite is the most abundant copper mineral (Parker et al., 2003), accounting for
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approximately 70% of the worlds copper reserves (Crdoba et al., 2008). Despite the fact that
8085% of the worlds copper is produced through pyrometallurgical processes, significant
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interest has developed in the extraction of copper from low-grade/low-quality ores and
concentrates via hydrometallurgical processes (Harmer et al., 2006).
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While copper oxide minerals readily leach in any acidic solutions, secondary copper sulfide
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minerals, such as chalcocite, can only be leached effectively in combination with acid and an
oxidant, such as ferric iron. In oxidative bioleaching processes, the bacteria oxidize ferrous ions
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to ferric ions, which oxidise the copper, and the continual regeneration of the ferric ions
improves the copper-leaching rate (Antonijevic and Bogdanovic, 2004; Clark and Norris, 1996;
Norris and Owen, 1993). However, the primary copper sulfides, chalcopyrite and enargite, are
highly refractory minerals even in acidic, ferric sulfate solutions; to improve their copper
leaching rate, high leaching temperatures and high concentration of strong oxidants are needed
to increase the oxidation kinetics (Crdoba et al., 2008). At high pressures and temperatures
above 180 C, chalcopyrite can be oxidized effectively in less than an hour. However, the
process has a very high oxygen demand for the oxidation of sulfide to sulfate, and the oxidation
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of some associated sulfide minerals, such as pyrite, will generate sulfuric acid (Dreisinger,
2005).

Medium temperature pressure oxidation (MT-POX) processes that operate at 150 C or lower,
such as the Cominco Engineering Services Ltd. (CESL) process, and the atmospheric leaching
(ATL) processes, such as the Albion process, are alternative processes that have lower capital
and operating costs (Barr et al., 2005; Mayhew et al., 2013; Turner and Hourn, 2016). In the

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MT-POX and ATL processes, a proportion of the sulfur from the sulfide minerals is oxidized to

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elemental sulfur, reducing the generation of excess acid and lowering the oxygen demand of

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the oxidative leaching process (Dreisinger, 2005; Brion, 1980; Viramontes-Gamboaet al., 2010;
Yin et al., 1995; Hackl et al., 1995). Despite the lower capital and operating costs, the leaching

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kinetics in MT-POX and ATL processes typically are slower than high-temperature, high-
pressure (HT/HP) autoclave operations. The reason is the wetting of the surfaces of the
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partially-reacted sulfide minerals with molten elemental sulfur, which reduces the reaction
kinetics in the mineral oxidation process (Dreisinger, 2005; Lattanzi et al., 2008; Govindaiah et
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al., 2015a; Havlik and Kammel, 1995; Havlik and Skrobian, 1990; Misra and Fuerstenau, 2005;
Balaza et al., 1991; Mathew et al., 2010; Govindaiah et al., 2015b; Padilla et al., 2008; Hol et al.,
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2012; Rivera-Vasquez, 2011; Escobar et al., 2000; Takatsugi et al., 2011). One common
industrial practice that is used to minimize wetting of the mineral surfaces and improve the
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leaching kinetics in the MT-POX processes is to add surfactants to the leach slurry. The
surfactants adsorb onto the surfaces of the partially-leached sulfide minerals and inhibit
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wetting of the surfaces with the molten elemental sulfur by making the surface hydrophilic
(Dreisinger, 2005; Halfyard and Hawboldt, 2011). Alternatively, it is probable that the
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surfactants adsorb onto the mineral surface and mitigate the minerals agglomeration via steric
hindrance as they form a progressively thicker and sticky sulphur product layer.

Enargite (Cu3AsS4) is another refractory copper sulfide mineral that commonly is associated
with gold and silver (Lattanzi et al., 2008). Conventional smelting technology has restrictions for
the treatment of concentrates that have high concentrations of arsenic due to the risk of the
accumulation of arsenic in the environment (Conner, 2014). Usually, the concentrator will pay
penalties for the treatment of concentrates with arsenic levels above 0.5%. Similar to the

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chalcopyrite and pyrite concentrates, the HT/HP oxidation of enargite in acidic sulfate media
(> 200 oC) results in the generation of sulfate, and lime can be used to neutralise the sulfate,
forming gypsum. MT-POX and ATL of enargite concentrates have similar challenges as
chalcopyrite concentrates, with slow oxidative leaching (Govindaiah et al., 2015a; Govindaiah et
al. 2015b).

The formation of elemental sulfur is a challenge in the hydrometallurgical zinc sulfide treatment

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processes. Pyrometallurgy is the industry standard route to recover zinc from sulfide mineral

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concentrates (Halfyard and Hawboldt, 2011). As an alternative to the pyrometallurgical option,

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the Sherritt direct pressure leach process at 150 oC has been commercially apllied at the Trail
zinc refinery, British Columbia, and since 1981 it has been used by other refineries (Halfyard

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and Hawboldt, 2011; Ozberk et al., 1995). The elemental sulfur content of direct leaching
residue (DLR) can exceed 70%; if the sulfur content of the DLR is below 70%, it can be separated
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through a sulfur flotation process and then recovered by melting and hot filtration. Due to the
high processing costs of flotation processing, the DLR is sometimes disposed in hazardous waste
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dumps, which are likely to be an environmental risk in the future (Halfyard and Hawboldt,
2011).
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Several researchers attempted to eliminate all of the above challenges presented by elemental
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sulfur via the development of low-cost, viable methods for separating sulfur. In this paper, we
present a summary of the research that has been conducted to decrease the passivating effect
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of molten sulfur during the leaching of copper sulfide and zinc sulfide, and to remove the
produced elemental sulfur from the leach residues.
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2. Treatment of elemental sulfur during the leaching of copper sulfides

2.1. Chalcopyrite

The ATL and MT-POX processes for chalcopyrite leaching produce elemental sulfur. The
chalcopyrite leaching reaction in chloride media is (Dutrizac, 1978):

CuFeS2 + 3.5FeCl3 0.5CuCl2 + 0.5CuCl + 4.5FeCl2 + 2So (1)

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In acidic ferric sulfate media, the reaction can be (Mateos, 1987):

CuFeS2 + 2Fe2(SO4)3 CuSO4 + 5FeSO4 + 2So (2)

In ammonia leaching conditions, the oxidation reaction is (Reilly and Scott, 1984):

CuFeS2 + 4NH3 + 6OH- Cu(NH3)42+ + 0.5S2O32- + So + Fe(OH)3 + 1.5H2O + 7e- (3)

The elemental sulfur produced in the chalcopyrite leaching can hinder the leaching reaction

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kinetics and also can be a challenge in the leach residue.

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One expensive method to eliminate the formation of passivating sulfur during the leaching

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process and to increase the leaching rate would be to oxidize elemental sulfur. Oxidative
leaching of chalcopyrite concentrate (32% copper, with particle size of -56+45 m) with ozone

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in a 0.5 M sulfuric acid solution was studied by Havlik and Skrobian (1990). It was shown that
the application of ozone as an oxidant prevents the formation of elemental sulfur by fully
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oxidizing the sulfides to sulfate. When the leaching temperature was increased from 1 to 75 oC,
two opposing parameters were competing during the chalcopyrite leaching process, i.e., (1) at
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higher temperatures, the leaching kinetics increase and (2) at higher temperatures, the
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solubility of ozone in the leach solution decreases. The study showed that 22 oC is the most
effective leaching temperature with ozone application (Havlik and Skrobian, 1990). However,
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the cost of ozone application in a leach process likely can eliminate the economic attractiveness
of a process.
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In another study, Havlik and Kammel (1995) studied the leaching kinetics of a chalcopyrite
concentrate (32% Cu) from Cuba in 1 M FeCl3 and 0.2 M HCl media with and without the
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addition of carbon tetrachloride (CCl4). Carbon tetrachloride was used as a solvent for
elemental sulfur. The results of the study confirmed that the kinetics of copper recovery in the
presence of CCl4 could be improved by 200% at low temperatures, while it was only about 45%
at elevated temperatures. Despite the attractive leaching results, the application of carbon
tetrachloride in an industrial leaching process is not attractive due to its health and
environmental problems.

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Misra and Fuerstenau (2005) used nano-silica (50 nm) in the atmospheric, oxidative, acidic
leaching (0.5 N H2SO4) of chalcopyrite concentrate with different oxidants, including FeCl3,
H2O2, and Fe2(SO4)3. In all of the experiments, it was observed that the addition of nano-silica
improves the leaching kinetics of chalcopyrite (Figs. 1(a)-(c)). The SEM micrograph and EDX
spectrum of the residues from the tests with H2O2 oxidant and with and without the addition of
nano-silica particles showed that a major constituent of the passivating layer in the absence of

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the nano-silica catalyst was elemental sulfur (Figs. 2(a) and (c)); however, by the addition of

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nano-silica to the leaching system, only a very small sulfur peak was detected by EDX analysis

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(Figs. 2(b) and (d)). The addition of nano-silica can potentially reduce the solid-liquid separation
efficiency of the leach residue, though this has not been discussed in the Misra and Fuerstenau
(2005) study.

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Fig. 1. Effect of leaching time on chalcopyrite (-37 m) dissolution in the absence and presence
of nano-silica (50 nm): (a) 5 g/L concentrate, 40 g/L FeCl3, 200 ml 0.5 N H2SO4, 75 oC; (b) 1.25

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g/L concentrate, 3.0 g/L H2O2, 400 ml 0.5 N H2SO4, 65 oC; (c) 5 g/L concentrate, 30 g/L Fe2(SO4)3,
200 ml 0.5 N H2SO4, 75 oC (Misra and Fuerstenau, 2005).

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Fig. 2. Secondary electron micrograph and EDX spectra of chalcopyrite leached in the absence
(a and c) and in the presence (b and d) of nanosilica (Misra and Fuerstenau, 2005).
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Balaza et al. (1991) chemically pre-leached chalcopyrite in a 0.25 M Fe2(SO4)3 + 0.25 M H2SO4
solution at 90 oC for 5-180 min, and then contacted the pre-leach residue with Acidithiobacillus
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ferrooxidans bacteria to study the copper recovery. By the application of X-ray photoelectron
spectroscopy (XPS), Balaza et al. (1991) showed that the amount of elemental sulfur generated
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on the surface of the chalcopyrite during the chemical pre-leaching increased linearly with the
pre-leaching time. Thus, by prolonging the pre-leaching operation, the bacteria in a subsequent
bacterial leaching operation will be forced to develop an activity to convert ferrous species to
ferric species and to oxidize more elemental sulfur to sulfate; the latter was expected to be the
rate-determining step in the bacterial leaching process. Balaza et al. (1991) showed that the
combination of the pre-leaching process in an acidic ferric medium for 5 min at 90 oC with a

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bacterial leaching process for 26 days at 30 oC on a rotary shaking machine produced 85%
copper recovery from chalcopyrite.

Mathew et al. (2010) suggested that polytetrafluoroethylene (PTFE), (C2F4)n, can act as a solid
sorbent for the molten sulfur that is generated during the MT-POX process below 160 oC.
Govindaiah et al. (2015a) studied the adsorption of molten elemental sulfur onto the surfaces
of the PTFE-TiO2 composite pellets during the chalcopyrite pressure leaching process. They

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showed that the adsorption of sulfur is a topological process that is governed by the surface

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area of the PTFE composite-pellet adsorbent, which is a relatively expensive material. Thus,

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Govindaiah et al. (2015a) added TiO2 as an inorganic filler for the PTFE beads. The composite
pellets of PTFE/TiO2 with TiO2 contents ranging from 0 to 35% (Fig. 3) were used as sulfur

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adsorbents in the MT-POX of chalcopyrite concentrate with a copper content of 30 wt%; the
leach solution was 50 g/L H2SO4, 2.5 g/L Fe2(SO4)3, and 20 g/L NaCl. Different adsorbents (TiO2,
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PTFE, and PTFE-TiO2 composite) were used in the pressure leaching experiments. The
temperature of the autoclave was set at 150 oC, and an oxygen overpressure of 100 psi was
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applied. The results showed that the PTFE leads to enhanced recovery of copper. With the
addition of the composite sulfur adsorbents that contained 35% TiO2, the copper extraction at
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80 minutes increased from 42% (without absorbent) to 89% (with composite absorbent) (Fig.
4). It also was suggested that the addition of TiO2 into the PTFE-TiO2 composite beads created
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new hydrophobic surfaces for the adsorption of sulfur. An excellent reusability of the PTFE/TiO2
adsorbent was observed, even after 10 leaching cycles (Govindaiah et al., 2015a).
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A combination of fine grinding and addition of surfactants, such as lignin sulfonate and/or
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quebracho, amounting to 2 to 5 kg per tonne of concentrate, was used in the Anglo American
Corp./University of British Columbia (AAC/UBC) chalcopyrite concentrate leaching process to
disperse the molten elemental sulfur and prevent passivation of the chalcopyrite (Fig. 5). In the
AAC/UBC process, which is an MT-POX process, the chalcopyrite concentrate (P80: 520 m) is
leached at 150 C in an acid sulfate system and with an oxygen overpressure condition (Fig. 6).
In a continuous pilot-plant trial, copper recovery was reported to be above 95% after an
autoclave leaching time of 2 h (Dreisinger, 2005).

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The CESL copper process is as a medium temperature pressure oxidation process at 150 C and
200 psi, designed for sulfide concentrates leaching. In this process 5 to 20 g/L chloride, as
sodium chloride, is added to the leach solution to catalyze the leach reaction. The main
advantages of the process are the fast and efficient leach kinetics, elimination of the need for
ultrafine grinding of the chalcopyrite mineral, and oxidation of sulfide to elemental sulfur thus
minimizing the oxygen consumption in the autoclave. The process also takes advantage of the

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addition of a specific reagent to minimize wetting of the chalcopyrite surface by molten sulfur

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that would otherwise slow the leaching kinetics. McDonald and Muir (2007) examined the

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effect of different additives on the dispersion of molten sulfur and recovery of copper in CESL
process and found that Sodium lignosulfonate is a better surfactant than Quebracho when
employed in equivalent amounts. But, they also found out that the dispersion of the sulfur

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results in more complete oxidation to sulfate and consequently a higher oxygen demand.
Therefore, a balance between the addition of surfactants and chloride ion for optimum copper
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recovery and minimum sulfur oxidation is needed. It is worth noting that the CESL process is a
proven technology for chalcopyrite treatment though the sulfur produced via the CESL process
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is not a saleable product due to its low quality.

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Fig. 3. Secondary electron micrograph images: (a) Pure PTFE; (b) PTFE/TiO2 composite with TiO2
at 20 wt%; (c) PTFE/ TiO2 composite with TiO2 at 35 wt% (Govindaiah et al., 2015a).

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Fig. 4. Effect of different types of elemental sulfur absorbents on copper extraction (Govindaiah

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et al., 2015a).

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Fig. 5. AAC/UBC pilot plant flowsheet for chalcopyrite leaching (reproduced from Dreisinger,
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2005).
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Fig. 6. Effect of particle size on leaching of chalcopyrite concentrate with surfactant addition at
150 oC (Dreisinger, 2005).

2.2. Enargite

Enargite, Cu3AsS4, is a refractory copper sulfide mineral that usually is a gold carrier (Lattanzi et

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al., 2008). The conventional enargite treatment process includes roasting to reduce the arsenic

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content, followed by smelting to recover copper and possibly gold. The hydrometallurgical

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treatment of enargite and other arsenic-containing sulfide minerals is an interesting alternative,
particularly because of its ability to treat high-arsenic concentrates and ores with less

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environmental risks and possibly lower costs. The atmospheric oxidative leaching of enargite
produces elemental sulfur, which covers the partially-reacted surfaces of the minerals and
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prevents further oxidation of the underlying mineral (Lattanzi et al., 2008):

Cu3AsS4 + 11Fe3+ + 4H2O 3Cu2+ + AsO43-+ 4So + 8H+ + 11Fe2+ (4)

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Lattanzi et al. (2008) showed that the ultrafine grinding of enargite partially oxidizes the
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mineral surface in the grinding mills, resulting in the formation of elemental sulfur:

Cu3AsS4 + 6.75O2 3CuSO4 + 0.5As2O3 + So (5)

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In equation 5, the copper sulfate (CuSO4) and arsenic oxide (As2O3) products are soluble in the
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grinding water, whereas the unreacted enargite and the elemental sulfur, along with other non-
reactive minerals, are in solid phases (Lattanzi et al., 2008).
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During the bioleaching of copper sulfides, iron-oxidizing bacteria can facilitate reaction (4) by
expediting the oxidation reaction of ferrous to the ferric. The sulfur-oxidizing bacteria also can
remove the elemental sulfur from the surfaces of the mineral by oxidizing it to soluble sulfate
species, thereby ultimately increasing copper leaching kinetics. The arsenic from the mineral is
released as arsenate into the solution and later precipitates as ferric arsenate or scorodite
(FeAsO42H2O), which decreases the As toxicity level of the leach solution (Escobar et al., 2000).

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Hol et al. (2012) studied the impact of the application of sulfur-reducing bacteria (SRB) to
convert elemental sulfur to hydrogen sulfide during atmospheric leaching of an enargitepyrite
gold concentrate (32 ppm Au, P80 of 32 m) that came from the Pascua Lama mine in Chile.
The objectives of the study were (1) to remove the elemental sulfur from the mineral surfaces
to improve the downstream gold recovery in cyanidation circuit and lower the cyanide
consumption and (2) to increase the extent of the oxidative leaching of enargite and pyrite,

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thereby improving the recovery of gold. The bio-reduction process increased the recovery of

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gold in the cyanidation tests from 48.9 to 69.6% for the native and bio-reduced samples,

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respectively.

Govindaiah et al. (2015b) used PTFE beads as absorbents for elemental sulfur in the pressure

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oxidation leaching of an enargite-pyrite flotation concentrate (+55 m fraction) to enhance the
copper leaching rate. The main minerals in the flotation concentrate were enargite (45.6%),
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pyrite (43%), sphalerite (2.6%), quartz (2.5%), and chalcopyrite (2.4%). Different leaching
solutions, including DI water, and solutions containing 7 g/L Cl (as NaCl), 20 g/L H2SO4, or both
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were used as the leaching media (Fig. 7). Govindaiah et al. (2015b) reported that the addition of
the PTFE beads clearly improved the copper leaching kinetics in all four leaching solutions, i.e.,
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water, sulfuric acid, hydrochloric acid, and a mixture of sulfuric and hydrochloric acids. The
catalytic effect of PTFE beads on the improved kinetics of copper leaching is linked to the
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hydrophobic properties of the mineral particles, so these particles preferentially adsorb on the
PTFE surfaces. The molten elemental sulfur that is produced by the leaching reaction adsorbs
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preferentially onto the surfaces of the PTFE. This reduced the agglomeration of the mineral
particles and reduced the passivation degree of the enargite surfaces, thus increasing the
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copper leaching kinetics (Govindaiah et al., 2015b). An interesting result from Govindaiah et
al.s study (2015b) was that the application of DI water appeared to be as effective as using
acids in the pressure oxidation process. They reported 74% copper recovery when the pressure
oxidation process (4 h and 100 psi of oxygen overpressure) was catalyzed with PTFE. This
recovery value is about the same recovery value as those tests with the acids (Fig. 7).

Govindaiah et al. (2015b) also studied the effect of temperature on the copper recovery in DI
water with and without the addition of PTFE beads (Fig. 8). In general, copper leaching at 130 C

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is not as fast as it is at higher temperatures. Basically, at 130 C (Fig. 8) the elemental sulfur that
was produced had high viscosity, and the transfer of the sulfur from the partially-leached
mineral surfaces to the surfaces of the PTFE beads was not as fast and efficient. For
temperatures between 170 and 210 C, Govindaiah et al. (2015b) reported about 96% recovery
of copper into the leach solution within 4 h and in the presence of PTFE beads, and most of the
arsenic (96%) was precipitated out as scorodite in the residue (Govindaiah et al., 2015b). It also

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was confirmed that the regeneration of PTFE beads was not necessary and that they were

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reusable in multiple leaching cycles.

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Fig. 7. Effect of various leaching solutions (0.85 L) on copper extraction from enargite
concentrate at 150 C with an initial pulp density of 10 wt%, a PTFE/enargite mass ratio of 4:1
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(when used), and 100 psi of oxygen overpressure (Govindaiah et al., 2015b).
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Fig. 8. Effect of temperature on copper leaching in DI water (0.85 L) with an initial pulp density
of 10 wt%, a PTFE/enargite mass ratio of 4:1 (when used), and 100 psi of oxygen overpressure

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Safarzadeh et al. (2012) examined acid bake-water leach (ABL) process for the treatment of
enargite concentrate. Baking the enargite concentrate at 200 C for 7 h, with concentrated
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sulfuric acid added at 5 g acid/g of contained copper, had resulted in about 90% copper
extraction achieved with only 1% of the arsenic being released to the gas phase. Based on the
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XRD and SEM analysis of the baked product, copper sulfate crystallites with different
morphologies and elemental sulfur were observed on the surface of enargite. In a series of
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other published works (Safarzadeh and Miller, 2014a, 2014b, 2014c) the researchers
investigated the effects of operating parameters on the extraction of copper and arsenic from
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enargite in ABL process; in all of those works, they did not provide a suggestion for recovery of
elemental sulfur from the leach residues but did claim that the residues of the ABL process are
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less complex than those of POX processes. ABL process appears to be an interesting however an
expensive process.

Although the atmospheric or medium temperature leaching of copper sulfides are known to
produce elemental sulfur, the focus of the literature mostly have been on the sulfur oxidation
or removal of the sulfur from the surface of the partially leached minerals during the leaching
process, rather than the separation of the elemental sulfur from the leach residues. This is
mainly because the atmospheric and medium temperature leaching of copper sulfides mostly

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have been practiced on the copper-only concentrates, or the value of the residue has been
insignificant. Thus, the residue could be directly sent to disposal. The authors expect that in the
near future the mining industry will show more interest in the ATL and MT-POX processing of
polymetallic copper sulfides, due to the high cost of TPOX process, and the environmental
challenges associated with the pyrometallurgical routes. Thus, sulfur removal from the residues
of the copper leaching processes, in order to prepare the residue for the next processing unit

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operations such as gold recovery, will be a center of focus. The sulfur removal from zinc

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leaching residues has been practised for several decades, and the next section will focus on the

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available technologies and newer developments.

The authors would like to acknowledge that in a different setting, CESLs MT-POX process

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applies intensive cyanide leach to recover the gold (and silver) value from the sulfur-containing
copper leaching residues by the application of higher cyanide and oxygen concentrations, to
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reduce and engineer the negative effect of sulfur prescience in the leach residue. The value
recovery from the sulfur-containing residues without the removal of sulfur is beyond the scope
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of this review study.

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3. 2. Treatment of elemental sulfur during the leaching of zinc sulfide ores, and in the
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residues

Zinc sulfide ores mainly have been treated by pyrometallurgical methods to recover zinc.
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Nevertheless, pyrometallurgical processes continue to be of concern due to the environmental

issues associated with SO2, arsenic, and mercury emissions (Halfyard and Hawboldt, 2011).
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Alternatively, hydrometallurgical processes have been applied in several operations to recover

the zinc value. The direct leaching process (also known as Sherritts Zinc Pressure Leach
process) was commercialized at the Trail, British Colombia, zinc refinery of Cominco Limited
(now Teck Resources) (Halfyard and Hawboldt, 2011). The process is shown in Fig. 9.

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Fig. 9. Flowsheet of the Teck zinc pressure leach process (reproduced from D'Odorico, 2004).
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Zinc pressure leaching is conducted based on the following reaction:

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ZnS + H2SO4 + 0.5O2 ZnSO4 + So + H2O (6)

Calcium lignosulfonate (C20H24CaO10S2) and/or quebracho at a concentration of 1 kg/ton are

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used in the process to inhibit the formation of a sulfur coating on the surfaces of the partially-
leached or fresh sphalerite particles (Halfyard and Hawboldt, 2011). The molten sulfur products
solidify as sulfidic micropellets (44-200 m) during the flash tank operation, and the solid sulfur
residues and unleached/unreacted sulfide minerals are separated from the direct leaching
residue (DLR) via a flotation process. The sulfur recovery flotation circuit would be practised to
produce a sulfide and sulfur concentrate if the sulfur content of DLR is less than 70%. Then, the
flotation concentrate is sent to a melting process at 145 oC to further process the elemental

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sulfur product (Halfyard and Hawboldt, 2011). Flotation of DLR for the recovery of the sulfur
concentrate can be eliminated if the sulfur content of DLR is above 70%.

The addition of the flotation step to recover sulfur from the low-sulfur residues potentially adds
to the costs of the sulfur removal process, so, in some cases, the sulfur-containing residues with
low sulfur content (< 70%) are disposed directly as hazardous wastes. This practice can
potentially create environmental challenges in the future. Thus, many studies have been

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conducted at laboratory and pilot scales to develop and verify novel, low-cost methods for

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removing sulfur from the low sulfur residues.

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Gu et al. (2010) investigated the effect of different leaching parameters on the pressure acid
leaching of zinc sulfide concentrate from the Huludao Zinc Plant in China in the presence of

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oxygen (reaction (6)). Sphalerite (78.4%) was the major mineral in the concentrate. Gu et al.
(2010) showed that the elemental sulfur that is produced seals off the underlying mineral and
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inhibits its further oxidation. A 74.5% recovery of zinc was achieved when the conditions were
as follows, i.e., acidic pressure oxidation of the concentrate for 1.5 h at 150 oC and 145 psi of
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oxygen over pressure, solid-to-liquid ratio of 1:4, concentrate particle size < 53 m, and stirring
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at 480 r/min. The addition of 1% lignosulfonate to inhibit sulfur coating increased the zinc
leaching recovery from 74.5% to above 90%.
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Peng et al. (2005) studied the leaching kinetics of a sphalerite concentrate (74.7% sphalerite,
5.7% pyrite, and 2.3% chalcopyrite) in an oxygenated H2SO4HNO3 solution, and they indicated
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that the leaching reaction was as follows:

3ZnS + 3H2SO4 + 2HNO3 3ZnSO4 + 2NO + 3So + 4H2O (7)

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2NO + O2 2NO2 (8)

3NO2 + H2O 2HNO3 + NO (9)

Peng et al. (2005) suggested that it is important to inhibit the adsorption of molten elemental
sulfur on the surfaces of the partially-leached mineral to increase the overall zinc recovery in
the leaching process. Tetrachloroethylene (C2Cl4) was added to the leaching solution to

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dissolve the elemental sulfur that is produced during the leaching process in the organic phase
at a temperature below the melting point of sulfur:

So + C2Cl4 So.C2Cl4 (10)

Then, the elemental sulfur was recovered by cooling the organic phase that contained the
sulfur:

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So.C2Cl4 (Cooling) So + C2Cl4 (11)

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Peng et al. (2005) recommended that the leaching should employ the following conditions, i.e.,

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2.0 M H2SO4, 0.2 M HNO3, 10:1 mL/g ratio of leaching solution to sphalerite concentrate, at 85
C, 14.5 psi oxygen overpressure, and the volumetric ratio of the organic solvent to the leach

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solution at 1:20 in order to recover about 88.2% Zn in 1.0 h (Fig. 10).
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Fig. 10. Sphalerite concentrate leaching with (10 mL) and without C2Cl4: temperature 85 C;
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liquid/solid of 10:1 mL/g, 200 mL solution containing 2.0 mol/L H2SO4 and 0.2 mol/L HNO3; 0.1
MPa O2 (Peng et al., 2005).
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Harvey et al. (1993) studied the acidic pressure leaching of a high iron sphalerite concentrate at
180 oC and concluded that reaction (6) is the overall leaching reaction. Increasing the leaching
temperature resulted in the oxidation of sulfur to sulfate:

2So + 2H2O + 3O2 2H2SO4 (12)

In order to determine the predominant control mechanism, Silva (2004) studied both diffusion
and reaction models in bacterial leaching of sphalerite. The bacterial leaching of sphalerite is

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conducted indirectly based on the following equations (Silva (2004); Fowler and Crundwell,
1998, 1999):

ZnS + 2Fe3+ Zn2+ + So + 2Fe2+ (13)

2Fe2+ + 0.5O2 + 2H+ (Bacteria) 2Fe3+ + H2O (14)

Elemental sulfur produced in reaction (13) can be oxidized using sulfur-oxidizing bacterium of

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genus Acidithiobacillus; subsequently, the resistance to diffusion should be decreased (Silva

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(2004); Fowler and Crundwell, 1998, 1999):

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So + 1.5O2 + H2O (Bacteria) SO42- + 2H+ (15)

Silva (2004) concluded that for bacterial leaching at 35 oC, both chemical reaction and

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molecular diffusion were effective. The diffusion-controlled process can be the result of an
incomplete biological removal of the elemental sulfur product layer or perhaps the result of
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lead sulfate or jarosite precipitates (Silva, 2004).
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Sodium sulfide leaching and carbon dioxide precipitation were used by Wang et al. (2015) to
recover elemental sulfur, without mercury, from a flotation sulfur concentrate (So: 84.9%, Stotal:
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89.5%, Zn: 5.9%, Iron: 2%) during the zinc pressure leaching process. After the leaching process,
the sulfur in the leach residue, and subsequently the unwanted mercury that also is present,
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were recovered by flotation; so treatment is needed to increase the assay of elemental sulfur
and to remove the mercury from the elemental sulfur so that it can be utilized (Wang et al.,
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2015). Fig. 11 shows the flowsheet of the process.

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Fig. 11. Na2S leachingCO2 precipitating methods to extract elemental sulfur from flotation
concentrate (reproduced from Wang et al., 2015).
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The mechanism is proposed as follows: (1) Reaction of the elemental sulfur with sodium sulfide
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in the solution to form a soluble polysulfide; the mercury reacts with the sulfide ions to produce
insoluble mercuric sulfide (Halfyard and Hawboldt, 2011; Wang et al., 2015; Sun et al., 2005):
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Na2S + (x1)So Na2Sx (16)

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Hg2+ + S2 HgS (17)

(2) Filtration of the polysulfide-containing solution to separate leach residue, which is rich in
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mercury. Then, the polysulfide-rich filtrate is decomposed with carbon dioxide to recover the
elemental sulfur:

Na2Sx + CO2 + H2O NaHS + NaHCO3 + (x1)So (18)

(3) Pure elemental sulfur is provided by filtration and drying. The filtrate containing sodium
hydrosulfide (NaHS) and bicarbonate (NaHCO3) can be used to regenerate sodium sulfide:

NaHS + NaHCO3 + CaO Na2S + CaCO3 + H2O (19)

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The sodium sulfide is recycled back to the leaching circuit, and the calcium carbonate can be
roasted to produce carbon dioxide and lime (CO2 + CaO) for reuse in reactions (18) and (19).
The results showed that elemental sulfur with a purity of 99.7% could be recovered using the
following conditions, i.e., 1.5 mol/L sodium sulfide concentration, liquid/solid ratio 6:1, leaching
time 30 min, room temperature, carbon dioxide flow rate 200 mL/min, and blowing time of 150
min (Wang et al., 2015).

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High-purity elemental sulfur, originally in a zinc-leaching residue obtained from the leaching of

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a sulfur-rich flotation concentrate (S: 64.7%, SiO2: 2.4%, Pb: 2.5%, Cu: 0.4%, Fe: 10.8%, Zn:

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1.2%), was separated from its non-sulfur constituents by Watanabe et al. (2000) via an efficient,
low-cost distillation and condensation method. This process includes heating the sulfur-

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containing residue to a temperature much less than the sulfur boiling point, i.e., 445 C, to
evaporate and separate the sulfur. Sulfur is known to have a high vapour pressure even in the
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liquid form at temperatures near its melting point (119 C) (Watanabe et al., 2000). Therefore,
the sulfur was heated to a temperature greater than its melting point, i.e., 119 C, and below
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140 C; then, the evolving sulfur-containing vapour was cooled to condense the sulfur (Fig. 12).
Almost 100%-pure sulfur was recovered with a yield of about 85%.
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In another attempt to recover elemental sulfur from zinc direct leach residue, Li et al. (2014a)
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used vacuum distillation process (Fig. 13). In the experiments, the sample was placed in a
tubular furnace equipped with a temperature controller and a vacuometer, and two
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condensers were used to cool the distillation gases. The solids were filtered before proceeding
to the vacuum pump. Under optimal operating conditions for particle sizes smaller than 0.147
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mm, 220 oC, -0.1 MPa in 30 min, the reported sulfur recovery rate and sulfur purity were higher
than 98% and 97.8%, respectively (Li et al., 2014a).

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Fig. 12. Apparatus for recovering sulfur by heating: in the reaction vessel, the sample is heated

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to 140 oC for 2 hours in the presence of N2 carrier gas (for conveying sulfur vapour to the

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cooling water in the flask). Solid sulfur is the final product (reproduced from Watanabe et al.,

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2000).

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Fig. 13. Experimental set-up for extraction of elemental sulfur from direct leaching residue
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using distillation (reproduced from Li et al., 2014a).

Li et al. (2014b) studied the extraction of elemental sulfur from zinc DLR using atmospheric
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distillation at the pilot scale (Fig. 14). The DLR (SiO2: 5.27%, Fe2O3: 9.06%, ZnO: 6.64%, and SO3:
74.75%) was fed into the distiller and heated, sulfur vapour was condensed, and the water
vapour was rejected. The water and unwanted sulfur particles were recovered in a cyclone and
scrubber before the gases were discharged to the environment. The distillation concentrate
(Fig. 14) was rich in metal elements, including zinc, which could be used for metal refining (Li et
al., 2014b).

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The experiments were conducted in batch, semi-batch, and continuous systems. The
experiments included different temperatures from 430 to 490 oC with feed amounts of 400 to
2032 kg in batch, 460 C with 250 kg/h in semi-batch and 460 C with 240 kg/h in continuous
tests. At the optimized conditions of the batch experiment with a feed amount of 1200 kg and a
temperature of 460 oC, elemental sulfur with a purity of about 96% and a recovery rate greater
than 85% were achieved. Based on the 0.59 and 1.24 KWh power requirements to handle 1.0 kg

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dry DLR and to produce 1.0 kg of elemental sulfur, respectively, it was concluded that this

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method was technologically and economically feasible (Li et al., 2014b).

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Fig. 14. Flowsheet for atmospheric distillation of elemental sulfur at the pilot scale (reproduced
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from Li et al., 2014b).

4. Conclusions
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Elemental sulfur has been identified as one of the most important products responsible for the
slow oxidative leaching of sulfide minerals in the ATL and MT-POX leaching processes. Wetting
of the surfaces of the partially-reacted mineral with molten elemental sulfur in the MT-POX
process and passivating the surface of the mineral with sulfur in the ATL process result in a
decrease in the metal recovery and create environmental risks. In addition, challenges of the
elemental sulfur in the leaching residue and decreasing of the efficiency of the solid/liquid
separation processes are some examples of the problems associated with the formation of

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elemental sulfur during the leaching of sulfide minerals. The proposed solutions to address the
elemental sulfur problems in hydrometallurgical processes of zinc and copper sulfide
concentrates can be categorized in three main groups:

1. Enhancing leaching kinetics: (a) dispersing the sulfur using surfactants. Surfactants, such as
calcium lignosulfonate and/or quebracho at concentrations of 1-5 kg/ton, are used in MT-POX
processes. The dispersant disperses the molten elemental sulfur and prevents the passivation

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of the sulfide minerals; (b) converting the sulfur to sulfate or to hydrogen sulfide. Oxidants,

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such as ozone (in sulfuric acid media), oxygen (acidic pressure oxidation), hydrogen peroxide (in

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sulfuric acid solution), and sulfur-oxidizing bacteria of genus Acidithiobacillus, were used to
oxidize and remove the elemental sulfur from the surfaces of the mineral and to convert it to

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soluble sulfate ions. Sulfur-reducing bacteria (SRB) also have been claimed to convert elemental
sulfur into hydrogen sulfide and to remove elemental sulfur from the surfaces of the mineral
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during the enargitepyrite gold concentrate leaching process.

2. Sulfur separation from residue, during or after the leaching process: (a) dissolving sulfur
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during leaching using organic solvents. Carbon tetrachloride (CCl4) in an FeCl3 + HCl medium
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and tetrachloroethylene (C2Cl4) in an H2SO4 + HNO3 medium are examples of the solvents that
are used in the chalcopyrite and sphalerite leaching processes, respectively. Then, the
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elemental sulfur can be recovered by cooling the sulfur-containing organic phases; (b) sodium
sulfide leaching and carbon dioxide precipitation to recover elemental sulfur from zinc
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concentrate DLR. Elemental sulfur with a purity of 99.7% can be recovered; (c) Solid sorbents to
recover S during the leaching process. Nano-silica, in the H2SO4 medium that contains H2O2
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oxidant, increased the copper leaching recovery from chalcopyrite concentrate by about 40%.
PTFE recently has been proposed as a promising solid sorbent for the liquid sulfur generated
during the medium-temperature, pressure leaching of chalcopyrite and enargite. The PTFE
increased the recovery of copper in the enargite leaching process (in DI water medium, 150 oC,
4 h and 100 psi of oxygen over pressure) from 17% in the absence of PTFE to 74%. Recently,
TiO2 was proposed as an inorganic filler for PTFE beads. In addition to PTFE, TiO2 can create a
new hydrophobic surface for sulfur adsorption. The PTFE/TiO2 adsorbent was reusable in the
process even after 10 leaching cycles.

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3. Flotation or distillation of the DLR: (a) flotation: in the Teck zinc pressure leaching process,
the flotation of DLR is applied when the sulfur content of the DLR is less than 70%. Then, the
flotation concentrate is sent to a melting process at 145 oC to recover the elemental sulfur; (b)
distillation and condensation: heating the DLR to a temperature greater than its melting point,
i.e., 119 C, and below 140 C and then cooling the evolving sulfur-containing vapour to
condense the sulfur. A pure sulfur product (almost 100%) was recovered with a yield of about

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85%; (c) vacuum distillation: DLR with particle sizes smaller than 0.147 mm was subjected to

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vacuum distillation at 220 oC, -0.1 MPa in 30 min; the sulfur recovery and purity were higher

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than 98% and 97.8%, respectively; (d) atmospheric distillation: in batch experiments at a
temperature of 460 oC, the elemental sulfur with a purity of about 96% and a recovery greater
than 85% were achieved. It also was claimed that this method is technologically and

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economically feasible.
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Acknowledgments
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The authors acknowledge the financial support of Queens University through the Research
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Initiation Grant (RIG).

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Highlights

The solutions proposed to address the elemental sulfur problems in some important
hydrometallurgical processes.
Dispersing the sulfur by surfactants and converting the sulfur to sulfate or to hydrogen
sulfide is proposed.
Dissolving sulfur during leaching using organic solvents is examined.
The role of sodium sulfide leaching and carbon dioxide precipitation to recover
elemental sulfur is reviewed.

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Solid sorbents to recover sulfur as well as flotation or distillation of the DLR are

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proposed as promising solutions.

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