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Mineral Processing and Extractive Metallurgy Review

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The Direct Leaching of Nickel Sulfide Flotation


Concentrates – A Historic and State-of-the-Art
Review Part I: Piloted Processes and Commercial
Operations

Nebeal Faris, Mark I. Pownceby, Warren J. Bruckard & Miao Chen

To cite this article: Nebeal Faris, Mark I. Pownceby, Warren J. Bruckard & Miao Chen (2022):
The Direct Leaching of Nickel Sulfide Flotation Concentrates – A Historic and State-of-the-Art
Review Part I: Piloted Processes and Commercial Operations, Mineral Processing and Extractive
Metallurgy Review, DOI: 10.1080/08827508.2022.2070617

To link to this article: https://doi.org/10.1080/08827508.2022.2070617

© 2022 The Author(s). Published with Published online: 16 May 2022.


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MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW
https://doi.org/10.1080/08827508.2022.2070617

The Direct Leaching of Nickel Sulfide Flotation Concentrates – A Historic and State-of-
the-Art Review Part I: Piloted Processes and Commercial Operations
Nebeal Farisa,b, Mark I. Pownceby a
, Warren J. Bruckarda, and Miao Chen a,b

a
CSIRO Mineral Resources, Private Bag 10 Clayton South, Victoria 3169, Australia; bSchool of Science, RMIT University, GPO Box 2476, Melbourne,
Victoria 3001, Australia

ABSTRACT KEYWORDS
The extraction of nickel (Ni) from sulfide resources commences with flotation to produce a concentrate Nickel; cobalt; pentlandite;
which is then smelted to produce a nickel-enriched phase called matte, and further refined to produce nickel sulfides;
pure Ni products as well as by-products, such as cobalt (Co), copper (Cu) and precious metals. However, hydrometallurgy
the traditional concentrate smelting-matte refining process, whilst technologically robust, is capital
intensive and suffers from several environmental and technical issues such as sulfur dioxide emissions,
poor recovery of cobalt and difficulty processing concentrates high in magnesia and arsenic without
appropriate blending with high grade concentrates to dilute the concentration of these species. The direct
hydrometallurgical processing of nickel sulfide concentrates and whole ores may be a remedy to these
issues and hydrometallurgy offers several advantages over pyrometallurgy such as potentially lower
capital costs, the ability to process lower grade materials and produce marketable metals or compounds
directly from ore/concentrate. Despite the advantages of hydrometallurgy over traditional base metal
sulfide smelting, the hydrometallurgical processing of nickel concentrates has been limited to a small
handful of commercial operations, some of which only produce an upgraded intermediate for pyrome­
tallurgical processing. In Part I of this three-part series, a comprehensive review of piloted processes for
direct hydrometallurgical processing of nickel sulfide concentrates is presented, followed by a survey of
industrial operations which have carried out direct leaching of nickel sulfide concentrates. A review of
research activities and challenges/opportunities in the direct hydrometallurgical processing of nickel
sulfide concentrates are presented in Part II and Part III of this series.

1. Introduction
beneficiation and less challenging to process, resulting in lower
Nickel (Ni) is an essential metal for society with stainless steels costs relative to Ni production from laterites (Elias 2002; Mudd
being its major end use, though high purity nickel sulfate, a key 2010). However, recent data from the United States Geological
raw material for production of lithium-ion battery (LIB) cath­ Survey (USGS) show that Ni production from laterite ores has
odes essential for electric vehicles (EVs) is a rapidly growing overtaken sulfide resources over the 2011–2016 period (McRae
market (McRae 2020a). Nickel demand has traditionally been 2018, 2020b). The key driver appears to be Chinese stainless-
driven by stainless steel production, either in the form of class 2 steel producers using NPI rather than class 1 nickel to reduce
(<99.8% Ni) nickel products such as nickel oxide, ferronickel manufacturing costs (Campagnol et al. 2017); Ni production
and nickel pig iron (NPI), or higher purity class 1 (>99.8% Ni) data from China show that approximately 60% of Ni produc­
nickel such as nickel powder, briquettes or electrowon cathode tion in 2016 was in the form of ferronickel and NPI (McRae
(Campagnol et al. 2017). Campagnol et al. (2017) have indi­ 2020b). Since 2014, NPI production has also expanded in
cated that demand for class 1 nickel in the form of high purity Indonesia, coinciding with the ban by the Indonesian govern­
nickel sulfate for lithium-ion batteries is expected to reach ment on the export of direct shipping nickel laterite ores
570,000 tonnes (Ni metal basis) in 2025. (McRae 2020b).
Terrestrial nickel resources are contained in sulfide and Lateritic ores are not typically amenable to beneficiation and
lateritic deposits, with 30–40% of the land-based nickel therefore direct processing of whole ore using hydrometallur­
resources being contained in sulfide deposits with the balance gical or pyrometallurgical techniques is necessary with the
in laterite deposits (Dalvi, Bacon, and Osborne 2004; Hoatson, choice of processing method being dependent on the type of
Jaireth, and Jaques 2006; Mudd 2010). Major nickel sulfide ore (Dalvi, Bacon, and Osborne 2004; Elias 2002; Marsh,
deposits are in Australia, Canada, Russia and Southern Africa Anderson, and Gray 2013). High pressure acid leaching
whilst most nickel laterite deposits are located in Indonesia, (HPAL) is the preferred method for the extraction of Ni and
New Caledonia, Brazil and the Philippines (Hoatson, Jaireth, Co from oxide (limonite) and clay silicate type ores to produce
and Jaques 2006). Despite laterites being more abundant than a diverse range of products (i.e. mixed sulfide precipitate,
sulfide deposits, Ni production has historically been derived mixed hydroxide precipitate, metal powder, cathode) whilst
from sulfides due to these resources being more amenable to saprolitic ores are generally processed via pyrometallurgy to

CONTACT Miao Chen Miao.Chen@csiro.au CSIRO Mineral Resources, Private Bag 10, Clayton South, Victoria 3169, Australia
© 2022 The Author(s). Published with license by Taylor & Francis Group, LLC.
This is an Open Access article distributed under the terms of the Creative Commons Attribution-NonCommercial-NoDerivatives License (http://creativecommons.org/licenses/by-nc-nd/4.0/),
which permits non-commercial re-use, distribution, and reproduction in any medium, provided the original work is properly cited, and is not altered, transformed, or built upon in any way.
2 N. FARIS ET AL.

produce either ferronickel or sulfide matte (Dalvi, Bacon, and smelting technology whilst matte converting is almost exclu­
Osborne 2004; Elias 2002; Marsh, Anderson, and Gray 2013). sively done using Peirce-Smith converters (Moskalyk and
Nickel laterite projects employing hydrometallurgical or pyr­ Alfantazi 2002; Warner et al. 2007).
ometallurgical processing have often suffered from high capital The objective of concentrate smelting is to remove part of
expenditure and cost blowouts, have required long ramp up the sulfur and iron present in the concentrate by oxidation;
times, suffered from technical issues relating to commissioning sulfur is oxidized to sulfur dioxide (SO2) whilst iron forms iron
and ramp up, and in the case of HPAL, have at times failed to oxide which is fluxed by reaction with silica to form an iron
achieve nameplate capacity (Jones et al. 2010; McDonald and Li silicate slag (Crundwell et al. 2011f). This iron silicate slag also
2020; Oxley, Smith, and Caceres 2016). The extraction of Ni removes any non-sulfide gangue present in the concentrate
from sulfide ores is much simpler relative to laterites and is which dissolves into the molten slag (Crundwell et al. 2011f).
dominated by pyrometallurgical processing. This typically Typical base metals content of concentrates utilized for smelt­
involves comminution and flotation to produce a nickel con­ ing contain a combined Ni, Cu and Co grade of 8% to above
centrate which is subsequently smelted and converted to pro­ 20%, though lower grade concentrates having a combined base
duce a sulfur-deficient, metal-enriched phase termed matte, metal concentration of 3–4% are smelted in Southern Africa
which is then refined to produce pure Ni, Cu, Co metal pro­ due to the high PGM content of these materials (Warner et al.
ducts and precious and platinum group metals (PGMs) where 2007). Concentrate smelting is carried out either by roasting-
applicable (Crundwell et al. 2011b). A simplified flow chart of electric furnace smelting or via flash smelting and the key
the flotation-smelting-matte refining process for treatment of process steps in both processes are presented in Figure 2; the
nickel sulfide ores is presented in Figure 1. There is great deal key principles of both methods are covered in detail elsewhere
of variation in the standard flow sheet with respect to flotation (Crundwell et al. 2011c, 2011f). The production details of both
practice (i.e. mineralogy, liberation size, reagents, etc.) and pyrometallurgical processing routes are presented in Table 1
converter matte refining, however concentrate smelting is including typical Ni and Cu grades in the concentrates, mattes
dominated by either flash smelting or roasting-electric furnace and slags. It can be seen from Table 1 that either pyrometal­
lurgical route is very efficient at recovering Ni, Cu and precious
metals to the matte. Base metal contents in slags produced
from flash smelting are generally higher and recoveries are
lower relative to the electric furnace route due to the more
oxidizing conditions employed, however slags are processed to
recover base metals through slag cleaning operations. Cobalt
recoveries are poor by either route (Matousek 1982; Warner
et al. 2007).
The final product from nickel concentrate smelting by
either route is a molten nickel sulfide enriched phase (matte)
which typically contains 15–40% Ni, 20–40% Fe, and 20–25%
S as well as Cu, Co and any PGMs (Crundwell et al. 2011a). The
molten matte is transferred to a converter where iron is oxi­
dized using air or oxygen and removed from the matte as an
iron silicate slag; the final product, termed converter matte,
typically contains 40–70% Ni, 0.5–4% Fe, 21–24% S as well as
Cu and Co (Crundwell et al. 2011a; Warner et al. 2007). There
is a great deal of variation with regards to the processing of
nickel converter matte to recover base and precious metals,
with direct hydrometallurgical processing of granulated con­
verter matte being practiced at some refineries (Warner et al.
2007). In other instances, such as mattes arising from smelting
of nickel-copper concentrates and concentrates high in PGMs,
slow cooling of the converter matte is carried out to enable
copper and nickel phase separation and the formation of coarse
sized crystals of chalcocite (Cu2S), heazlewoodite (Ni3S2) and
a metallic alloy phase enriched in precious and platinum group
metals; the cooled matte is beneficiated to produce separate Cu
and Ni-sulfide concentrates and a PGM-enriched concentrate
for further processing (Bulatovic 2007; Crundwell et al. 2011e;
Warner et al. 2007). Magnetic separation is carried out at
Anglo American Platinum’s refinery in Rustenburg, South
Africa, on slow-cooled mattes to recover the PGMs, with the
non-magnetic fraction (nickel-copper matte) being processed
Figure 1. Simplified traditional process flowsheet for the extraction of Ni, Cu and via hydrometallurgy in a dedicated base metals refinery produ­
Co from nickel sulfide resources. cing copper cathode and metallic nickel and cobalt powders
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 3

Figure 2. Process steps during the pyrometallurgical processing of nickel sulfide concentrates to produce nickel converter matte via flash smelting or the roasting-
electric furnace melting route. Adapted from Crundwell et al. (2011f).

Table 1. Production details of nickel concentrate smelting via the roasting-electric ● Starting from a nickel flotation concentrate of grade 5–
furnace smelting route and the flash smelting route. Data for roasting-electric 20% Ni, smelting and converting produces a nickel matte
furnace smelting and flash smelting adapted from Crundwell et al. (2011c, 2011f). containing 40–70% Ni, resulting in a considerable reduc­
Roasting-electric furnace Flash smeltingb,c tion in size of downstream leaching and refining equip­
Smelting process meltinga (Outotec & Inco)
ment relative to direct leaching of flotation concentrates,
Typical concentrate 5–14% Ni, 0.3–4.5% Cu, 5–15% Ni, 0.3–12%
grades 0.2–0.5% Co, 31–43% Fe Cu,
● Precious metals report to the matte and are more con­
0.2–0.4% Co, 30– centrated relative to the original flotation concentrates
43% Fe
%Ni recovery to matte 98 95
Ni grade in matte (wt%) 13–36 17–65 Against these advantages are several drawbacks such as:
Ni grade in slag (wt%) 0.1–0.4 0.2–4
%Co recovery to matte 50–80 26–70 ● Difficulty processing nickel concentrates high in arsenic
Co grade in matte (wt%) 0.7–1 0.4–0.8
Co grade in slag (wt%) 0.1–0.2 0.1–0.5 (As) and magnesia (MgO), which can render many con­
%Cu recovery to matte 98 80–93 centrates, particularly those produced from disseminated
Cu grade in matte (wt%) 1–11 1.5–25 sulfide ores and talc-carbonate ores, unsuitable if they
%Cu grade in slag (wt%) – 0.1–1.3
Recovery of precious 98–99 95 cannot be blended with higher quality concentrates to
metals (%) reduce the concentration of the deleterious species,
Based on production details of three Ni smelters – Falconbridge (Canada), ● Poor recovery of cobalt to the matte phase during smelt­
Thompson (Canada) and Norilsk (Russia). ing and converting, where typically 30–50% of cobalt is
Based on production details of seven Ni smelters – Kalgoorlie (Australia), Selebi
Phikwe (Botswana), Gansu (China), Norilsk (Russia), and Harjavalta (Finland), and lost to the metallurgical slag (Matousek 1982; Warner
two Ni smelters in Sudbury (Canada). et al. 2007),
Figures do not consider slag cleaning which is typically performed either ex-situ in ● High capital cost associated with concentrate smelting
a separate furnace or as an extension of the flash smelter.
and matte converting, including the capture of SO2 and
its conversion to sulfuric acid. The latter can only be
justified where there is a market for the sulfuric acid
(Crundwell et al. 2011d). Processes for the smelting of nickel that is produced (Lu et al. 2000),
flotation concentrates to produce matte followed by matte ● Plant hygiene issues relating to the use of ladles and
refining to produce Ni, Co and Cu products are well estab­ launders during pyrometallurgical processing (Dutrizac
lished. The primary advantages of nickel sulfide concentrate 1992).
smelting are the following (Crundwell et al. 2011b, 2011c,
2011d, 2011f): Elevated MgO grade (as talc, orthopyroxene etc.) in nickel
smelter feeds cause operational problems for the smelter due to
● Combustion of part of the sulfur and iron in the concen­ MgO raising the slag liquidus temperature and viscosity, lead­
trate can supply most of the energy requirements for smelt­ ing to poor slag-matte separation and higher metal losses due
ing (flash smelting only) and converting, with the added to entrainment (Eksteen, Oraby, and Nguyen 2020; Lotter et al.
advantage of removing a large part of the iron and sulfur 2008). This necessitates furnace operation at higher tempera­
from the concentrate as slag and sulfur dioxide (SO2), ture, which shortens the life of the furnace refractories. The
respectively, simplifying downstream matte refining, MgO content in the flotation concentrate(s) must be limited to
4 N. FARIS ET AL.

below 7–10% to prevent operational problems during smelting The purpose of Part I of this three-part series is to review
(Feng et al. 2012; Senior and Thomas 2005). Arsenic in the and summarize piloted leaching processes as applied to the
smelter feed is also problematic both from an environmental direct hydrometallurgical processing of nickel sulfide flotation
and operational perspective. Toguri, Babaie, and Sridhar concentrates and secondly, to survey commercial nickel opera­
(1995) has shown that the presence of As complicates the tions which have implemented hydrometallurgical processing.
refining of Cu-Ni mattes, leading to a decrease in grain size An overview of the geology and mineralogy of nickel sulfide
of chalcocite and alloy phases during cooling and altering the deposits, as well as current beneficiation practice is also pro­
morphology of chalcocite (from dendritic to spherical in the vided. Following an examination of pilot plant developments
presence of As). Whilst As can sometimes be rejected at the and commercial operations concerning the hydrometallurgy of
concentrator, this can be an issue when the As is present as nickel sulfide concentrates, laboratory research activities con­
niccolite (NiAs) and gersdorffite (NiAsS), which will result in cerning direct leaching of nickel sulfide concentrates are
nickel losses to the mill tailings. reviewed in Part II and Part III of this series and the challenges
Other situations where smelting may be unjustified include and research opportunities relating to nickel sulfide concen­
if the size of the resource to be processed is too small to justify trate hydrometallurgy are discussed.
the high capital cost associated with a dedicated smelter and
matte refining facility, or when the transport cost to ship nickel
2. Nickel sulfide deposits
concentrate(s) to a toll smelter is prohibitively high (Fleming
et al. 2000). Under these circumstances, direct hydrometallur­ Nickel sulfide deposits are found on most continents, however
gical processing of nickel sulfide concentrates can be a viable major deposits are found in Russia, Australia, Canada, and
alternative, and many of the technical, economic and environ­ Southern Africa (Hoatson, Jaireth, and Jaques 2006). Canada
mental challenges imposed on smelting have spurred research and Russia possess the largest resources of nickel sulfides,
and development activities around hydrometallurgical pro­ followed by Australia and South Africa; however, Australia
cesses for the extraction of Ni, Co and other base metals (Cu, has the largest nickel resources when laterites are also consid­
Zn) from sulfide concentrates. Direct hydrometallurgical pro­ ered (Hoatson, Jaireth, and Jaques 2006). All nickel sulfide
cessing of whole nickel sulfide ores has also received consider­ deposits are magmatic in origin and are broadly characterized
able attention, particularly bioleaching, which was the subject as either sulfide rich (>5%) or sulfide poor (<5%); for sulfide
of a review by Watling (2008). Despite the level of research and rich deposits, Ni and Cu are of primary economic interest
development over the years on nickel concentrate hydrometal­ whilst for sulfide poor deposits, generally PGMs are of eco­
lurgy, the adoption of hydrometallurgical processes for the nomic importance (Naldrett 1999; Song, Wang, and Chen
extraction of Ni, Co and Cu from nickel flotation concentrates 2011). The major nickel sulfide deposits including the nickel
remains low, particularly given several operations utilize some grade, contained nickel metal and year of discovery are pre­
form of hydrometallurgical processing to produce an upgraded sented in Table 2; typical Ni and Cu concentrations in mag­
sulfide product for smelting, or the operation originally built matic Ni-Cu sulfide deposits are 0.7–3% Ni and 0.2–2% Cu
for processing sulfide concentrates has switched over to other (Eckstrand and Hulbert 2007); the deposits of the Bushveld
nickel sulfide feedstocks. Igneous Complex (South Africa) are lower grade but possess

Table 2. Nickel grade, contained nickel metal (in tonnes) and year of discovery of major nickel sulfide deposits across the globe; data adapted from Hoatson, Jaireth,
and Jaques (2006) unless stated otherwise.
Nickel grade Contained Ni metal
Deposit (% Ni) (tonnes) Year of discovery
Australia
Kambalda, WA 3.30% 1,388,820 1966
Honeymoon Well, WA 0.75% 1,011,000 1973
Perseverance, WA 1.05% 2,480,640 1971
Mt Keith, WA 0.57% 3,411,420 1968
Yakabindie, WA 0.58% 1,682,000 1970
Nebo-Babel, WA* 0.47% 1,200,000 2000
Canada
Voisey’s Bay 1.59% 2,173,530 1993
Thompson 2.32% 3,486,960 1956
Sudbury 1.20% 19,776,000 1856
Russia
Noril’sk – Talnakh 1.84% 23,128,800 Noril’sk discovered in 1926, Talnakh in 1960
Pechenga 1.18% 4,000,200 1912
South Africa
Merensky reef, Bushveld complex 0.15% 6,313,500 1924
Platreef, Bushveld complex 0.41% 6,547,700 1925
China
Jinchuan, Gansu province 1.06% 5,459,000 1958
USA
Duluth complex, Minnesota 0.2% 8,000,000 1948
*Based on mineral resource and ore reserves estimate by OZ Minerals (2020).
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 5

high concentrations of PGMs for which they are primarily contains Ni, either in solid solution or as fine pentlandite
mined. The variation in Ni grade among some of the major intergrowths (Rezaei et al. 2017; Toguri 1975). Typically,
deposits is indicative of the proportion of high-grade massive the Ni concentration in solid solution in pyrrhotite is 0.4–
sulfide ore to low grade disseminated sulfide ore (Barnes, 0.6% and the presence of micron-size inclusions of pen­
Barnes, and Perring 2007). It can be seen from Table 2 that tlandite can raise the nickel content even higher (Rezaei
the Sudbury complex (Canada) and the Noril’sk-Talnakh et al. 2017; Toguri 1975). Hence during beneficiation of
deposits (Russia) are the largest sulfidic nickel deposits, being nickel sulfide deposits, nickel loss due to pyrrhotite rejec­
far larger than the other listed deposits based on contained Ni tion is inevitable.
metal alone. Whilst Australia possesses significant reserves of
sulfidic nickel and is ranked after Canada and Russia, the
2.2. Ore textures
deposits are much smaller.
Nickel sulfide ores are broadly classified into the following
categories: massive sulfide ore, matrix ore (also termed
2.1. Sulfide mineralogy
net-textured ore) and disseminated sulfide ore, the distinc­
A list of economically important nickel sulfide and tion being based on the sulfide content and silicate texture
arsenide minerals, as well as common sulfidic gangue in (Barnes and Lightfoot 2005). Massive sulfide ores consist
nickel sulfide deposits is presented in Table 3. Pentlandite of 75–100% sulfides as pyrrhotite, pentlandite and chalco­
is the most important nickel sulfide mineral and com­ pyrite, with or without minor pyrite (Barnes et al. 2018;
monly occurs with pyrrhotite and chalcopyrite. Other Barnes, Barnes, and Perring 2007). Where silicate inclu­
nickel sulfides listed in Table 3 can be important where sions are present in massive ores, they are generally dis­
alteration has taken place. Violarite is a supergene altera­ persed and isolated (Barnes et al. 2017; Jones 1996).
tion product of pentlandite and typically occurs in pyrite- Matrix sulfide ores comprise silicate inclusions in
violarite and transition zones above the primary zone a matrix of sulfide, the sulfide making up 30–70% of the
(massive pentlandite-pyrrhotite ore) (Marston et al. 1981; ore (Barnes et al. 2017). Disseminated sulfide ores contain
Nickel, Ross, and Thornber 1974) and can be economic­ between 1% and 33% sulfides dispersed in a silicate
ally important during the mining of some massive nickel matrix, the sulfides are not interconnected and are present
sulfide ores. Millerite forms as an alteration product of as patches in the silicate interstices or as globules (Barnes
pentlandite (Bide, Hetherington, and Gunn 2008; Holwell and Lightfoot 2005). The presence of multiple ore tex­
et al. 2017) and is an important nickel sulfide mineral in tures/types in a single deposit is not uncommon; for
some deposits such as Mt Keith, Black Swan and the Otter example, the Jinchuan deposit (Gansu province, China)
Shoot, Kambalda (Dowling et al. 2004; Grguric et al. 2007; contains both disseminated and matrix ore (Naldrett
Keele and Nickel 1974). Niccolite and gersdorffite can 2004) whilst all three ore textures are found at the
occur in nickel sulfide deposits as a result of hydrothermal Noril’sk-Talnakh camp (Barnes et al. 2018; Eckstrand
alteration; their presence in nickel concentrates is unde­ and Hulbert 2007). The massive sulfide ores at Noril’sk-
sirable due to the deleterious effects of As during smelting Talnakh are high grade, containing 3.42% Ni and 5.38%
and typically requires dilution to an acceptable level by Cu, but are of lower tonnage (88.7 Mt) relative to the
blending with low As concentrates (Grguric et al. 2007). lower grade disseminated ore (1706.3 Mt) which grades
Pyrrhotite, an iron sulfide, is the primary gangue sulfide 0.51% Ni and 1.02% Cu (Eckstrand and Hulbert 2007).
that occurs in nickel sulfide deposits though it typically Consequently, different flotation regimes have been

Table 3. Economically important nickel sulfide and arsenide minerals and their mode of occurrence in nickel sulfide deposits listed in terms of increasing Ni content (wt
%) and sulfidic gangue typically present in nickel sulfide deposits.
Chemical
Name formula Ni content (wt%) Mode of occurrence
Nickel sulfide minerals
Pentlandite (Fe, Ni)9 34.21 Mafic intrusions
S8
Violarite FeNi2S4 38.93 Supergene alteration of pentlandite-
pyrrhotite assemblages
Millerite NiS 64.67 Replacement product of pentlandite
Nickel arsenide minerals
Gersdorffite NiAsS 35.42 Hydrothermal replacement of pentlandite
Niccolite (nickeline) NiAs 43.93
Sulfidic gangue
Pyrrhotite Fe(1-x)S 0.4–0.6 Mafic intrusions
Pyrite FeS2 Variable, secondary pyrites can have Ni contents as high as 12%*. Primary Mafic intrusions (primary), supergene
pyrites can have Co contents as high as 2.37%† and can be an important alteration of pentlandite-pyrrhotite
host for this element. assemblages (secondary)
*Nickel, Ross and Thornber (1974).
†Watmuff (1974).
6 N. FARIS ET AL.

employed for processing the various types of Ni-Cu sulfide 3. Piloted processes and commercial operations
ores present at the Noril’sk-Talnakh camp (Kozyrev et al.
In response to the technical and environmental hurdles
2002).
presented by the traditional concentrate smelting-matte
refining route, the direct leaching of nickel sulfide flota­
tion concentrates has been intensely researched and
2.3. Beneficiation practice a number of these processes have been piloted and, in
Nickel sulfide ores are subjected to mineral beneficiation to some cases, have seen commercial implementation.
reject sulfidic and non-sulfidic gangue and produce a nickel Several nickel processing operations have practiced hydro­
concentrate grading from 5% to 25% Ni suitable for smelting metallurgical processing of nickel sulfide flotation concen­
(MäKinen and Taskinen 2008). Beneficiation is accomplished trates or whole ore at commercial scale and these are
through comminution and froth flotation (refer to Figure 1); summarized in Table 4. It can be seen in Table 4 that
in some instances, magnetic separation is employed before there is wide variability in terms of the feedstocks pro­
or after flotation to reject monoclinic pyrrhotite which is cessed, finished nickel products and leaching technology
ferromagnetic (Agar 1991; Bulatovic 2007). The choice of employed. A number of these operations are now closed
unit operations and operating parameters is largely dictated or no longer process flotation concentrates, having under­
by the type of ore being processed i.e. massive sulfide ore vs gone modifications to the original refineries to accommo­
disseminated sulfide ore which subsequently influences the date changes in feedstock (i.e. Kwinana, WA and Fort
liberation size and choice of flotation collectors and depres­ Saskatchewan, Canada). Other operations such as the
sants for separation of the values from the gangue. Other Nadezhdin mill (Russia) and the Cosmic Boy nickel con­
factors to consider include if the ore has been altered, which centrator (West Australia) carry out hydrometallurgical
can bring about mineralogical and textural changes; the processing to produce upgraded intermediates which are
effects of supergene alteration and serpentinization on nickel blended with flotation concentrates destined for smelting.
sulfide flotation have been well documented (Eltham and The processing of nickeliferous pyrrhotite concentrates is
Tilyard 1973; Kerr 2002; Mani et al. 1997; Mishra, Viljoen, practiced at the Nadezhdin mill (Russia) whilst historic
and Mouri 2013; Sizgoric 1981). Flotation practice differs by production took place in Canada (refer to Table 4). The
geographical location. Bulk sulfide flotation is generally car­ Canadian operations are unique in that roast-leach type
ried out on Western Australian nickel ores which tend to be processes were utilized to extract base metals from the
low in copper and contain substantial concentrations of pyrrhotite and produce an iron oxide residue suitable for
magnesium bearing minerals and hydrophobic gangue such production of iron ore pellets destined for steel making.
as talc (Bulatovic 2007; Eltham and Tilyard 1973; Pietrobon The purpose of this section is to summarize piloted pro­
et al. 1997). Bulk sulfide flotation is also carried out on ores cesses that have been developed to extract Ni directly from
from the Merensky Reef and UG-2 chromitite in South flotation concentrates and review several commercial
Africa due to the association of PGMs with base metal operations that have practised direct hydrometallurgical
sulfides in these ores (Xiao and Laplante 2004); the concen­ processing. While a number of these operations are now
trates are lower grade (3–4% combined base metals) but closed or no longer process flotation concentrates,
possess high concentrations of PGMs (100–400 g/t) a description has been provided for historical purposes.
(Warner et al. 2007). Flotation practice in Russia and
Canada differs from Western Australia where the deposits 3.1. Ammoniacal leaching processes
tend to be massive copper-nickel sulfide ores. In these ores,
pyrrhotite is the major gangue mineral and flotation is The ability of ammonia to selectively dissolve Cu, Ni, Co and
carried out to reject pyrrhotite and produce separate copper Zn from their ores and concentrates has formed the basis for
and nickel concentrates. Magnetic separation is generally several commercially developed leaching processes. The first
incorporated in the flowsheets to remove monoclinic pyr­ commercial operations utilizing ammonia-ammonium carbo­
rhotite (Agar 1991; Bulatovic 2007). Pyrrhotite rejection is nate solution as a lixiviant were deployed to extract Cu from
necessary as the smelting of pyrrhotite generates large quan­ mill tailings by Kennecott in Alaska, and Calumet and Heca in
tities of SO2 but yields very little nickel (Senior, Shannon, Michigan, USA (Forward and Mackiw 1955; Meng and Han
and Trahar 1994). Pyrrhotite rejection however must be 1996). Anaconda’s Arbiter process and BHP’s Escondida pro­
balanced against Ni losses during beneficiation since pyrrho­ cess were developed to extract copper from sulfide flotation
tite contains Ni in solid solution or as exsolved pentlandite concentrates utilizing ammonia-ammonium sulfate as
that is too fine to liberate (Bulatovic 2007; Kerr 2002; Senior, a lixiviant (Duyvesteyn and Sabacky 1993; Kuhn, Arbiter, and
Shannon, and Trahar 1994). Sequential flotation is employed Kling 1974). Ammonia-ammonium lixiviants have been uti­
to process massive sulfide ore from the Noril’sk-Talnakh lized for the extraction of Ni and Co from lateritic ores via the
deposit in Russia and produce separate copper, nickel and Caron process, which involves reduction roasting followed by
pyrrhotite concentrates (Bulatovic 2007; Kozyrev et al. 2002); ammonia-ammonium carbonate leaching (Caron 1950) and
the pyrrhotite concentrate has a high concentration of Ni, was in use at the Yabulu refinery in Queensland for processing
Cu and PGMs and is processed further in a dedicated hydro­ laterite ores (now in care and maintenance) and by Inco (now
metallurgical facility to recover the contained metals (refer to Vale) until 1982 for treating pyrrhotite concentrates via
Section 3.2.2). a modified process (see Section 3.6.2). The only
Table 4. Commercial nickel operations that have processed nickel-bearing sulfide concentrates via hydrometallurgical methods.
Leaching
Operation Location Operator process employed Feed to refinery Final Ni products Operational status Reference(s)
Ammoniacal pressure leaching
Fort Canada Sherritt Sherritt-Gordon Concentrate from Lynn Lake; 1954 –1970s, mix of Nickel briquettes and powder Still operating Forward (1953); Forward and
Saskatchewan International Limited ammonia pressure concentrate and matte; 1970–1980s mixed Mackiw (1955); Kerfoot
leach sulfide precipitate from Moa Bay (Cuba); 1991– (1989); Kerfoot and
present Cordingley (1997)
Kwinana Western Australia BHP Ni West Sherritt-Gordon Concentrate(s); 1970 – 1975, Nickel briquettes and powder; plan to Still operating Deng (1993), Wishaw (1993);
(formerly owned by ammonia pressure Concentrate(s) + flash smelter matte; 1975–1985, produce battery grade nickel sulfate Woodward (2014);
WMC leach matte only; 1985 – present after completion of brownfield Woodward and Bahri
Resources) expansion (2007); Anon (2021)
Sulfuric acid pressure oxidation
Garfield cobalt refinery USA Calera Mining Co. Sulfuric acid pressure Cobaltite concentrate from the Blackbird mine, Co-Ni granules grading 95.6% Co and Plant shut in 1959 due to Fassell (1962); Meddings and
oxidation Idaho (USA) 3.9% Ni shortage of ore Evans (1971); Berezowsky
(2000)
Fredericktown refinery USA National Lead Co. Sulfuric acid pressure Pyritic concentrate produced as a by-product of Nickel powder Plant shut in 1960 due to Fassell (1962); Meddings and
oxidation copper-lead mining shortage of feed Evans (1971); Mitchell
(1957); Berezowsky (2000)
Long Harbor Canada Vale Limited Sulfuric acid pressure Concentrate from Voisey’s Bay (Canada) Nickel cathode Still operating Crundwell et al. (2011b);
oxidation preceded Stevens et al. (2009)
by atmospheric
chlorine leach
Kokkola works Finland Outokumpu Oy Sulfuric acid pressure Ni concentrate from the Hitura mine (Finland, now Nickel chemicals Site is operating as a cobalt Nyman et al. (1992),
oxidation (HIKO) closed) refinery by Umicore. Status of Berezowsky (2000), Cooke
the pressure leach plant (2021); Törmänen and
unknown. Tuomela (2021)
Nadezhdin mill Russia Nornickel Sulfuric acid pressure Pyrrhotite concentrates from the Talnakh deposit(s) Non-ferrous metals precipitated from Still operating Deng (1992, 1993); Berezowsky
(Formerly known as oxidation grading 2–5% Ni, 1–2% Cu and up to 15 g/tonne solution after leaching and a Ni-Cu-Co (2000); Kitay, Mechev, and
Noril’sk Mining PGMs -PGM concentrate is recovered for Volkov (1991)
and Metallurgy smelting
Corporation)
Bioleaching
Talvivaara Finland Terrafame Ltd Heap bioleach Black schist ore from Sotkamo deposit, grading Mixed nickel-cobalt sulfide precipitate; Still operating Riekkola-Vanhanen (2007,
0.27% Ni, 0.56% Zn, 0.14% Cu MSP is being processed further to 2013); Watling (2008);
produce Ni and Co sulfates Törmänen and Tuomela
(2021)
Vuonos Finland Elementis (formerly Stirred tank bioleaching Nickel concentrate by-product from talc mining at Ni-Co mixed hydroxide precipitate (MHP) Plant only periodically Laukka et al. (2018); Neale et al.
Mondo Minerals) Sotkamo and Vuonos operational according to (2016, 2015), Törmänen and
Törmänen and Tuomela Tuomela (2021)
(2021)
Cosmic Boy nickel concentrator Western Australia Western Areas Stirred tank bioleaching Cleaner tailings stream from flotation grading Ni recovered from solution by Still operating Fewings and Seet (2014);
Limited (BioHeapTM) 18.3% Ni precipitation as a sulfide and blended Fewings et al. (2015, 2016)
into final flotation concentrate
Roast-leach
Falconbridge iron ore plant Canada Falconbridge Ltd. Sulfation roasting Pyrrhotite concentrate (1.13% Ni) from Ni (& Cu, Co) recovered from solution by Plant shut in 1972 Rezaei et al. (2017), Thornhill
Falconbridge operations precipitation as a sulfide (1954, 1961)
Inco iron ore recovery plant Canada Inco Ltd. (now Vale Modified Caron process Pyrrhotite concentrate (0.75% Ni) from Copper Cliff Nickel oxide product grading 77% Ni, Reduction roast-leach section of Conard (2013)’; Inco Staff
(IORP) Ltd) or Clarabelle operations 0.15% Co and 0.15% S the plant shut in 1982. (1956); Rezaei et al. (2017);
Oxidizing roaster closed in Queneau, Sproule, and Illis
1991. (1949)
Kokkola works Finland Outokumpu Oy Sulfation roasting Pyrite-pyrrhotite concentrate from Outokumpu Mixed Cu-Ni-Zn sulfide precipitate fed to Roaster operated between Deng (1992); Palperi and
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW

copper mine grading 0.67% Co and 0.37% Ni the smelter at Harjavalta (Finland); 1966–1987. Co and Ni Aaltonen (1971); Sauni et al.
cobalt metal produced production continued after (2010)
roaster shutdown
7
8

Table 5. Summary of hydrometallurgical processes developed for the direct leaching of nickel sulfide flotation concentrates and status of the technology.
Typical Ni
grade in Operating Total oxidation of sulfide to
Process Developer feed Lixiviant Operating Pressure (absolute) temperature sulfate (Y/N) Commercial status Remarks Reference(s)
Pressure oxidation processes
Sherritt-Gordon Sherritt International 10–16% 801–1101 kPa 70–95°C Y In operation at Fort Both refineries no Deng (1993); Forward
N. FARIS ET AL.

NH3-(NH4)2SO4-air
Saskatchewan longer treat (1953); Forward and
(Canada) and flotation Mackiw (1955)
Kwinana (WA) concentrates
CESL Teck Resources Limited 2–20% H2SO4-O2 +8–12 g/L 1481 kPa 115–175°C N Has not been Feed ground to Defreyne et al. (2006);
chloride & 5–10 g/L commercially a P80 of 45 µm Jones (1996); Jones,
Cu(II) deployed for Hestrin and Moore
processing Ni (1998); Jones, Mayhew
concentrates and O’Conner (2009);
Jones et al. (2010);
Jones, Moore and
Stocker (2003)
Activox® Western Minerals Technology Pty 4–12% H2SO4-O2 +4 g/L 500–1100 kPa 80–110°C N Demonstrated at the POX preceded by Adams and Johnson
Ltd chloride Tati Nickel Project ultra-fine (2001), Corrans,
(Botswana), full grinding (P80 of Johnson and Angove
scale plant never 5–15 µm) (1993); Johnson and
built Evans (1998), Johnson,
Evans and Turner
(2000); Palmer and
Johnson (2005); Robles,
Cronje and Nel (2009)
PLATSOLTM International PGM Technologies 3–15% H2SO4-O2 +5–20 g/L 790 kPa 225°C Y Developed to treat Flotation Dreisinger et al. (2005);
Ltd NaCl polymetallic concentrate Ferron and Fleming
concentrates from ground to P80 of (2001); Ferron and
Duluth complex 15 µm Fleming (2002); Ferron
(Minnesota); has et al. (2000, 2002);
not been Fleming et al. (2000)
commercially
deployed
Kell Process Lifezone Limited – H2SO4-O2 500–3000 kPa 170–230°C Y Process developed to PGM-enriched leach Adams, Liddell and
treat PGM-bearing residue Holohan (2011); Adams,
sulfide processed Liddell, and Smith
concentrates; has further via (2015); Liddell (1999);
not been a roast-chlorine Liddell and Adams
commercially leach process (2012, 2013); Liddell
deployed et al. (2011, 2019)
Voisey’s Bay Vale Limited 5–25% 1st stage; Cl2-O2 1st stage – atmospheric 1st stage; N In operation at Long Concentrate ground Crundwell et al. (2011b);
Process 2nd stage; 2nd stage – 40–90°C Harbor (Canada) to 20 µm prior to Kerfoot et al. (2001);
H2SO4-O2 601–1101 kPa 2nd stage; leaching Stevens et al. (2009)
100–150°C
HIKO Outokumpu 5–7% H2SO4-O2 601 kPa <110°C N Developed to treat – Nyman et al. (1992),
Hitura Berezowsky (2000)
concentrate
(Finland)
(Continued)
Table 5. (Continued).
Typical Ni
grade in Operating Total oxidation of sulfide to
Process Developer feed Lixiviant Operating Pressure (absolute) temperature sulfate (Y/N) Commercial status Remarks Reference(s)
IGO Process IGO Limited – H2SO4-O2 +1–5 g/L 800–1200 kPa O2 pressure (Low 100–120°C (Low N (Low temp. POX) Has not been Main feature of IP is Grassi et al. (2019)
chloride temp. POX) temp. POX) Y (High temp. POX) commercially a method for
300 kPa O2 pressure (High temp. T > 200°C (High deployed production of
POX) temp. POX) nickel sulfate
hydrate from
leach liquor via
SX. Ultra-fine
grinding for low
temperature POX
Bioleaching processes
BioNIC® BHP 3–15% Mesophiles in acid- Atmospheric 30–45°C N Successfully Stirred tank Cole et al. (1997); Dew
Limited ferric sulfate media demonstrated but bioleach process et al. (1999); Gilbertson
using air as the not commercially (2000); Heinzle, Miller
oxidant deployed and Nagel (1999);
Norton, Coetzee, and
Barnett (1998); Rorke,
Basson, and Miller
(2001)
BacTech BacTech Limited 3–7.5% Thermophiles in acid- Atmospheric 45–55°C N Successfully Stirred tank Fewings and
ferric sulfate media demonstrated but bioleach process Wilathgamuwa (1998);
using air as the not commercially King and Budden
oxidant deployed (1996); Miller et al.
(1999); Miller (1997);
Taylor, Fairley, and
Winby (1997)
BioHeapTM BioHeap Limited (subsidiary of – Proprietary bacterial Atmospheric 15–95°C N Process is in use at Bacterial cultures Fewings and Seet (2012);
Western Areas Limited) culture in a sulfate (Temp. range Western Areas can be used for Fewings and Seet
medium above pH 2 microbes are Limited’s Cosmic heap, column (2014); Fewings et al.
tolerant to) Boy nickel and stirred tank (2015, 2016)
concentrator to leaching of
treat flotation whole ores and
cleaner tailings concentrates
Atmospheric pressure chemical leaching processes
HydroNic Outotec 13–32% 1st stage; CuCl2-HCl- Atmospheric 90–110°C N Has not been Either O2 or Cl2 can Haavanlammi et al. (2006),
brine commercially be used as the Karonen, Tiihonen, and
2nd stage; HCl-brine-O2 deployed oxidant in Haavanlammi (2009)
or Cl2 the second stage
leach
Intec Intec Limited 3–6% 1st stage; H2SO4-brine- Atmospheric 1st stage; N Successfully tested Concentrate ground Moyes and Houlis (2003)
Nickel air 80–90°C on a Ni-Cu-PGM to P80 of 25 µm.
Process 2nd stage; brine-BrCl2- 2nd stage; concentrate, not Brine in both
100°C commercially leach stages
deployed contains Cl− &
Br−
Albion ProcessTM Glencore (formerly Xstrata) – O2 + H2SO4 ± ferrous Atmospheric 93–98°C Sulfide oxidation can be Process in use for Concentrates Hourn and Turner (2012);
and ferric sulfate controlled by varying pH processing zinc, ground to P80 of Hourn, Turner, and
gold and copper 10–12 µm using Holzberger (1996),
concentrates; has an IsaMillTM Stieper (2018)
not been
commercially
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW

applied to the
processing of
nickel sulfide
9

concentrates
10 N. FARIS ET AL.

commercialized ammonia leaching process to date for the The operations at Fort Saskatchewan and Kwinana have
direct treatment of nickel sulfide concentrates is the Sherritt- demonstrated the adaptability of the Sherritt-Gordon ammo­
Gordon ammonia pressure leaching process which is currently nia pressure leach technology to processing different nickel
in use at Fort Saskatchewan, Canada, and Kwinana, Western sulfide feedstocks (flotation concentrates, matte or mixed sul­
Australia. The Sherritt-Gordon process is essentially a pressure fide precipitate). A significant advantage of the leach process
oxidation process carried out in aqueous ammonia- for concentrates is its selectivity toward Ni, Cu and Co, with
ammonium sulfate at elevated temperature using air as an iron present in pentlandite, chalcopyrite and pyrrhotite being
oxidant; the key operating characteristics and features of the converted to a hydrous ferric oxide residue (Forward and
process are listed in Table 5 and compared against other Mackiw 1955). Pyrite present in the concentrate does not
piloted and commercialized processes. The leaching technol­ react in the ammoniacal solution and reports to the residue;
ogy was developed to process nickel concentrate from Lynn this does however mean that any Ni and Co present in pyrite
Lake (Canada) grading 10–16% Ni, 1–2% Cu and 0.3–0.4% Co, are not dissolved during leaching (Forward and Mackiw 1955).
where a hydrometallurgical process was deemed to be more Other advantages of the Sherritt-Gordon ammonia leach pro­
cost effective than concentrate smelting and matte refining cess are that metallic nickel can be recovered directly from
(Forward 1953; Forward and Mackiw 1955; Kerfoot 1989). solution by hydrogen reduction, and part of the ammonia
In the Sherritt-Gordon Process, base metals are dissolved can be recovered for re-use in the leaching stage. The main
from the sulfide mineral particles by reaction with oxygen, disadvantages of the Sherritt-Gordon ammonia leach process
water and ammonia; ferrous iron is oxidized and precipitated are the high cost of ammonia relative to sulfuric acid, though
as hydrous ferric oxide (Forward 1953; Forward and Mackiw this is partially offset by recovery and recycling, the generation
1955). Sulfidic sulfur (S2-) is oxidized to thiosulfate (S2O32-) of ammonium sulfate [(NH4)2SO4] as a by-product, which
which then undergoes further oxidation by dissolved oxygen in requires disposal if there is no market for it, and cobalt recov­
solution to ultimately form sulfate (SO42-) and sulfamate (NH2 ery and refining is considerably more complex relative to acid-
SO32-) via a series of sequential reactions involving intermedi­ based leaching processes. Cobalt refining at Fort Saskatchewan
ates such as trithionate (S3O62-) (Forward 1953; Forward and involves complex multi-stage processing of cobalt intermedi­
Mackiw 1955). Dissolved copper in solution is believed to play ates (MSP or Co(III) hexamine sulfate) via leaching, recrystal­
a catalytic role in oxidation of thiosulfate to trithionate, sulfate lization and hydrogen reduction; by contrast cobalt recovery is
and sulfamate (Forward 1953). Batch leaching tests by Forward simpler in acid sulfate systems where cobalt separation from
(1953) showed that the nickel dissolution rate was influenced nickel is well established and is achieved by conventional
by factors such as temperature, oxygen partial pressure and free solvent extraction and electrowinning (SX-EW).
ammonia concentration; 95% of Ni could be extracted in under
an hour by leaching at 220°F (104.4°C). Higher leaching tem­ 3.1.1. Fort Saskatchewan, Canada
peratures and oxygen partial pressures, and longer retention The ammonia pressure leach process was originally developed
times favor the oxidation of thiosulfate and trithionate to to treat Ni-Cu-Co flotation concentrate from Sherritt-Gordon
sulfate and sulfamate, however, a key aspect of the Sherritt- Mines’ Lynn Lake concentrator in Canada (Deng 1994;
Gordon process is the retention of a portion of the unsaturated Forward 1953; Forward and Mackiw 1955; Kerfoot 1989).
sulfur containing ions in solution for subsequent copper Once the Lynn Lake Mine became exhausted (mid 1970s) the
removal (Forward 1953; Forward and Mackiw 1955). Copper refinery continued to operate, processing pentlandite concen­
removal is achieved by boiling the solution (termed “copper trates from across Canada and nickel mattes from overseas
boil”), where Cu(II) ions react with thiosulfate and trithionate (Kerfoot and Cordingley 1997). The Fort Saskatchewan nickel
in solution, precipitating copper as covellite (CuS) and chalco­ refinery continues to operate to this day, still employing
cite (Cu2S) (Forward 1953; Forward and Mackiw 1955). ammonia pressure leaching; however, since 1990 mixed Ni-
Precious and platinum group metals present in nickel matte Co sulfide precipitate produced as an intermediate from nickel
are reported to be partially extracted during ammoniacal pres­ laterite processing at Moa Bay (Cuba) is the primary feed to
sure leaching and are subsequently precipitated during the this refinery (Kerfoot and Cordingley 1997; Kofluk and
“copper boil” stage, reporting to the copper sulfide precipitate Freeman 2006). The flowsheet for the original refinery opera­
(Wishaw 1993). The copper-free solution produced from the tion at Fort Saskatchewan for concentrate processing is pre­
‘copper boil’ is treated in an autoclave at 245°C and air pressure sented in Figure 3 and involved ammonia pressure leaching in
of 4100 kPa to destroy residual unsaturated sulfur compounds a train of autoclaves operating at a temperature range of 80–
and ammonium sulfamate present in solution (termed oxydro­ 95°C and used compressed air as the oxidant at a pressure of
lysis) prior to metallic nickel recovery by pressure hydrogen 800 kPa (Kerfoot and Cordingley 1997). Nickel, cobalt and
reduction (Forward 1953; Wishaw 1993). The oxydrolysis step copper are leached into solution as their ammine complexes
is necessary to prevent sulfur contamination in the final nickel whilst sulfur is oxidized to sulfate, sulfamate and unsaturated
product and to remove sulfamate, which is a herbicide and sulfur compounds such as trithionate, thiosulfate etc (Forward
would not be permissible in the final ammonium sulfate by- 1953; Forward and Mackiw 1955). Iron present in the concen­
product if used as a fertilizer (Wishaw 1993). The final pro­ trate is oxidized and precipitates as a hydrous ferric oxide
ducts from the Sherritt-Gordon process are metallic nickel residue (Forward and Mackiw 1955). Copper is removed
powder or briquettes, cobalt metal powder, briquette or sulfide from the leach liquor by precipitation as its sulfide by reaction
precipitate, and ammonium sulfate (Forward 1953; Wishaw with unsaturated sulfur compounds present in the liquor
1993). (Forward 1953; Forward and Mackiw 1955). An interesting
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 11

Figure 3. Simplified process flowsheet of the Sherritt-Gordon ammonia pressure leach process for leaching of Ni sulfide concentrates and recovery of Ni via pressure
hydrogen reduction; refining of the mixed sulfide precipitate has been omitted. Typical operating conditions of some unit operations in the Sherritt-Gordon process are
presented along with overall metal recoveries during processing of a nickel concentrate grading 10–14% Ni. Adapted from Forward (1953), Forward and Mackiw (1955),
Kerfoot and Cordingley (1997) and Wishaw (1993).

feature of the Sherritt-Gordon ammonia leach process is con­ Metallic Ni powder is produced via hydrogen reduction of
trol of the degree of sulfur oxidation in the autoclaves to ensure the copper-free solution in an autoclave at elevated tempera­
there is sufficient unsaturated sulfur compounds present in the ture and pressure and the resultant powder is briquetted
liquor for subsequent copper sulfide precipitation. Following (Forward 1953; Forward and Mackiw 1955). The solution
on from copper precipitation, further removal of residual from Ni reduction is treated with H2S to precipitate Ni and
unsaturated sulfur compounds and sulfamate in the Ni-Co Co as a mixed sulfide precipitate (MSP) and the barren solution
leach liquor is carried out by boiling in an autoclave is then processed further to recover ammonium sulfate as a by-
(Forward 1953; Forward and Mackiw 1955). The process product (Forward 1953; Forward and Mackiw 1955; Mackiw
chemistry of the copper removal and oxydrolysis stages are et al. 1958). The MSP product is further processed in a cobalt
discussed in detail by Forward (1953) and Forward and refinery, the main process steps of which are depicted in
Mackiw (1955). Figure 4; leaching is carried out via sulfuric acid pressure

Figure 4. Cobalt recovery from mixed sulfide precipitate (MSP) as originally practiced at Fort Saskatchewan (Canada) prior to 1990. Adapted from Forward (1953) and
Mackiw et al. (1958).
12 N. FARIS ET AL.

oxidation in an autoclave at 121°C and pressure of 790 kPa were stated to be higher Ni tenors in the leach liquor, an
(absolute) using air as an oxidant (Mackiw et al. 1958). The increase in Ni throughput, reduced cooling requirements in
leach solution is purified to remove dissolved iron by adjusting the autoclaves due to the lower sulfur content of the matte feed,
the pH to 4.9–5.1 using ammonia and sparging air to oxidize and generation of a smaller volume of leach residue (Deng
any ferrous iron to the ferric state (Mackiw et al. 1958). After 1993, 1994; Wishaw 1993). The operating conditions of the
iron removal, solid ammonium sulfate is added to increase the autoclave train at the Kwinana refinery processing flash fur­
concentration of (NH4)2SO4 in solution to the level required nace smelter matte grading 66 wt% Ni (ground to a P90 of 106
for cobalt reduction, and to remove Ni from solution as nickel µm), are a temperature range of 85–95°C and a pressure of
ammonium sulfate which is recycled to the nickel reduction 750–1000 kPa using compressed air as the oxidant (Wishaw
circuit (Forward 1953; Mackiw et al. 1958). Cobalt is recovered 1993; Woodward 2014; Woodward and Bahri 2007). The Ni-
from solution by hydrogen reduction at elevated temperature Cu-Corich ammoniacal solution is processed in a similar man­
and pressure in an autoclave to form cobalt powder (Mackiw ner to the original Sherritt-Gordon process at Fort
et al. 1958). Saskatchewan which was previously described (refer to
The refinery at Fort Saskatchewan has undergone significant Figure 3). The primary difference is that further processing of
modifications to the leaching and cobalt refining circuit due to the MSP product for recovery of cobalt values does not take
changes in the feed, with the refinery switching over to the place (Wishaw 1993). The refinery at Kwinana has undergone
processing of MSP from Moa Bay, Cuba. The MSP grades 55 wt an expansion with the addition of a plant to produce 100,000
% Ni and contains high concentrations of cobalt (5 wt%) and tonnes per annum of nickel sulfate (Anon, 2021) , a key ingre­
could not be processed satisfactorily in the original refinery dient in LIB cathodes used in electric vehicles.
(Kerfoot and Cordingley 1997). Mixed sulfide precipitate from
Moa Bay comprises 80% of the feed to the refinery, the balance
3.2. Sulfuric acid pressure oxidation processes
being nickel matte and nickel sulfate by-product from copper
refineries (Kerfoot and Cordingley 1997). Nickel and cobalt are Sulfuric acid pressure oxidation processes have been commer­
dissolved from the MSP by pressure leaching in aqueous cially employed since the 1980s for processing of Ni-Cu mattes,
ammonia using air as an oxidant; nickel matte (70 wt% Ni) is zinc concentrates and refractory gold concentrates
dissolved in a separate autoclave train also via ammonia pres­ (Berezowsky et al. 1991) and have seen limited use in the
sure leaching (Kerfoot and Cordingley 1997). The combined processing of nickel sulfide concentrates. The sulfuric acid
Ni-Co leach liquor is subjected to Ni-Co separation by pre­ required for oxygen pressure leaching can be introduced
cipitating cobalt as a Co(III) hexamine salt, which has a low through recycling of raffinates from solvent extraction-
solubility in saturated ammoniacal solution, through the addi­ electrowinning circuits and/or can be generated in-situ during
tion of anhydrous ammonia (Kerfoot and Cordingley 1997). leaching from hydrolysis of ferric iron and oxidation of part or
The Ni-rich solution is processed in the exact same sequence of all the elemental sulfur. Oxygen pressure leaching processes are
operations previously described i.e. copper sulfide precipita­ characterized according to the operating temperature at which
tion, oxydrolysis and hydrogen reduction (Kerfoot and leaching is performed which has an effect on sulfur speciation
Cordingley 1997). Copper sulfide precipitation is however and oxygen consumption during leaching; low-temperature
achieved through the addition of elemental sulfur and SO2, oxidation (100–110°C) takes place below the melting point of
rather than relying on unsaturated sulfur compounds present elemental sulfur (113–119°C), intermediate temperature oxi­
in the leach liquor (Kerfoot and Cordingley 1997). The cobalt­ dation (120–180°C) takes place above the melting point of
(III) hexamine sulfate is processed in a separate circuit which elemental sulfur but below a temperature at which majority
involves repulping in water to dissolve any precipitated nickel of the sulfur is further oxidized to sulfate whilst high-
hexamine sulfate; the purified cobalt(III) hexamine sulfate is temperature pressure oxidation is typically carried out at
re-dissolved in ammonium sulfate solution followed by Co(III) 180–220°C where sulfur is fully oxidized to sulfate
reduction to Co(II) using metallic cobalt powder and finally (Berezowsky 2000; Honey, Muir, and Hunt 1997). Further
hydrogen reduction in an autoclave at high temperature and details of the process chemistry during oxygen pressure leach­
pressure to produce high-grade metallic cobalt powder ing of nickel sulfide concentrates are discussed by Berezowsky
(Kerfoot and Cordingley 1997). A portion of this metallic (2000). Sulfuric acid pressure oxidation processes for the treat­
cobalt powder is recycled to the Co(III) reduction stage with ment of nickel flotation concentrates are by far the most
the balance being briquetted (Kerfoot and Cordingley 1997). numerous and advanced with respect to pilot plant develop­
ment and commercial deployment. The key features of the
3.1.2. Kwinana, Western Australia piloted processes are presented in Table 5. Several nickel pro­
The Sherritt-Gordon ammonia pressure leach process is cessing operations have practiced pressure oxidation which are
employed at BHP Nickel West’s refinery in Kwinana, WA presented in Table 4. Two of these operations have been closed
(formerly owned by WMC Resources) and was originally (Fredericktown and Garfield, both in the USA) but have been
built to process nickel flotation concentrates from Kambalda. briefly described for historical purposes.
The plant was commissioned in 1970, however, with the com­
missioning of the Kalgoorlie nickel smelter in 1973, co- 3.2.1. Piloted pressure leach processes
processing of matte and concentrate commenced, with the 3.2.1.2 Activox®. The Activox® process was originally devel­
refinery switching to an all-matte feed in 1985 (Deng 1994; oped by Western Minerals Technology (WMT) for oxidative
Wishaw 1993). Some advantages of switching to all matte feed leaching of base metal sulfide concentrates (Johnson, Evans,
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 13

and Turner 2000) and has also been applied to treatment of processing of nickel sulfide concentrates (Jones, Hestrin, and
refractory gold ores (Corrans, Johnson, and Angove 1993). The Moore 1998). The CESL process is a medium temperature
Activox® process is essentially a low temperature (80–110°C), pressure oxidation process taking place under an oxygen pres­
pressure oxidation process utilizing oxygen gas as the oxidant, sure of 1379 kPa (gauge) and temperature above the melting
whereby base metals are leached from the concentrate whilst point of sulfur (120°C) but below 160°C to limit oxidation of
sulfide is oxidized to elemental sulfur, thus reducing the oxy­ elemental sulfur to sulfate. The first step in the CESL process is
gen requirement for leaching versus high temperature, high re-grinding of flotation concentrate(s) in a ball mill to a P95 of
pressure oxidation processes (Corrans, Johnson, and Angove 45 µm to liberate the sulfide minerals and improve leaching
1993; Johnson, Evans, and Turner 2000). Elemental sulfur kinetics (Jones, Hestrin, and Moore 1998; Mayhew et al. 2013).
reports to the leach residue and since the leaching process Oxidative dissolution of concentrates takes place in an acidic
operates below the melting point of sulfur (approximately sulfate solution containing up to 60 g/L H2SO4, 12 g/L chloride
120°C), there is no need for the addition of a sulfur dispersing and 5–10 g/L Cu(II), the role of chloride being to limit oxida­
agent during leaching. The leaching media is an acid-sulfate tion of elemental sulfur to sulfate (Jones, 1996; Jones, Hestrin,
system, with the sulfuric acid being generated in situ by oxida­ and Moore 1998). Brown and Papangelakis (2005) have also
tion of sulfide minerals in the feed (Johnson, Evans, and shown that chloride ions have a dispersing effect on elemental
Turner 2000). The concentrate to be leached is subjected to sulfur and it is possible that chloride in the CESL process serves
ultra-fine milling down to a P80 of 10 µm, thereby improving an additional function as a sulfur dispersing agent during
leaching kinetics in subsequent pressure oxidation (Corrans, leaching. In the absence of any suitable sulfur dispersing
Johnson, and Angove 1993; Johnson, Evans, and Turner 2000; agent, sulfide mineral dissolution kinetics would likely be
Palmer and Johnson 2005). Chloride addition during Activox® inhibited due to encapsulation of unreacted sulfides by molten
leaching has been stated to be beneficial for copper extraction elemental sulfur (Brown and Papangelakis 2005; Tong and
(Adams and Johnson 2001) which is consistent with the find­ Dreisinger 2009). The specific role of copper ions in the
ings by Subramanian and Ferrajuolo 1976) and McDonald and CESL process is not stated, however WMC Resources pre­
Muir (2007). Typical residence times for leaching nickel sulfide viously recognized the benefits of copper ions in combination
concentrates are reported to be 1–2 hours (Johnson, Evans, and with chloride during pressure oxidation of nickel sulfide con­
Turner 2000), chalcopyrite being refractory requires longer centrates which formed the basis for a patent (Crossley et al.
times (up to 5 hours) (Corrans, Johnson, and Angove 1993). 1998). It may be that in the presence of sufficient chloride ions
Precious metals are not leached in the process and report to the in solution, the Cu(II)/Cu(I) couple functions as a redox med­
leach residue from which they are recovered by conventional iator during oxygen pressure leaching. Iron sulfides in the
means (Johnson, Evans, and Turner 2000; Palmer and Johnson concentrate(s) are oxidized and precipitated as hematite; in
2005). Iron is initially leached from the concentrate but under­ the case of pyrrhotite, oxidation also produces elemental sulfur
goes hydrolytic precipitation, forming goethite and hematite whilst sulfide in pyrite is oxidized to sulfuric acid (Defreyne
(Corrans, Johnson, and Angove 1993; Palmer and Johnson et al. 2006). Whilst only 50% to 75% of the pyrite is reported to
2005). There is no guarantee of goethite formation and the undergo oxidation in the CESL process, its presence in con­
study by McDonald and Muir (2007) on chalcopyrite leaching centrates is stated to be undesirable as it increases oxygen
under Activox® conditions (108°C 700 kPa O2 pressure) found consumption and heat generation during pressure oxidation
that goethite formation only occurred during leaching with 10 and generates sulfuric acid which must be neutralized down­
g/L Cl−. Leaching with sulfuric acid and chloride resulted in stream (Defreyne et al. 2006). The heat generation due to pyrite
formation of natrojarosite and poorly crystalline iron oxyhydr­ oxidation may not be an issue if the process can be operated
oxides such as 2-line ferrihydrite (McDonald and Muir 2007). autogenously whilst the acid generation from pyrite might also
Metal recoveries during the leaching of a range of sulfide not be a problem if a use can be found for the acid such as in
concentrates using the Activox® process have been reported a heap leach operation.
to be greater than 95% for Ni and Co, and 75–90% for Cu, with Once the base metals have been leached into solution, the
40–80% conversion of sulfidic sulfur to elemental sulfur autoclave leach slurry is subjected to solid–liquid separation
(Palmer and Johnson 2005). Activox® leaching technology has and the leach liquor is neutralized with limestone to remove
been applied to the treatment of a variety of nickel sulfide iron and aluminum from solution (Jones et al. 2010; Mayhew
concentrates from Western Australia and Africa (Corrans, et al. 2013). Copper can be recovered as cathode via solvent
Johnson, and Angove 1993; Johnson, Evans, and Turner extraction and electrowinning (SX-EW) whilst Ni and Co can
2000), and was the chosen leaching technology for the be recovered as a mixed hydroxide precipitate (MHP), mixed
Yakabindie Nickel Project, Western Australia, and the Tati sulfide precipitate (MSP), or separated via SX to produce
nickel project, Botswana (Johnson, Evans, and Turner 2000; individual products (Jones et al. 2010; Jones, Mayhew, and
Palmer and Johnson 2005; Robles, Cronje, and Nel 2009). The O’Conner 2009; Mayhew et al. 2013). The CESL process has
technology has not been applied commercially for the proces­ been tested on a range of nickel concentrates ranging in Ni
sing of nickel flotation concentrates. grade from 2.1 to 20.4 wt% at bench and pilot plant scale,
including concentrates high in MgO arising from the flotation
3.2.1.2. CESL process. The CESL process was originally of disseminated Ni sulfide ores which are not suitable for
developed by Cominco (now Teck Resources Limited) for the smelting (Jones et al. 2010; Jones, Hestrin, and Moore 1998;
hydrometallurgical processing of copper sulfide concentrates, Jones, Mayhew, and O’Conner 2009; Mayhew et al. 2013). High
as an alternative to smelting, but was also adapted for the Ni and Co recoveries have been reported for a range of
14 N. FARIS ET AL.

concentrates leached using the CESL process, being above 95% from flotation concentrates as an alternative to smelting.
for both elements (Jones, Hestrin, and Moore 1998; Jones, The first stage in the Kell Process is high-temperature
Mayhew, and O’Conner 2009). Despite being tested at bench pressure oxidation (170–230°C) in a sulfate medium
and pilot plant scale, the CESL process has not been deployed using oxygen gas to dissolve base metals and oxidize
commercially for the processing of nickel sulfide concentrates. sulfidic sulfur to sulfate; precious and platinum group
metals are retained in the leach residue (Liddell and
3.2.1.3. PlatsolTM. PLATSOLTM leaching technology was ori­ Adams 2012; Liddell et al. 2019). By comparison, PGMs
ginally developed by International PGM Technologies Limited are intentionally dissolved in the PLATSOLTM process,
at SGS Lakefield Research (Canada) for processing bulk poly­ also utilizing high-temperature pressure oxidation, via
metallic sulfide flotation concentrates containing Cu, Ni, Co, the addition of 5–20 g/L NaCl. The leach liquor arising
gold (Au) and PGMs from the NorthMet deposit (Duluth from the pressure leaching stage (Kell process) is pro­
Gabbro, Minnesota), owned by Polymet Mining Corporation cessed to recover base metals whilst the leach residue is
(Dreisinger et al. 2005; Ferron et al. 2002; Fleming et al. 2000). further processed to recover Au, Ag and PGMs (Liddell
The bulk sulfide concentrates were considered uneconomical and Adams 2012; Liddell et al. 2019). The leach residue
for smelting and hence a hydrometallurgical process was an may be subjected to a HCl leach at ambient pressure to
attractive alternative to development of a dedicated smelting dissolve silver and residual base metals retained in the
facility or shipping flotation concentrate to toll smelters residue followed by roasting of the residue at 500–
(Fleming et al. 2000). The leaching technology was also tested 1000°C to convert PGM minerals to a readily leachable
on a range of different base metal sulfide concentrates contain­ form (Liddell et al. 2019). Test work performed by Adams,
ing a range of Ni grades from 3 to 15 wt% as well as Co, Cu and Liddell, and Holohan (2011) found that reducing condi­
PGMs (Ferron et al. 2000, 2002; Fleming et al. 2000). The tions during roasting are ideal for subsequent PGM recov­
leaching process is essentially a high-temperature pressure ery. Recovery of precious and platinum group metals from
oxidation process carried out at 225°C utilizing oxygen gas as the roasted leach residue takes place via an ambient pres­
the oxidant in sulfuric acid media containing dissolved chlor­ sure oxidative leach in a chloride medium using chlorine
ide (Dreisinger et al. 2005; Ferron and Fleming 2001); base and gas as an oxidant (Liddell et al. 2019). The process has
precious metals are dissolved from concentrates under the been tested on a range of PGM bearing sulfide concen­
conditions employed and total oxidation of sulfidic sulfur to trates, primarily from Southern Africa and average base
sulfate takes place (Fleming et al. 2000). Most of the iron metals (Ni, Cu, Co) recoveries are 96–98% whilst Pt and
(>90%) in the concentrate reports to the leach residue as Pd recoveries are 98% (Liddell et al. 2019).
hematite (Ferron et al. 2000; Fleming et al. 2000). Key features
of the process are the addition of an ultra-fine milling stage 3.2.1.5. IGO processTM. IGO Limited, an ASX listed nickel
(P80 15–20 µm) and chloride addition (5–20 g/L NaCl) which miner, has recently patented a process for production of
facilitates dissolution of Au and PGMs during leaching via high purity/battery grade nickel sulfate directly from nickel
formation of soluble chloro complexes (Ferron et al. 2000; sulfide concentrates via oxygen pressure leaching, solution
Fleming et al. 2000). Base metals recovery during leaching neutralization and purification, and solvent extraction to
was reported to be unaffected by fine grinding or chloride produce nickel sulfate hydrate crystals (Grassi et al. 2019).
addition, however recoveries of Au, Pt and Pd were improved The main feature of the invention is the stripping of nickel
both when ultra-fine milling and chloride addition were from the loaded organic phase using a sulfuric acid solution
employed (Fleming et al. 2000). Gold recoveries during leach­ saturated in Ni such that nickel sulfate hexahydrate crystals
ing were also reportedly affected by the grinding media, with are immediately precipitated from solution (Grassi et al.
ceramic media giving the best results during leaching versus 2019). Nickel dissolution from the concentrate is proposed
steel grinding media, which was believed to be due to cementa­ to take place either via low temperature (100 – 120°C) or
tion of dissolved gold onto iron powder produced during high temperature (>200°C) pressure oxygen leaching. For the
attrition grinding using steel media (Fleming et al. 2000). At former case, ultra-fine grinding (P80 6.6 µm) improved nickel
the high temperatures employed, leaching kinetics were very leaching from the concentrate (Grassi et al. 2019) just like in
rapid with more than 95% of the Ni, Cu and Co being leached Activox®. Grassi et al. (2019) reported near complete extrac­
from concentrates in the first 20 minutes with longer retention tion of base metals within 60 min during high-temperature
times (up to 180 min) being necessary to dissolve the precious pressure leaching; however, the resultant leach liquors con­
metals (Dreisinger et al. 2005; Ferron and Fleming 2002; tained high concentrations of dissolved iron (up to 22 g/L
Ferron et al. 2000). A demonstration plant utilizing total Fe, mostly as Fe(III)) and free acid (up to 78 g/L H2
PLATSOLTM leaching technology was built at SGS Lakefield SO4) which would increase limestone consumption in down­
for processing bulk sulfide flotation concentrate produced stream neutralization. The high iron and acid concentrations
from the NorthMet deposit (Ferron and Fleming 2001, 2002); in the leach liquor is not necessarily an issue if a use can be
however, the leaching technology does not appear to have been found for them, such as leaching nickel sulfide flotation
industrially implemented. tailings or nickel oxide ores, though this is not mentioned
in the invention. The IGO ProcessTM has not been commer­
3.2.1.4. Kell process. The Kell process is a multi-step cially deployed; however, IGO Limited has indicated that
hydrometallurgical process that has been developed for they are assessing opportunities for partnership/collaboration
the extraction of base metals, gold, silver and PGMs to leverage the technology (IGO Limited 2020).
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 15

3.2.2. Commercial operations grade, high magnesia (10% MgO) nickel sulfide flotation con­
3.2.2.1. Garfield Cobalt Refinery, USA. The Garfield cobalt centrate from the Hitura mine (Finland) grading 5–7% Ni. The
refinery in Utah, USA, operated by Calera Mining Company plant used a pressure oxidation process (HIKO process – refer
was the first application of sulfuric acid pressure oxidation to to Table 5) in autoclaves at temperatures below the melting
the processing of nickel-bearing sulfides (Berezowsky 2000). point of sulfur (<120°C) with oxygen gas at 500 kPa pressure
The plant was operational from 1953 to 1959 and shut down (Berezowsky 2000; Nyman et al. 1992). Additional details of the
due to a shortage of ore (Meddings and Evans 1971). The plant HIKO process such as acid addition to the leach charge, con­
processed a sulfide concentrate from the Blackbird Mine in centrate feed particle size, leaching time and degree of sulfide
Idaho (USA) grading 17.5% Co, 1.0% Ni and 0.5% Cu; major conversion to elemental sulfur are unknown (Berezowsky
sulfide minerals in the concentrate were cobaltite (CoAsS) and 2000). The leach solution was subjected to iron precipitation
pyrite with minor gersdorffite, chalcopyrite and arsenopyrite using limestone followed by copper precipitation as a sulfide
(Berezowsky 2000). The pressure leaching process in use at the using H2S (Nyman et al. 1992). Following on from iron and
refinery involved total pressure oxidation at 375°F (190.6°C) copper removal, the solution was subjected to SX using di-
and a total pressure of 3600 kPa using air as the oxidant in 2-ethylhexyl phosphoric acid (D2EHPA) to remove calcium
a lead and brick lined autoclave (Berezowsky 2000). Under followed by separation of cobalt (and magnesium) from nickel
these conditions, 95–97% of the Co was leached (Berezowsky using Ionquest 801, an organophosphorus-based extractant
2000); the extraction efficiencies for Ni and Cu have not been (Nyman et al. 1992). The raffinate from Co/Mg SX was then
stated. Majority of the iron and arsenic in the concentrate was sent to Ni SX; the final products were purified Ni and Co
precipitated as basic iron sulfate and ferric arsenate (Meddings chemicals (Nyman et al. 1992); no details however are given
and Evans 1971). The leach slurry from the autoclave was of the Ni SX circuit i.e. type of extractant used, nor the Co
neutralized to remove residual arsenic and iron, and copper refining circuit after Co/Mg SX. The status of the pressure
was recovered by cementation with cobalt powder (Meddings leaching plant is unknown though the refinery has changed
and Evans 1971). Cobalt and Ni recovery was via pressure ownership a number of times and is currently a cobalt refinery
hydrogen reduction to produce an impure product after operated by Umicore (Cooke 2021; Törmänen and Tuomela
adjustment of the solution with ammonia to produce the 2021) and the nickel mine that supplied concentrate to the
desired ammonia to metal ratio in solution (molar ratio of 2) leaching plant has been closed since 2015 (Björkman 2019).
for reduction (Meddings and Evans 1971). Construction and A simplified process flow diagram of the HIKO process used at
operation of the plant was rushed, and no piloting of the the Kokkola refinery is presented in Figure 5.
process occurred, as such the plant was plagued with numerous
issues due to the abrasive and corrosive nature of the slurry 3.2.2.4. Long Harbour, Canada. Hydrometallurgical proces­
(Berezowsky 2000). sing of nickel flotation concentrate is carried out by Vale
Limited at Long Harbor using nickel concentrate produced
3.2.2.2. Fredericktown metals refinery, USA. The from the Voisey’s Bay nickel deposit; the first shipment of
Fredericktown refinery in Missouri, USA, operated by metallic nickel produced from the plant occurring in 2015
National Lead Company was the second commercial plant to (Anon 2015). A simplified flowsheet of the Voisey’s Bay
utilize sulfuric acid pressure oxidation in the processing of Process is presented in Figure 6 and the key features of the
nickel-bearing sulfide concentrates (Berezowsky 2000). The leaching stages are summarized in Table 5. The process com­
plant was operational between 1954 and 1960 and like the mences with regrinding of the flotation concentrate to below
Garfield refinery was closed due to lack of feed (Meddings 20 µm followed by a first stage leach in sulfuric acid (return
and Evans 1971). The feed to the leach plant was a flotation electrolyte from Ni-electrowinning) at ambient pressure using
concentrate grading 5.0% Ni, 4.2% Co and 4.8% Cu, as siegen­ a mixture of chlorine gas and oxygen as the oxidant (produced
ite and chalcopyrite, produced as a by-product of copper-lead from the Ni-electrowinning circuit). This is followed by
mining (Berezowsky 2000; Meddings and Evans 1971). The a second stage leach at elevated pressure using oxygen as the
pressure leaching process in use at the refinery involved total oxidant in an autoclave (Crundwell et al. 2011b; Kerfoot et al.
pressure oxidation at 232°C and a total pressure of 5300 kPa 2001; Stevens et al. 2009). The clarified leach solution produced
using air as the oxidant (Berezowsky 2000). Most of the iron from the two-stage leach process undergoes a first stage of iron
was precipitated in the autoclave as basic iron sulfate and removal where 95% of the iron is removed by raising the pH to
further removal of iron post-pressure leaching took place 3 using limestone and aerating with oxygen to oxidize any
through pH adjustment and aeration to oxidize residual fer­ ferrous iron in the solution to the ferric state (Stevens et al.
rous iron (Meddings and Evans 1971). Metallic Ni, Cu and Co 2009). Following on from the first iron removal stage, copper is
products were recovered by pressure hydrogen reduction recovered from the solution via solvent extraction-
(Meddings and Evans 1971). electrowinning (SX-EW) using LIX 84, a commercially avail­
able hydroxyoxime extractant (Stevens et al. 2009). The raffi­
3.2.2.3. Kokkola refinery, Finland. There has been a long nate from Cu SX undergoes a second stage of iron removal,
history of Ni/Co refining at Kokkola by Outokumpu Oy, start­ followed by cadmium removal (by sulfide precipitation) and
ing with Ni and Co extraction from pyrite-pyrrhotite concen­ finally an impurity SX stage using D2EHPA to remove calcium,
trate from the Outokumpu copper mine via sulfation roasting magnesium and other impurities (Fe, Pb, Zn, Mn) prior to
between 1966 and 1987 (refer to Section 3.6.3). From cobalt solvent extraction (Crundwell et al. 2011b; Stevens et al.
December 1991, the Kokkola refinery began processing a low 2009). The purified raffinate is then subjected to Co SX-EW
16 N. FARIS ET AL.

Figure 5. Simplified process flow diagram of the Outokumpu HIKO process used at the Kokkola refinery (Finland) for processing of nickel sulfide concentrates via low
temperature pressure oxidation and recovery of nickel and cobalt chemicals. Operating conditions of the leaching process and metal extractions during leaching for
a given nickel concentrate are presented. Adapted from Nyman et al. (1992) Honey, Muir, and Hunt (1997) and Berezowsky (2000).

Figure 6. Simplified process flow diagram for the hydrometallurgical processing of nickel concentrate from Voisey’s Bay (Canada) at Vale’s Long Harbour operations to
produce Ni, Cu and Co cathode via a combination of pressure oxidation, solvent extraction (SX) and electrowinning (EW). Some unit operations such as hydroxide re-
leaching after solid/liquid separation and cadmium removal prior to impurity SX have been omitted for simplicity. Adapted from Crundwell et al. (2011b), Kerfoot et al.
(2001) and Stevens et al. (2009). Conditions utilized in atmospheric pre-leach and pressure oxidation and extraction efficiencies are based on the original patent filed by
Kerfoot et al. (2001) and may not reflect actual conditions in current use.

using Cyanex 272, an organophosphinic acid extractant. The Deng 1992, 1993; Klyushnikov et al. 2021). Nickeliferous pyr­
raffinate from Co SX is sent to the Ni electrowinning circuit; rhotite concentrates are processed to recover the base and
the final products produced at Long Harbor are nickel cathode, platinum group metals content via a combination of autoclave
copper cathode and cobalt rounds (Crundwell et al. 2011b; pressure leaching and residue flotation at the Nadezhdin mill,
Stevens et al. 2009). operated by Noril’sk Mining and Metallurgy Corporation (now
Nornickel) (Deng 1992, 1993). The autoclaves were commis­
3.2.2.5. Nadezhdin mill, Russia. Flotation of massive sulfide sioned in 1979 and involved leaching pyrrhotite concentrates
ores from the Noril’sk-Talnakh ore field (Siberia) produces at 125–135°C and pressure of 1.5 MPa, using 80% O2 as the
three products, copper concentrate, nickel concentrate and oxidant with addition of 4 kg/t of lignin sulfonic acid salts as
pyrrhotite concentrate (Bulatovic 2007; Kozyrev et al. 2002). a sulfur dispersing agent (Berezowsky 2000; Deng 1992, 1993).
The pyrrhotite concentrates produced typically contain 2–5% The leaching process results in oxidation of 96% of the pyr­
Ni, 1–4% Cu and up to 15 g/t of PGMs (Berezowsky 2000; rhotite in the concentrate and conversion of 65% of sulfidic
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 17

sulfur in the feed to elemental sulfur; 67% of the Ni is initially 3.3. Atmospheric sulfuric acid leaching
leached into solution but is subsequently precipitated from the
The only processes developed to date employing chemical leach­
leached slurry as a sulfide (Deng 1992, 1993). Precipitation of
ing of nickel concentrates in a sulfate medium at atmospheric
dissolved base metals is carried out by treating the leach pulp
pressure are the Intec Nickel Process developed by Intec Limited,
with metallic iron at 90°C which together with elemental sulfur
and the Albion ProcessTM developed by Glencore (formerly
present in the leach slurry precipitates the dissolved metals as
Xstrata). Neither of these processes have been deployed commer­
their sulfides (Berezowsky 2000).
cially for the processing of nickel sulfide concentrates though the
The precipitated base metal sulfides along with Albion ProcessTM has been commercially deployed for processing
unreacted sulfides and PGMs are separated from elemental gold, copper and zinc concentrates and may therefore be suitable
sulfur and iron oxides via sequential flotation (Deng 1992, for leaching of nickel flotation concentrates. The key features of
1993). Firstly, flotation is carried out to reject iron oxides both processes are presented in Table 5 and are briefly described
formed during pressure oxidation and recover an elemen­ below.
tal sulfur-metal sulfide flotation concentrate (Berezowsky
2000). The concentrate is then treated in an autoclave at 3.3.1. Intec Nickel Process
110–130°C and pH 9–10 with addition of 5–7 g/L Na2S to The Intec Nickel Process is a two-stage atmospheric leaching
disintegrate the concentrate into a mixture of elemental process developed for processing base metal sulfide concen­
sulfur and metal sulfides; the pulp is then subjected to trates containing precious metals and PGMs. Much of the
flotation to produce a sulfide concentrate and an elemental development work for the Intec Process focused on copper
sulfur product (Berezowsky 2000). The final nickel grade extraction from copper sulfide concentrates (Moyes and
in the concentrate is 8–10% with an overall recovery of Houlis 2003; Palmer and Johnson 2005). The first stage leach
base and platinum group metals to the final concentrate of involves carrying out oxidative dissolution of reground flota­
80–85% (Berezowsky 2000). The base and platinum group tion concentrate (ground to P80 25 µm) at 80°C in a sulfuric
metal enriched product is then combined with the nickel acid solution containing halides (Cl-, Br-) using air (21% O2) as
concentrate produced from the beneficiation circuit and an oxidant (Moyes and Houlis 2003). Nickel, copper and cobalt
processed further via flash smelting (Berezowsky 2000; dissolution efficiencies in the first leaching stage were reported
Klyushnikov et al. 2021). A simplified process flow dia­ to be greater than 95%, with approximately 50% of the Au and
gram is presented in Figure 7. The pressure oxidation PGMs dissolving in this leaching stage (Moyes and Houlis
autoclaves at the Nadezhdin mill do not have sufficient 2003); the residence time for the first leaching stage was not
capacity to process all the nickeliferous pyrrhotite concen­ stated. The second leaching stage, termed the “Halex leach”,
trate produced and as such, a large proportion of the involves the extraction of un-leached Au, Pt, Pd and remaining
concentrate is diverted to stockpile (Klyushnikov et al. base metals from the first stage leach residue. Leaching is
2021; Moskalyk and Alfantazi 2002). carried out at 100°C using spent electrolyte from the Cu- and

Figure 7. Simplified process flow diagram for the hydrometallurgical processing of nickeliferous pyrrhotite concentrates from Talnakh (Russia) at the Nadezhdin mill via
a combination of pressure oxidation, non-ferrous metal sulfide precipitation and flotation to recover a sulfide concentrate for flash smelting and elemental sulfur.
Operating conditions of major unit operations and overall nickel recovery and final nickel product grade during processing of a pyrrhotite concentrate grading 2.2% Ni
are presented (from Berezowsky 2000). Adapted from Kitay, Mechev, and Volkov (1991) and Berezowsky (2000).
18 N. FARIS ET AL.

Ni-electrowinning circuits, where electrogenerated BrCl2- halide ions such as in the CESL, Voisey’s Bay or Intec
serves as the oxidant (Moyes and Houlis 2003). Base metal processes which were previously described. Advantages of
recoveries in the second stage leach were again reported to be chloride lixiviants have been stated to be a high recovery of
greater than 95%, with 86% of the Au, and 87% of the Pd also metals during leaching, ability to regenerate and recycle the
being leached; Pt recoveries were poor however with only 54% lixiviants, inertness of pyrite in chloride media and reduced
extraction (Moyes and Houlis 2003). Recovery of precious formation of sulfate during leaching (Dutrizac 1992).
metals post-leaching is by precipitation using either sodium Against these advantages however are several limitations
hydrogen sulfide (NaHS) or pyrrhotite-rich nickel concentrate, such as the lack of selectivity of chloride lixiviants during
and copper and nickel are recovered in separate electro- leaching which can complicate downstream liquor purifica­
winning circuits as cathode. tion and lixiviant regeneration/recycling and the corrosivity
of chlorides toward many common materials of construc­
3.3.2. Albion ProcessTM tion (Dutrizac 1992; Forward and Warren 1960; Honey,
The Albion ProcessTM is an atmospheric oxidative leaching Muir, and Hunt 1997). Despite the disadvantages, chloride-
process which is preceded by an ultra-fine grinding stage. based leaching processes have been successfully utilized for
The process was developed to treat a range of sulfide concen­ processing nickel mattes with these processes in current use
trates containing base and precious metals and was originally at the Falconbridge Nikkelverk refinery (Norway), the
developed by MIM Holdings/Xstrata (Hourn and Turner 2012; Niihama nickel refinery (Japan) and Sandouville-Le Havre
Hourn, Turner, and Holzberger 1996) with Glencore (France) (Kerfoot and Weir 1988; Makino et al. 1996;
Technology (a subsidiary of Glencore) being the licensor of Stensholt, Zachariasen, and Lund 1986). A common theme
the process/technology after the purchase of Xstrata. The ori­ to all three matte leach processes is the use of chlorine gas
ginal patent for the Albion ProcessTM covered the ultra-fine as an oxidant in conjunction with either Cu(II)
grinding of base metal sulfide concentrate or ore to a P80 of 20 (Falconbridge, Niihama) or Fe(III) (Sandouville) (Muir
µm or less followed by leaching in a sulfuric acid medium and Ho 2006).
containing dissolved ferric and ferrous iron with sparging of Despite the successful application of chloride leaching in
air, oxygen-enriched air or pure oxygen at temperatures nickel matte refining, the only chloride-based leaching pro­
between 60°C and the boiling point of the solution (Hourn, cess developed at scale for processing nickel sulfide concen­
Turner and Holzberger 1996). The first step in the Albion trates is the HydroNic process developed by Outotec Oyj
ProcessTM is the fine grinding of the sulfide-bearing material (Karonen, Tiihonen, and Haavanlammi 2009) and key details
in an IsaMillTM to a P80 of 10–12 µm followed by leaching of of the process are summarized in Table 5. HydroNic
the milled material in specially designed agitated leaching tanks employs a two-stage leaching process to dissolve Ni, Co
at 93–98°C with oxygen injection using Hypersparge™ technol­ and Cu from base metal sulfide concentrates. In the first
ogy which can deliver oxygen at supersonic velocities (450– stage, nickel is leached from pentlandite by reaction with
550 m.s−1) (Hourn and Turner 2012). No external heating or copper(II) chloride dissolved in a sodium chloride solution
cooling requirements are required for the leaching process, the recycled from the second leach stage, with Ni and Fe being
heat being generated from oxidation of sulfidic sulfur and leached into solution (as their chlorides) whilst copper is
cooling being achieved via water evaporation. Sulfidic sulfur precipitated as copper(I) sulfide (Cu2S). This leaching stage
is oxidized to elemental sulfur and sulfate, with the degree of is non-oxidative and is a cementation process. In the second
elemental sulfur oxidation to sulfate being controlled by the stage of leaching, the concentrate is leached under oxidative
pulp pH. Processing of base metal sulfide concentrate via the conditions using oxygen or chlorine gas as the oxidant. Iron
Albion ProcessTM is carried out under acidic conditions whilst is hydrolyzed and precipitated from solution during leaching
the processing of refractory gold concentrates is carried out whilst sulfide in the concentrate is oxidized to elemental
under neutral conditions (pH 5–7) to oxidize elemental sulfur sulfur and sulfate. The solution from the second leaching
to sulfate. The Albion ProcessTM has been commercially stage is recycled to the first stage to remove copper from
deployed for the processing of sphalerite, refractory gold con­ solution via cementation as Cu2S. After copper removal, the
centrates (Hourn and Turner 2012) and most recently, chalco­ solution is treated further with caustic (NaOH) and lime­
pyrite concentrate at Sable Zinc (Zambia) (Stieper 2018). The stone to precipitate iron (as oxyhydroxide) and sulfate (as
process has not been industrially applied to the processing of gypsum) from solution. After iron/sulfate removal, Ni and
nickel sulfide concentrates and information on processing of Co are precipitated from solution as a mixed hydroxide by
nickel sulfide concentrates is limited; the original patent by neutralization with MgO. The patent for the HydroNic pro­
Hourn, Turner, and Holzberger (1996) only had one applica­ cess was filed by Outotec Oyj in 2006 (Haavanlammi et al.
tion of the Albion ProcessTM to the processing of a low-grade 2006). Interestingly, another patent was filed by Outotec Oyj
nickel concentrate (1.7% Ni as pentlandite) which was milled in the same year for a chloride leach process for treatment of
to a P80 of 5 µm prior to leaching at atmospheric pressure. nickel sulfide ore and concentrates, key differences in this
process were the absence of a non-oxidative leaching step,
copper(II) was precipitated from the leach liquor as ataca­
3.4. Chloride-based leaching processes
mite (Cu2(OH)3Cl) which was returned to the leaching stage
Chloride leaching involves the dissolution of base metal and copper recovery after nickel hydroxide precipitation in
sulfide concentrates, ores or mattes exclusively in chloride the form of cuprous hydroxide (CuOH) from which copper
media as opposed to sulfate-media with the addition of metal was recovered via hydrogen reduction (Krebs et al.,
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 19

2006). The hydronic process has been tested on a range of 3.5.1. Piloted processes
nickel concentrate grades; however, it does not appear to Three bacterial leaching processes have been developed for the
have been implemented at an industrial scale. processing of nickel sulfide bearing material; the processes are
BioNIC® (BHP Limited), BacTech (BacTech Limited) and the
BioHeapTM process (BioHeap Limited, a subsidiary of Western
3.5. Bioleaching processes
Areas Limited). The BioNIC® and BacTech processes are stirred
Bioleaching generally involves the dissolution of sulfide ores/ tank bacterial leaching processes that have been successfully
concentrates in an acidic sulfate medium where ferric ions act piloted on a range of nickel concentrates and a review of these
as an oxidant, oxidizing the sulfide minerals to elemental sulfur processes and pilot plant operations has been covered by
with release of metal ions into solution (Watling 2006). The Watling (2008) in a review on the bioleaching of nickel-copper
microorganisms in bioleaching serve a dual purpose of regen­ sulfides. Neither of these processes progressed beyond pilot plant
erating ferric ions by oxidation of ferrous iron and generation scale. The BioHeapTM process developed by BioHeap Limited,
of sulfuric acid via oxidation elemental sulfur (Watling 2006). a subsidiary of Western Areas Limited, is in current use at
Some reasons for considering bioleaching for the processing of Western Areas Limited’s Cosmic Boy nickel concentrator in
sulfide ores/concentrates stated by Miller (1997) are simple Western Australia and the process and operations are described
equipment requirements and flexibility of bioleach processes below.
with respect to variation in concentrate/ore head grade and
mineralogy (Miller 1997). Potential disadvantages of bioleach­ 3.5.2. Commercial bioleach operations
ing are the slow reaction kinetics and sensitivity of the micro­ 3.5.2.1. Talvivaara heap bioleaching operation, Finland.
organisms to temperature, mineral pulp density, agitation rate The operation at Talvivaara is the only Ni sulfide heap bioleach­
and chloride concentration in process water (Astudillo and ing operation, processing a black schist ore from the Sotkamo
Acevedo 2008; Bailey and Hansford 1993; Honey, Muir, and deposit (Finland), containing 0.23–0.27% Ni, 0.5–0.56% Zn,
Hunt 1997; Nemati and Harrison 2000). Many of these limita­ 0.13–0.14% Cu and 0.02% Co (Crundwell et al. 2011b; Riekkola-
tions are dependent on the bacterial strain and in the case of Vanhanen 2013; Watling 2008). The principal sulfide minerals in
chloride concentration, can be addressed through the develop­ the ore are pyrrhotite, pyrite, sphalerite, pentlandite, violarite
ment of halotolerant bacterial strains such as in the BioHeapTM and chalcopyrite whilst non-sulfidic gangue phases are graphite,
process described below (Section 3.5.2.3). A summary of quartz, mica, anorthite and microcline (Riekkola-Vanhanen
piloted bacterial leaching processes and commercial operations 2007, 2013; Watling 2008). Ore from the mine is subjected to
employing bioleaching for processing of nickel sulfide flotation four stages of crushing to a P80 of 8 mm followed by agglomera­
concentrates is described. After sulfuric acid pressure oxida­ tion with bacteria and sulfuric acid, stacking of the agglomerates
tion, bioleaching processes are second with respect to the to form heaps and leaching of the heaps with a sulfuric acid
number of developed technologies and industrial deployment. solution at pH 1.8 (Crundwell et al. 2011b; Riekkola-Vanhanen
The key features of the piloted processes are presented in 2007, 2013; Watling 2008). Metal values (Zn, Ni, Co, Cu) are
Table 5 whilst a summary of commercial operations utilizing recovered from the pregnant leach solution by sequential pre­
bioleaching technologies are presented in Table 4. cipitation as their sulfides using H2S (Crundwell et al. 2011b;

Figure 8. Simplified process flow diagram for the hydrometallurgical processing of black schist ore from the Sotkamo deposit at the Talvivaara heap bioleaching
operation (Finland) including expected leaching recoveries for the base metals and product grades. a copper product had not been produced at the time of reporting by
Riekkola-Vanhanen (2013). Adapted from Riekkola-Vanhanen (2013).
20 N. FARIS ET AL.

Riekkola-Vanhanen 2013). A simplified process flow diagram of concentrate is subjected to a bioleaching process which was
the Talvivaara heap bioleaching operation is presented in developed in conjunction with Mintek; the leaching conditions
Figure 8. The mine is still operational and is currently being are a temperature range of 41–49°C pH range of 1.3–1.6 and
run by Terrafame Limited, a Finnish state-owned mining com­ a pulp density of 15–17% solids (Laukka et al. 2018; Neale et al.
pany which purchased the operation from the parent company 2015). The overall residence time in the bioleaching circuit is 9.5
(Talvivaara Mining Company) after declaring bankruptcy days and nickel and cobalt extractions are reported to be 87.8%
(Sairinen, Tiainen, and Mononen 2017). Recently, Terrafame and 90.7%, respectively (Laukka et al. 2018). The leach slurry is
plans on exploiting another nearby black schist ore body neutralized to pH 3.5 using limestone to precipitate iron and
(Kolmisoppi) which is currently undergoing environmental arsenic from solution followed by solid–liquid separation
assessment (Törmänen and Tuomela 2021). Terrafame intends (Laukka et al. 2018; Neale et al. 2015). The nickel-rich solution
to begin production of battery grade Ni and Co sulfates starting is subsequently treated with magnesia (MgO) slurry to precipi­
from the MSP produced from the heap leach operation, with tate Ni and Co as a mixed hydroxide precipitate (MHP) (Neale
pressure oxidation of the MSP being the first step in the process et al. 2016). The raffinate produced from MHP precipitation is
(Törmänen and Tuomela 2021). Based on a recent company treated with lime (CaO) to precipitate residual Ni and the pre­
announcement, production ramp-up of the battery chemicals cipitate is recycled to iron-arsenic precipitation circuit to re-
plant started in June 2021 and first delivery of products to dissolve residual Ni (Neale et al. 2016). Törmänen and
customers in July 2021 (Anon 2021). Tuomela (2021) have indicated that the bioleach plant has only
been operational periodically with the nickel sulfide concentrate
3.5.2.2. Mondo nickel project, Finland. Talc processing by-product presumably being sold on the market at other times.
operations at Sotkomo and Vuonos in Finland operated by
Mondo Minerals (now Elementis) produce nickel sulfide con­ 3.5.2.3. Cosmic boy nickel concentrator, Western Australia.
centrate grading 8.70% Ni as a by-product (Neale et al. 2015). The Cosmic Boy nickel concentrator in Western Australia is
The primary sulfide minerals in order of decreasing abundance owned and operated by Western Areas Limited (Fewings and
in the concentrate are pyrrhotite, pentlandite, pyrite and gers­ Seet 2014). The concentrator batch processes high grade nickel
dorffite (Neale et al. 2015). In the past the concentrate was sulfide ore from the Flying Fox (5.1% Ni grade) and Spotted
typically sold to toll smelters, however the high arsenic content Quoll (5.6% Ni grade) underground nickel mines in Western
(1.56% As) had made this option less feasible (Neale et al. 2015). Areas Limited’s Forrestania operations (Fewings and Seet 2014;
To produce a more valuable product and increase revenue, Fewings et al. 2015). The output from the concentrator is sold
a hydrometallurgical plant was built to process 12,000 tonnes to nickel smelters; however, the processing of ore from the
per annum of concentrate and recover nickel and cobalt as Spotted Quoll mine presents challenges as the ore has a high
a mixed hydroxide precipitate (Neale et al. 2015); a simplified arsenic content and the arsenic is present as niccolite and
process flow diagram of the hydrometallurgical process in use is gersdorffite (Fewings and Seet 2014; Fewings et al. 2015).
depicted in Figure 9. Nickel concentrate from both operations is Niccolite and gersdorffite are rejected during flotation using
combined and processed in a beneficiation circuit where feed is cyanide as a depressant at pH 9.8 to 10.5, though this results in
re-ground to a P80 of 30–40 µm followed by magnetic separation a loss of Ni to the tailings (Fewings et al. 2016). The cleaner
to reject pyrrhotite, and flotation to remove talc and magnesite, tailings arising from processing Spotted Quoll ore grade 18.3%
to produce an upgraded concentrate containing 12.4% Ni Ni and 6.4% As (Fewings et al. 2016). To recover Ni values
(Laukka et al. 2018; Neale et al. 2015, 2016). The nickel from the cleaner tailings, Western Areas Limited has

Figure 9. Simplified process flow diagram for the bioleaching of nickel concentrate produced as a by-product of talc mining at Mondo Minerals (now Elementis) Vuonos
talc concentrator operations in Finland. the beneficiation circuit has been omitted for simplicity. Operating conditions of major unit operations and final nickel product
grade during processing of nickel concentrate grading 10.49% Ni are presented. Adapted from Neale et al. (2015), Neale et al. (2016).
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 21

implemented a bioleach process based on proprietary their mill operations and one operation in Finland, the
BioHeapTM technology, whereby Ni is leached from the flota­ Kokkola refinery, treating pyrite-pyrrhotite concentrates. It
tion cleaner tailings whilst As and Fe are rejected as an envir­ appears there was an economic incentive at the time for these
onmentally stable precipitate (Fewings and Seet 2014; Fewings operations to extract iron and base metal values from iron
et al. 2015, 2016). sulfide concentrates produced as a by-product of copper/nickel
A key feature of the BioHeapTM process is the use of pro­ mining, rather than diverting them to tailings. The
prietary bacterial cultures which are tolerant to arsenic and Falconbridge and Inco pyrrhotite processing plants have been
high concentrations of total dissolved salts (TDS) (up to 200 g/ closed since 1972 and 1982, respectively (Rezaei et al. 2017),
L TDS) with a wide temperature range of operation (15–95°C) whilst the pyrite roaster at the Kokkola refinery in Finland shut
(Fewings and Seet 2012). Leaching using proprietary in 1987 (Sauni et al. 2010), however brief descriptions are
BioHeapTM cultures is reported to take place at elevated pH provided for historical purposes. Since the closure of the
(above pH 2) (Fewings and Seet 2012) unlike the more com­ Canadian plants, nickeliferous pyrrhotite is rejected to the
mon acid ferric sulfate leaching processes utilizing mesophilic tailings at Canadian mill operations and there is
and thermophilic microorganisms. The reported benefits of a considerable amount of pyrrhotite in tailings storage areas,
bioleaching above pH 2 is lower acid consumption and simpler where it is a potential source of acid mine drainage but is also
downstream neutralization due to reduced dissolution of of potential economic value due to the contained Ni (Peek,
gangue minerals and rejection of iron during leaching Barnes, and Tuzun 2011; Rezaei et al. 2017).
(Fewings and Seet 2012). The operating conditions of the
leach circuit are reported to be a pH between 2.8 and 3.5 at 3.6.1. Falconbridge iron ore plant
55°C in stirred tank reactors using treated process water con­ The Falconbridge iron ore plant was operated between 1955
taining 50 g/L TDS (Fewings et al. 2016); the residence time in and 1972 and processed pyrrhotite concentrate via a sulfation
the bioleaching circuit is reported to be 5–7 days (Fewings et al. roast-leach process to recover Fe in the form of a hematite
2015). The process water is treated with Caro’s acid (H2SO5) to product and base metals (Ni, Cu, Co) as a sulfide precipitate
destroy cyanide which was reported to cause some retardation which is subsequently smelted (Rezaei et al. 2017). Pyrrhotite
of Ni leaching (Fewings et al. 2015). The Ni is subsequently concentrate was subjected to oxidative roasting in the pre­
recovered from the leach liquor by precipitation using sodium sence of Na2SO4 (4–5% by weight of the pyrrhotite feed) at
sulfide (Na2S) to produce a nickel sulfide precipitate grading 680°C (Rezaei et al. 2017; Thornhill 1961) which converted
45–65% Ni, which is blended with the final flotation concen­ the base metals to their respective sulfates and iron to hema­
trate (Fewings et al. 2016). A process flow diagram of the tite. There were no provisions to capture SO2 from the roast­
BioHeapTM leach process implemented at the Cosmic Boy ers which was discharged directly into the atmosphere (Rezaei
nickel concentrator is presented in Figure 10. et al. 2017). The calcine from the roasters was leached in water
to dissolve the base metal salts and recover an iron oxide leach
residue which was dried and pelletized, producing an iron
3.6. Roast-leach processes
oxide product grading 66% Fe, 0.1% Ni, 2.2% SiO2 and 0.5%
Roasting of nickel bearing sulfide concentrates followed by S (Rezaei et al. 2017). The leach liquor is treated with pyr­
leaching has been practised at two operations in Canada, the rhotite concentrate to reduce ferric iron in the liquor to the
Falconbridge iron ore plant and the Inco iron ore recovery divalent state, followed by precipitation of base metals as their
plant, both treating nickeliferous pyrrhotite concentrates from sulfides via addition of elemental sulfur, Na2S and iron

Figure 10. Simplified process flow diagram for bacterial leaching (BioHeaptm) of high arsenic nickel flotation cleaner tailings at the Cosmic Boy nickel concentrator,
Forrestania Nickel Project (western Australia), owned and operated by Western Areas Limited. Adapted from Fewings et al. (2016).
22 N. FARIS ET AL.

borings which produces a sulfide precipitate typically grading Aaltonen 1971; Sauni et al. 2010). The pyrite-pyrrhotite
20.28–20.91% Ni, 1.85–2.30% Cu and 0.44–0.49% Co at an concentrate graded 0.67% Co, 0.37% Ni, 0.28% Cu and
overall Ni recovery of 82.2% (Thornhill 1961). The plant was 0.4% Zn (Palperi and Aaltonen 1971). A two-stage roasting
shut in 1972 due to the introduction of environmental reg­ process was employed whereby part of the concentrate was
ulations which imposed annual limits on SO2 emissions from roasted to produce an oxide calcine (termed dead roasting)
smelters (Potvin and Negusanti 1995). Further operational which was then combined with fresh sulfide concentrate
details of the Falconbridge iron ore process are provided by and sodium sulfate in the second roasting stage where
Thornhill (1961) whilst technical details of the roasting pro­ sulfation of the base metals takes place at 680°C (Deng
cess and sulfide precipitation method are provided in the 1992; Palperi and Aaltonen 1971). The rationale for this
relevant patents (Thornhill 1954, 1960; Thornhill and two-stage roasting approach was (a) finely divided ferric
Coulter 1966). oxide produced from dead roasting catalyses SO2 oxidation
to SO3 which reacts with metal oxides to form their sulfates
3.6.2. Inco iron ore recovery plant and (b) addition of fresh concentrate to the second stage
Inco (now Vale) operated a modified Caron process between maintained a desirable atmosphere for sulfation and sup­
1956 and 1982 and extracted iron, sulfur, Ni and Cu from plied heat for roasting (Palperi and Aaltonen 1971). The
pyrrhotite concentrate recovered from the Copper Cliff or SO2 produced from roasting was sent to a sulfuric acid
Clarabelle mills in the form of iron oxide pellets, sulfuric plant whilst the iron oxide leach residue (termed purple
acid, nickel oxide (NiO) and copper sulfide (CuS) (Conard ore) grading 64.3% Fe (Palperi and Aaltonen 1971) was
2013; Rezaei et al. 2017). The reduction roast/leach sectio presumably sold. Nickel, Cu and Zn were recovered from
n of the plant was shut in 1982 amid an economic downturn the leach liquor by precipitation as their sulfides, with the
whilst the pyrrhotite roasters continued to operate supplying sulfide precipitate being smelted and refined at Harjavalta
sulfuric acid to the market until 1991 (Rezaei et al. 2017). (Finland) (Palperi and Aaltonen 1971). Metallic cobalt was
Conard (2013) indicated that production of NiO continued recovered by hydrogen reduction of a cobalt-ammonium
until the mid-1990s, though with the shutdown of the reduc­ sulfate solution (Palperi and Aaltonen 1971). The sulfation
tion kiln, the feed was metallic Ni powder from Inco’s Copper roasting plant reportedly closed in 1987 (Sauni et al. 2010),
Cliff nickel refinery. ahead of the closure of the Outokumpu copper mine in
The first stage in the process was an oxidizing roast of 1989, though the production of cobalt products at Kokkola
the pyrrhotite concentrate at 760°C to produce an iron continues to this day and a cobalt refinery is currently
oxide calcine and SO2; the SO2 stream was sent to operated by Umicore (Törmänen and Tuomela 2021).
a sulfuric acid plant whilst the calcine was transferred to
the reduction kiln (Conard 2013). The Ni present in pyr­
4. Summary
rhotite was oxidized to nickel ferrite (NiFe2O4) (Conard
2013; Rezaei et al. 2017). In the reduction kiln, Ni in nickel A summary of the advantages, disadvantages, and commercial
ferrite was reduced to a mixture of Fe-Ni alloy and nickel progress of each of the various leaching systems that have been
sulfide whilst hematite in the calcine was reduced to mag­ employed for direct extraction of nickel from flotation concen­
netite using partially combusted natural gas (Conard 2013; trates is presented in Table 6. It can be seen from Table 6 that
Rezaei et al. 2017). The reduced calcine was leached in sulfate-based leaching technologies, particularly pressure oxi­
aerated ammonia-ammonium carbonate lixiviant at 55°C dation and bioleaching, are the most advanced with regards to
to dissolve Ni and other base metals in the calcine the number of processes that have been piloted and commer­
(Conard 2013). The iron oxide leach residue was sent to cially deployed at nickel sulfide processing operations. Both
a pelletizing plant to produce hematite pellets grading 67% technologies are well established, having enjoyed success in
Fe (Conard 2013). Copper (along with some Co) was recov­ other industries and therefore pose a low technical risk relative
ered from the leach liquor by precipitation as a sulfide to other less established leaching technologies. Other factors to
using sodium hydrosulfide (NaHS) with the precipitate consider in selection of a process/technology for direct leach­
being sent to a smelter (Conard 2013). Nickel was recov­ ing of nickel sulfide concentrates besides the track record/
ered from the leach liquor after Cu removal by precipita­ experience in other industries is the flexibility/adaptability of
tion as a basic nickel carbonate using soda ash (Na2CO3) the process to changes in feed composition and the types of
and calcination at 550°C to produce an acid-soluble nickel finished nickel products that can be produced i.e. intermediates
oxide product grading 77% Ni and 0.15% Co (Conard such as MHP or MSP, or class 1 nickel (>99.8% Ni) products
2013). such as electrowon cathode, metallic Ni briquettes or powder,
or high-purity nickel sulfate. Some of the processes are sum­
3.6.3. Kokkola refinery, Finland marized in Table 6 such as nitric acid leaching have not
The Kokkola refinery operated by Outokumpu Oyj pro­ progressed beyond laboratory scale investigation and therefore
cessed pyrite-pyrrhotite flotation concentrate recovered as remain unproven at large scale. It is interesting to note that
a by-product from the Outokumpu copper mine for recov­ despite the success of chloride-based leaching processes in the
ery of base metals between 1966 and 1987 (Palperi and commercial processing of nickel mattes, chloride-based
Table 6. Comparison of leaching processes that have been evaluated for the direct leaching of nickel sulfide flotation concentrates and commercial progress.
Leaching system Advantages Disadvantages Commercial progress
Ammoniacal - Highly selective for metals which form soluble amine complexes (Ni, - Ammonia is expensive, though it can be partly recovered for reuse - Sherritt-Gordon Process originally developed to treat flotation concentrates and is in use
leaching: Co, Cu & Zn) - Ammonium sulfate by-product requires disposal if there is no market for it. Where it is to at two locations (Fort Saskatchewan, Canada & Kwinana, Western Australia); however,
- Sherritt-Gordon - Iron, aluminum, magnesium & calcium rejected during leaching as be used for fertilizer applications, must meet specifications with respect to metals and both operations no longer process nickel flotation concentrates. Fort Saskatchewan is
process insoluble residues sulfamate content, the latter being herbicidal. processing MSP and Kwinana is processing nickel matte.
(ammoniacal - Fast leaching kinetics - Cobalt refining more complex relative to other processes
pressure - Ni metal powder can be produced directly from the resultant leach
leaching) liquor
- Pyrite is inert, though any Ni/Co associated with pyrite is not extracted
Acid sulfate - Pressure leaching is conducted by well-established technologies - Autoclaves and oxygen gas represent significant capital and operating costs for pressure - Numerous pressure oxidation processes have been piloted (Activox®, PLATSOLTM, CESL,
leaching: - Pressure oxidation processes can be operated autogenously i.e. no oxidation processes Kell process)
- Pressure oxidation external heat input - Recovery of Au, Ag and PGMs from the leach residue can be difficult depending on the - Pressure oxidation has been commercially deployed at the Kokkola refinery (Finland),
-Co-processing of - Sulfuric acid is a low cost lixiviant, can also be generated in situ from chosen leach conditions Long Harbor (Voisey’s Bay Process, Canada), the Nadezhdin mill (Russia),
Ni-laterites oxidation of part or all the elemental sulfur produced during leaching - Iron precipitation products generally unsuitable for steel making due to sulfur & Zn/Cu Fredericktown and Garfield refineries (USA). The US operations are now closed but
& sulfides or recycling SX and EW raffinates to the leaching stage content were the first commercial operations to utilize pressure oxidation to process nickel
- Atmospheric - High degree of flexibility with respect to type of products that can be - Ca/Mg-bearing silicate minerals can pose problems with regards to acid consumption & bearing sulfide concentrates.
leaching produced (cathode, MHP, MSP, sulfate salts) silica gelling, and dissolved Mg ions can be problematic for Ni/Co SX and effluent - Co-processing of laterites and sulfides appears promising but is currently limited to
- Depending on the chosen leach conditions, oxidation of sulfide to treatment laboratory/pilot investigations
elemental sulfur can be favored (which reduces the amount of - Potentially slow dissolution kinetics at ambient pressure for stirred tank leaching - Albion ProcessTM (atmospheric leaching process) expected to be suitable for nickel
oxidant required) processes unless ultra-fine grinding is utilized such as in the Albion ProcessTM or sulfide processing based on commercial success in processing of gold, zinc and copper
- Pyrite is generally inert (depends on leach conditions), though any Ni/ through the addition of halide salts such as in the Intec Nickel Process concentrates
Co associated with pyrite may not be extracted
- Arsenic can be managed by precipitation as stable ferric arsenate
- Iron hydrolysis products are typically well-crystalline and readily
filterable (depends on leach conditions)
Chloride leaching: - Fast leaching kinetics - Chloride ion is corrosive and therefore exotic materials of construction are required for - Chlorine leach processes have been successfully employed for extraction of Ni and Co
- Ferric & cupric - Oxidation of sulfide to elemental sulfur favored, and As(III) to As(V) the leaching vessels from mattes at Nikkelverk (Falconbridge process), Sandouville-Le Havre and Niihama
chloride leaching which is precipitated as ferric arsenate phases - Impurity buildup can occur from recycling of chloride lixiviants, necessitating their (MCLE process) but have not been utilized for processing nickel flotation concentrates
- Gaseous oxidants - Elemental sulfur formed at temperatures below melting point is removal once the concentration becomes intolerable - Atmospheric chloride leach processes have been patented (Outotec, Jaguar Nickel Inc.)
(oxygen, porous, facilitating more complete leaching of base metals - Use of chlorine gas as an oxidant for leaching poses a hazard to humans and the but have not seen industrial deployment
chlorine, and - Leaching can be carried out at atmospheric pressure & lixiviants can be environment. ‘Wet’ chlorine gas also corrosive, requiring exotic materials of
their mixtures) regenerated for reuse construction for leaching vessels
- Precious metals and PGMs are soluble in chloride lixiviants though - Recovery of Au and PGMs from the leach residue can be difficult where the residues are
rejection to the leach residue is possible through control of the ORP contaminated with iron hydrolysis products and elemental sulfur
- Pyrite is inert, though any Ni/Co associated with pyrite is not extracted -Advantages of chloride media such as producing sulfur textures ideal for facilitating base
- Ni & Co electrowinning from chloride media is well established metal sulfide dissolution, and limited oxidation of sulfur to sulfate can be equally
addressed in sulfate/sulfuric acid systems with addition of chloride salts (Activox®,
CESL process)
Nitric acid leaching - Nitric acid serves as both the lixiviant and the oxidant, simplifying - Sulfur oxidation to SO42- undesirable as it consumes excess nitric acid and the sulfate - Direct Nickel Process (DNi ProcessTM) has been piloted for processing nickel laterite ores
reagent requirements for leaching. It is also a strong oxidizing agent must be subsequently removed from the leach liquor for nitric acid regeneration - Very few published studies on leaching of Ni-sulfide concentrates in nitric acid solutions
- Nitric acid can be regenerated from hydrolysis of ferric nitrate solutions, - Metals recovery by electrowinning or H2 reduction likely to require transfer of the
scrubbing of NOx gases evolved during leaching and thermal dissolved metals from a nitrate medium into a sulfate or chloride system
decomposition of nitrate salts such as Mg(NO3)2 if recovered - Potential for degradation of organic extractants due to residual nitric acid in leach
- Hematite produced from hydrolysis of nitrate solutions is ‘cleaner’ and liquors
more marketable i.e. low sulfur, base metal contaminants compared - Environmental limits on discharge of nitrate & NOx gases means recovery and re-use of
to sulfate-based routes reagent must be rigorous
- Stainless steels can be used as materials of construction for leaching -Benefits of nitric acid can be addressed in sulfate systems by adding of small quantities of
vessels nitrates/nitrites to function as an oxidation catalyst i.e. Nitrogen Species Catalyzed
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW

- Arsenic can be managed by precipitation as stable ferric arsenate (NSC) pressure leaching, or used exclusively as an oxidant
(Continued)
23
24
N. FARIS ET AL.

Table 6. (Continued).
Leaching system Advantages Disadvantages Commercial progress
Bacterial leaching: - Processing equipment is simpler relative to other competing - Slow leaching kinetics which translates to long residence times; 5–10 days being typical - Three bioleaching processes for treatment of nickel sulfide concentrates have been
- Mesophiles (T < technologies for continuous stirred tank bioleaching piloted: BioNIC® (BHP Limited) BacTech (BacTech Limited) and BioHeapTM (Western
45° C) - High degree of flexibility with respect to type of products that can be - Microbes may be sensitive to chloride content in water which poses problems for Areas Limited); the latter having been implemented at a nickel sulfide concentrator
- Moderate produced (cathode, MHP, MSP, sulfate salts) regions where only saline waters are available. Microbes may also be sensitive to pulp - Bioleaching of nickel sulfide concentrates has been implemented at two operations for
thermophiles - Bioleaching processes are stated to be flexible with regards to density and shear rate which affects throughput and equipment sizing. Finally, treating low volumes of material; in both cases the concentrates being processed were
and thermophilic concentrate head grades and mineralogy microbes may be sensitive to leaching temperature which affects throughput and high in arsenic (as niccolite and gersdorffite)
archaea - Bioleaching is suitable for the processing of polymetallic concentrates cooling requirements for bioleach processes - Bio-heap leaching is in use in Finland for processing of a base metals (Ni, Cu, Zn, Co)
(55–85° C) containing gold, silver and PGMs in addition to base metals - Iron precipitation product may be poorly crystalline & voluminous with poor settling & bearing black schist
filtration properties; base metal losses could occur through adsorption & entrainment
- Poor rejection of As during leaching; As is solubilized as As(III) which must be oxidized to
As(V) for precipitation from solution
Roast-leach - Iron conversion to an insoluble iron oxide during oxidizing roasting - Gaseous emissions from roasting processes requires emissions abatement equipment or - A modified Caron process was in use by Inco Ltd. at their Copper Cliff Operations for
processes: processes can result in minimal iron dissolution in subsequent a sulfuric acid plant which significantly increases capital cost. Arsenic may be recovery of iron and base metals from pyrrhotite concentrates. The plant is no longer
- Oxidizing roast & leaching stages & could also enable the recovery of iron oxide as volatilized during roasting operational
Caron-type a by-product - Nickel ferrites if formed during oxidizing roasting processes limit Ni recovery during - The Falconbridge iron ore plant in Canada and the Kokkola works in Finland utilized
processes - Conversion of base metal sulfides to sulfates or chlorides during salt subsequent leaching processes sulfation roasting to recover iron and base metals from pyrrhotite and pyrite-
- Chloridizing and sulfation roasting means water or dilute acids can be used as the - Use of alkali sulfates or chlorides for roasting could be problematic for disposal of pyrrhotite concentrates. Both plants are no longer operational
roasting lixiviant in leaching effluents - Chloridizing roasting and reduction roasting + leaching processes have only been tested
- Sulfation roasting - Reduction roasting converts many ‘refractory’ sulfides to a more - Roasting processes can be energy intensive at laboratory scale for the processing of nickel sulfide concentrates
- Reduction reactive form amenable to subsequent leaching via non-oxidative - Reduction roasting followed by non-oxidative leaching generates H2S, a toxic gas,
roasting dissolution whose emissions must be managed such as by the Claus process or other suitable
technologies
- Non-oxidative leaching of reduced sulfide concentrates require high concentrations of
mineral acids which can require the use of exotic materials of construction, thereby
increasing capital cost. Regeneration and recycling of the lixiviant would also be
required for this approach to be economical
MINERAL PROCESSING AND EXTRACTIVE METALLURGY REVIEW 25

leaching has not seen use for direct processing of nickel sulfide Anon, July 29, 2021. Terrafame’s net sales in the first half of 2021 amounted to
concentrates. Despite the number of technologies that have EUR 185.0 million – Battery chemicals plant’s ramp-up started. Accessed
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