Minerals Engineering 131 (2019) 170–184

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

The beneficiation of lithium minerals from hard rock ores: A review T

Bogale Tadesse , Fidele Makuei, Boris Albijanic, Laurence Dyer
⁎

Western Australian School of Mines, Curtin University, Egan St, Kalgoorlie, WA 6430, Australia

ARTICLE INFO ABSTRACT

Keywords: The demand for lithium minerals has increased considerably in recent years due to the application of lithium
Beneficiation compounds in lithium ion battery technology, portable electronic gadgets and power storage systems.
Lithium minerals Spodumene is the main lithium bearing mineral which is currently being explored and processed due to its high
Spodumene lithium content and the extensive occurrence of deposits. This literature review focuses on the various techni-
Dense media separation
ques used in the beneficiation of lithium minerals from hard rock pegmatite ores. Dense media separation and
Flotation
flotation are the main beneficiation methods used for the separation of lithium minerals from ores. The close
similarity in chemical and physical properties between lithium minerals and associated gangue minerals com-
plicates the beneficiation of lithium minerals from ores. Surface chemistry of minerals, type of collector, pulp
pH, chemical pre-treatment methods, and the presence of slimes play key roles in lithium minerals flotation. This
review also deals with the beneficiation flowsheets employed at some of the larger lithium processing plants in
the world. Spodumene from pegmatite deposits is expected to be the main source of lithium from ores at present
although future sources would most probably include other minerals such as lepidolite, petalite, zinnwaldite,
jadarite and hectorite.

1. Introduction reserve, insecurity and political instability in oil producing countries,

Lithium is a soft, silver-white coloured, and the lightest alkaline
metal with an atomic weight of 6.939. Lithium compounds such as li-
thium carbonate, lithium hydroxide and lithium bromide are used in
glass, ceramics, lubricant and grease manufacturing to improve extreme
temperature resistance, in aluminium production, as catalysts in the
pharmaceutical and rubber industries, and in air conditioning and de-
humidification systems (Ebensperger et al., 2005; Peiro et al., 2013).
However, a recent application of lithium ion technology in electric
automobiles has put more demand on lithium minerals (Ebensperger
et al., 2005; Peiro et al., 2013). Fig. 1 shows world lithium production
and consumption between 2005 and 2017 (Jaskula, 2015; US
Geological Survey, 2018). The general trend suggests increasing pro-
duction and consumption for lithium. The increase in global lithium
production was estimated at 13% in 2017 as compared with production
in 2016 (US Geological Survey, 2018). The price of battery-grade li-
thium carbonate in 2017 was 13,900 USD/t, which represents a 61%
increase in price from that of 2016 (US Geological Survey, 2018).
Although renewable energy resources are growing at considerable
rate, the majority of the world’s energy still comes from fossil fuels
(Scrosati and Garche, 2010). There are several issues associated with
the usage of fossil fuels including higher demand for oil, depletion of oil
emission of greenhouse gases and issues of climate change (Grosjean
et al., 2012; Scrosati and Garche, 2010). Lithium is playing a critical
role as an engineering material in mitigation of issues that stem from
consumption of fossil fuels. For example, the application of lithium ion
battery in an electrical vehicle and hybrid cars is expected to minimize
the potential environmental impact of pollution from conventional
vehicles (Grosjean et al., 2012). Also, lithium ion battery is expected to
provide storage for power from renewable energy sources such as solar
and wind power (Scrosati and Garche, 2010). Batteries, and glass and
ceramics manufacturing account for the main global end-use con-
sumption for lithium; the estimated share of other markets is shown in
Fig. 2 (US Geological survey, 2018).
There are two economic sources of lithium; brines and hard rock
ores. The majority of the global lithium production, greater than 60%,
is produced from brines while lithium ores accounted for the remaining
production (Ebensperger et al., 2005). Table 1 summarises the world’s
major lithium producers from ores and brines, and the total reserves.
The lithium production in Chile and Argentina is mainly sourced from
brines. The major producers of lithium concentrates from hard rock
ores are Australia, Canada, Zimbabwe, Portugal and Brazil (US
Geological survey, 2018).
In 2011, 85% of world lithium production from ores came from

⁎
Corresponding author.
E-mail address: Bogale.tadesse@curtin.edu.au (B. Tadesse).

https://doi.org/10.1016/j.mineng.2018.11.023
Received 25 July 2018; Received in revised form 10 September 2018; Accepted 13 November 2018
Available online 19 November 2018
0892-6875/ Crown Copyright © 2018 Published by Elsevier Ltd. All rights reserved.
B. Tadesse et al. Minerals Engineering 131 (2019) 170–184

Fig. 1. Estimated world lithium production (excluding U.S. production) and consumption (Jaskula, 2015; US Geological Survey, 2018).

lithium from lithium bearing economic ores. Physical separation tech-

niques such as heavy media and magnetic separation, flotation and
optical sorting of lithium ores have been reviewed. Due to the limited
literature on beneficiation of other lithium minerals, a large part of this
review focuses on beneficiation of spodumene from pegmatite ores.

2. Mineralogy of lithium bearing minerals

Lithium ores often occur as hard rock complex aluminium silicate

deposits known as pegmatites (Bale and May 1989; Colton, 1957).
Pegmatites are intrusive igneous rocks mainly composed of interlocking
mineral grains of quartz, feldspar, spodumene, mica (Colton, 1957).
The lithium pegmatite ores contain lithium minerals such as spodu-
mene, petalite, lepidolite and amblygonite (Bulatovic, 2015). Other li-
thium minerals such as zinnwaldite, triphylite and eucryptite are also
Fig. 2. Global lithium end-use market shares (US Geological Survey, 2018). reported in the literature (Colton, 1957; Grosjean et al., 2012). Among
the lithium-rich pegmatite minerals, spodumene is of primary economic
Table 1 importance. Table 3 shows lithium minerals of economic significance
Global lithium production and reserves (brines and deposits) in tons (US and their physical properties. The typical lithium grade in exploitable
Geological survey, 2018). pegmatite deposits ranges from about 1.25–4% Li2O (Bale and May,
1989).
Mine production Reserves

2016 2017 2.1. Spodumene

Argentina 5800 5500 2,000,000
Australia 14,100 18,700 1,600,000 Spodumene is a monoclinic pyroxene with a single-chain structure
Brazil 200 200 48,000 consisting of lithium aluminum silicate, and is tabular hard rock which
Chile 14,300 14,100 7,500,000 is insoluble dilute acids (Bulatovic, 2015). It has a prominent long-
China 2300 3000 3,200,000 itudinal cleavage. Fig. 3 shows a photograph of spodumene crystals for
Portugal 400 400 60,000
a sample collected from Bald Hill Mine in Western Australia. Spodu-
Zimbabwe 1000 1000 23,000
World total (rounded) 38,000 43,000 16,000,000 mene is the main lithium bearing silicate mineral which is currently
being explored and processed due to its high Li content and the oc-
currence of extensive deposits (Garret, 2004). Spodumene is found in
Australia’s Greenbushes spodumene pegmatite deposit as a lithium pegmatite deposits in association with other silicate minerals such as
mineral concentrate which is exported to China to produce lithium feldspar, micas, and quartz (Bulatovic, 2015). A typical pegmatite Li ore
carbonate and lithium hydroxide (Peiro et al., 2013). The major known from Kings Mountain, North Carolina, has a composition of 20 wt%
global lithium mineral deposits and estimated resources that are con- spodumene, 7% muscovite, 43% feldspar and 30% quartz while pure
tained in ores only are given in Table 2. The scope of this review is spodumene contains 8.0% Li2O, 27.4% Al2O3 and 64.6% SiO2 (Moon
limited to the recovery of lithium minerals from ores only as per and Fuerstenau, 2003). Greenbushes in Western Australia is the largest
Table 2. lithium mine in the world from which high grade lithium concentrate is
To meet the increasing demand for lithium, there is a need to op- recovered in the form of spodumene (Garret, 2004; US Geological
timize and improve its beneficiation and extraction from ores. survey, 2018). Other recently commissioned lithium mines in Australia
Processing of lithium ore, like most minerals, begins with beneficiation concentrating spodumene from hard rocks include Bald Hill, Mt Cattlin
prior to extraction of its compounds in downstream processes. The aim and Mt Marion. Spodumene is commonly concentrated by heavy media
of this review is to consolidate current literature on beneficiation of separation, froth flotation and/or magnetic separation. Prior to

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B. Tadesse et al. Minerals Engineering 131 (2019) 170–184

Table 2
Major known global lithium mineral deposits and estimated resources contained in ores only (modified from Vikström et al., 2013).
Country Deposit examples Main mineral(s) Estimated resources (Mt)

Afghanistan Helmand Basin, Katawaz Basin, Taghawkor Spodumene n.a

Australia Greenbushes, Mt Marion, Mt Cattlin, Bald Hill Spodumene 0.79
Austria Koralpe Spodumene 0.10
Brazil Aracuai/Cachoeira, Mibra/Minas Gerais Petalite, Spodumene 0.92
Canada Barraute/Quebec, Bernic Lake/Tanco, James Bay, La Corne, La Motte, Yellowknife Spodumene 2.41
China Daoxian, Gajika, Jaijika, Maerkang, Ningdu, Yichun Lepidolite, petalite, spodumene 2.40
Congo Kitotolo, Manono Spodumene 3.80
Finland Länttä Spodumene 0.68
Mali Bougouni Amblygonite 0.03
Portugal Barroso Petalite 0.01
Namibia Karibib Petalite 0.15
Russia Belerechenskoe, Etykinskoe, Goltsovoe, Kolmorzerskoe, Voronietundrovskoe Spodumene, lepidolite 3.69
Serbia Jadar Valley Jadarite 1.00
USA Bessemer City, Kings Mountain Belt, McDermitt/Kings Valley, North Carolina Spodumene, hectorite 13.8
Zimbabwe Barkam, Bikita, Kamativi, Masvingo Spodumene, petalite 0.73

leaching, natural spodumene (α-spodumene) is converted to irrever-

sible β-spodumene by heating at about 1000–1100 °C because the β-
spodumene phase is much more reactive and less resistant to ordinary
chemical agents. Sulphuric acid and alkaline (e.g., Ca(OH)2) digestion
methods are industrial processes used for the extraction of lithium from
spodumene with typical final products such as lithium carbonate and
lithium hydroxide (Rosales et al., 2014).

2.2. Petalite

Petalite is a monoclinic mineral with a framework silicate structure

which is commonly associated with other pegmatites such as spodu-
mene, eucrypite and lepidolite. The theoretical lithium content of pe-
talite is 2.27% (4.88% Li2O) although Li content in many deposits vary
from 1.4 to 2.2% Li (3.0–4.7% Li2O). Large deposits of petalite occur in
Zimbabwe, Canada, Brazil, and Australia. A significant amount of pe-
talite has also been reported in Namibia, China, and Russia
(Wietelmann and Bauer, 2003; Garret, 2004). A less common lithium
mineral, eucryptite, occurs mainly in combination with petalite. Nat-
Fig. 3. A photograph of high grade spodumene ore sample collected from Bald
ural petalite is converted to β-spodumene at high temperatures to make
Hill mine site in Western Australia showing characteristic longitudinal and
it amenable to leaching (Garret, 2004). elongated tabular cleavages.

2.3. Lepidolite
Lepidolite is a mica with complex and variable composition and is
used in the production of glasses and ceramics. Its Li content can vary
significantly from 1.39% (3.0% Li2O) to 3.58% Li (7.7% Li2O).
Lepidolite is not as widely distributed in pegmatites as compared with
spodumene. Commercial lepidolite deposits are found in Zimbabwe,
Canada, Namibia, Brazil, Portugal and Argentina (Garret, 2004). Lepi-
dolites also contain significant amounts of rubidium and thus are im-
portant sources of Rb in addition to Li (Wietelmann and Bauer, 2003).
The main gangue minerals found in association with lepidolite include
calcite, muscovite, feldspar and quartz, which need to be separated to
enrich lepidolite. Flotation can be used to separate calcite, muscovite,
feldspar and/or quartz from lepidolite (Choi et al, 2012). Sulphuric acid
digestion at temperatures higher than 250 °C is one method used for the
extraction of Li from lepidolite.
2.4. Amblygonite
Amblygonite is the fluorine-rich end member of a lithium alumino-
phosphate group. Its theoretical lithium content is 4.76% (10.2% Li2O),
but most economic ores contain 3.5–4.4% Li (7.5–9.5% Li2O). Although
sizeable deposits are relatively rare, it is mined in Canada, Brazil,
Surinam, Zimbabwe, Rwanda, Mozambique, Namibia, and South Africa
(Garret, 2004). Dense media separation and flotation are used in the

Table 3
Common lithium minerals of economic values (Bulatovic, 2015; Chelgani et al., 2015; Grosjean et al., 2012).
Mineral Formula Content % Li2O SG Hardness

Theoretical Actual

Spodumene LiAl[SiO3]2 8.1 4.5–8.0 3.1–3.2 6.5–7

Petalite LiAlSi4O10 4.89 2–4 2.4–2.5 6–6.5
Lepidolite KLiAl2Si3O10(OH,F)3 5.9 1.2–5.9 2.8–2.9 2–3
Amblygonite LiAl[PO4][F,OH] 10.1 4.5–10 3.0–3.2 5.5–6
Zinnwaldite K[Li,Al,Fe]3[Al,Si]4O10[F,OH]2 4.13 3.3–7.7 2.9–3.2 2–3
Eucryptite LiAlSiO4 11.9 11.9 2.67 6.5

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B. Tadesse et al.
separation of amblygonite from other lithium minerals and silicate
gangue (Bulatovic, 2015). When amblygonite and spodumene are pre-
sent in the same ore, amblygonite is usually pre-floated because it
contaminates the spodumene with phosphate and fluorine (Garret,
2004). The presence of fluorine in lithium ores is undesirable due to the
formation of LiF and toxic H2F2 during downstream processing. Am-
blygonite is relatively acid soluble in comparison with other silicates.
2.5. Zinnwaldite
Zinnwaldite is considered as an impure variety of lepidolite with
relatively high iron content (up to 11.5% Fe as FeO) and MnO (3.2%)
(Paukov et al., 2010). The high iron content of Zinnwaldite combined
with the relatively low Li2O in ores makes it relatively unattractive as
lithium source. Significant reserve of zinnwaldite is located in the Czech
Republic/Cinovec, Erzgebirge at the German/Czech border assaying
67 wt% quartz, 20 wt% zinnwaldite, 8 wt% topaz, 3 wt% muscovite and
2 wt% trace minerals (e.g. cassiterite, wolframite, kaolinite, columbite
and limonite) (Chelgani et al., 2015; Leißner et al., 2016; Wietelmann
and Bauer, 2003). Zinnwaldite wastes from the processing of Sn–W
ores, which was previously mined Cínovec deposit, was suggested to be
an accessible raw material for lithium and rubidium production
(Jandová et al., 2010). Zinnwaldite has been floated using collectors of
the Aeromine series from tin-tungsten tailings (Jandová and Vu, 2008;
Samkova, 2009). Zinnwaldite has significant magnetic properties due to
a relatively high content of iron and thus can be enriched using mag-
netic separation. The use of magnetic separation followed by water
leaching and precipitation can produce a Li2CO3 concentrate of > 99%
purity (Jandová et al., 2009).
2.6. Eucryptite
Eucryptite ores were once an important source for lithium and
contain an average of 2.1–3.0% Li (4.5–6.5% Li2O). It is also used for
glass manufacturing. The Bikita deposit in Zimbabwe has an average
grade of 2.34% Li (5.0% Li2O). However, eucryptite deposits are fairly
uncommon and often found in small tonnages (Garret, 2004). Eu-
cryptite can be leached directly by strong acids without the need for
roasting.
2.7. Other Li occurrences
Lithium-bearing clays are regarded as additional sources of lithium.
Among these clays is hectorite (Na0.33[Mg,Li]3Si4O10[F,OH]2), a trioc-
tahedral smectite rich in lithium and magnesium, which contains
0.7–1.3% Li2O and 0.3–0.6% Li. The best known hectorite deposit with
0.7% Li is found in Hector, California (Foshag, and Woodford, 1936).
Jadarite (LiNaSiB3O7(OH)) is a lithium-boron containing mineral found
in Serbia (Mohr et al., 2012). A less common lithium-bearing smectite
from Kings Mountain, North Carolina, known as swinefordite is re-
ported to have the highest lithium content known in clays with Li2O
content ranging from 4.29 to 5.66 wt% (Tien et al., 1975).
3. Beneficiation of lithium ores
The major techniques used in the beneficiation of lithium minerals
are shown in a generalised flowsheet in Fig. 4, and include gravity se-
paration (DMS), magnetic separation, and froth flotation. Sorting is also
being recognised as a potential method in recent years. Dense media
separation is usually employed for coarse gangue rejection, but can also
be used to produce lithium concentrates from high grade ores. Flotation
is used for processing fine particle size feed, and where high grade
concentrates are required. Magnetic separation is used to remove large
quantities of iron bearing gangue minerals to make the concentrate
suitable for use in ceramics and glass manufacturing. These separation
techniques will be reviewed in the following sections.
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Minerals Engineering 131 (2019) 170–184
3.1. Gravity and dense media separation
The beneficiation of pegmatite ore in the presence of other valuable
minerals such as those containing tin and tantalum in addition to the
lithium minerals increases the complexity of processing. This may in-
volve additional operation to remove these minerals as by products. For
example, in the treatment of Bernic lake pegmatite, spiral circuits are
used to remove and concentrate tantalum minerals (Ferguson et al.,
2000). Also, in the processing of Greenbushes’ pegmatite ore, the bulk
flotation concentrate is treated with gravity separation techniques such
as spiral and shaking table to remove heavy minerals, e.g., SnO2, Ta2O5
and Fe2O3 (Bale and May, 1989).
Dense media separation (DMS) or heavy media separation is a pre-
concentration technique used to reject gangue minerals prior to
grinding. DMS exploits the difference in specific gravity between the
target and gangue minerals, and is commonly used in the separation of
spodumene from other gangue silicates. The specific gravity of spodu-
mene is between 3.1 and 3.2; this makes it slightly heavier than most
gangue minerals such as quartz (2.65), albite (2.60) and muscovite
(2.8). The spodumene, therefore, sinks while gangue minerals float in
dense medium of appropriate specific gravity, and thus separated from
each other.
It is claimed that the first DMS plant employed for pegmatite ore
processing was at the Edison mine in the US in 1949 (Munson and
Clarke, 1955). At the Edison mine, a ferrosilicon and magnetite mixture
was used to obtain a medium of specific gravity of 2.70. It was reported
that the spodumene concentrate from this operation assayed at 5.36%
Li2O with recovery of 47.4% (Munson and Clarke, 1955). In a similar
medium, DMS on a spodumene deposit from North Carolina with
−10 mm + 212 µm feed size and head grade of 1.3% Li2O resulted in a
concentrate grade of 3.5% Li2O with recovery of 50–60% (Redeker,
1979). The increase in DMS feed size at Kings Mountain operations due
to issues in washing and screening led to reduced lithium recovery.
Subsequently, the DMS operation was decommissioned in the early
1970s and was replaced by flotation to concentrate spodumene
(Redeker, 1979). In an ore containing feldspar, quartz and muscovite
from Portugal, bromoform was used as dense medium to achieve spo-
dumene recovery of 61.1% with 5.17% Li2O (Amarante et al., 1999).
Smaller feed size (−4.7 mm) resulted in higher spodumene recovery
and grade due to the better degree of spodumene liberation achieved
(Amarante et al., 1999). In a related study involving 4 series of dense
medium separators a concentrate grade of 6.4% Li2O and spodumene
recovery of 45% was obtained for a particle size fraction of
−9.51 + 0.5 mm using media with SG between 2.6 and 3.0
(Aghamirian et al., 2012).
Several factors affect the efficiency of DMS in pegmatite minerals
beneficiation. Firstly, the gangue (e.g., iron bearing silicates such as
amphibole) and the target minerals (e.g., spodumene) have only small
differences in SG and therefore tend not to be separated from each
other. Secondly, in the case of spodumene, the mineralogical transfor-
mation of spodumene to micaceous and clay minerals reduces the SG of
spodumene as compared with its pure form and as a result, there is
effectively little difference in SG between the gangue minerals and
spodumene (Munson and Clarke, 1955). The spodumene behaves like
micaceous and clay minerals in heavy media separation and thus its
separation is affected. Thirdly, spodumene is reported to break into
acicular particles that tend to float with gangue minerals (Munson and
Clarke, 1955). These factors contribute to the poor recoveries obtained
in spodumene beneficiation using DMS. Despite these shortcomings,
DMS is still an attractive pre-concentration process for spodumene ore
processing at coarse particle size (typically the −850 + 500 µm size
fraction). It can be used in the production of coarse grain spodumene
concentrate which is used in ceramic and glass manufacturing
(Aghamirian et al., 2012). DMS is typically used for coarse gangue re-
jection in beneficiation of pegmatite ores (Ferguson et al., 2000) with
the undersize feeding a flotation circuit. However, it is important to
B. Tadesse et al.
Fig. 4. Generalized flowsheet for concentrating lithium minerals from hard rock ores.
note that the success of dense media separation is dependent on the
degree of liberation of spodumene at coarsest grain size (Aghamirian
et al., 2012).
3.2. Magnetic separation
Lithium pegmatite ores are associated with gangue such as iron-
bearing minerals that are difficult to separate from lithium minerals by
DMS and/or flotation. The iron present in pegmatite ores is in the form
of iron bearing minerals including amphibole and tourmaline (Bale and
May, 1989) and as a dispersed molecular iron in spodumene crystal
structure which imparts a characteristic colour in spodumene (Banks
et al., 1953). Although the iron content in spodumene for ceramics
production should be no greater than 0.5% Fe2O3, the iron content of
spodumene concentrate used for production of lithium compounds does
not present a challenge during chemical processing (Banks et al., 1953).
Magnetic separation can be used prior to flotation to remove large
quantities of iron bearing gangue minerals or following flotation to
make the concentrate suitable for use in ceramics and glass manu-
facturing. For example, the processing of Greenbushes’ pegmatite in-
volves the application of wet high intensity magnetic separator to re-
move iron bearing minerals such as tourmaline prior to spodumene
flotation. The non-magnetic product is screened at 400 µm to obtain a
spodumene concentrate assaying 7.5–7.7% Li2O and less than 0.1%
Fe2O3 (Bale and May 1989). The magnetic separation studies conducted
with +149 µm spodumene concentrate indicated that the non-magnetic
fraction of the concentrate was 18.6 wt% and assayed at > 7.35% Li2O
and < 0.5% Fe2O3 (McVay and Browning, 1962; Jirestig and Forssberg,
1994).
The high magnetic susceptibility of zinnwaldite, due to its high iron
content, makes it suitable for beneficiation with magnetic separation
techniques. For example, magnetic susceptibility of zinnwaldite of
about 270 × 10−9 m3 kg−1 was reported (Leißner et al., 2016). It is
important to highlight that automated mineralogy can be used as a way
of evaluating the efficiency of the magnetic separation (Leißner et al.,
2016). Magnetic separation has been shown to be effective in
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Minerals Engineering 131 (2019) 170–184
separating zinnwaldite from tin-tungsten mining tailings in the Czech
Republic (Botula et al., 2005). Botula et al., (2005) showed that zinn-
waldite can be recovered into the magnetic concentrate fraction in a
relatively broad magnetic induction range (3500–7200 × 10−4 Tesla)
due to its strong magnetic properties. The use of wet high intensity
magnetic separation on a zinnwaldite flotation concentrate at Trelavour
Downs and Rostowrack mine in the UK resulted in a 2.07% Li2O con-
centrate at a recovery of 73%. The magnetic fraction was identified as
being predominantly zinnwaldite (Siame and Pascoe, 2011).
3.3. Sensor-based sorting
Sorting is a technique used to separate materials based on various
properties including colour, density or electromagnetic properties. Ore
sorting can be done by either manual hand sorting and automated
mechanical sorting. The hand sorting technique exploits mineral
properties such as weight (density) and colour of an ore where in-
dividuals with an experience and knowledge of these characteristics
identify and separate valuable ore from gangue by hand (Fenby, 2014).
In the early days of ore beneficiation, hand sorting was used to separate
spodumene (Munson and Clarke, 1955) and gold ores (Barton and
Peverett, 1980). However, the need to process a large tonnage of low
grade ore, and the need for fine milling to improve mineral liberation
led to the decline in the application of hand sorting in mineral pro-
cessing (Wills and Finch, 2016). Consequently, automated ore sorting
techniques are becoming more dominant in recent years (Von
Ketelhodt, 2009; Wills and Finch, 2016).
Studies conducted on the use of automated sorting in lithium ore
beneficiation are scarce. Spodumene is known to exhibit a range of
colour spectrum such as white, gray, dark-brown, black, red, green,
blue, pink, dull and soapy depending on the level of alteration of the
mineral and the presence of impurities. Brandt and Haus (2010) re-
ported a selective separation of lithium pegmatite ore from quartz and a
K-feldspar using a combination of electrodynamic fragmentation and
optical sorting. This technique exploits the differences in colour, mor-
phology and grain size of the minerals in the ore. It was claimed to
B. Tadesse et al.
produce high grade spodumene, quartz and feldspar concentrates
(Brandt and Haus, 2010). However, the study did not specify the grade
and recovery obtained for spodumene by this technique (Brandt and
Haus, 2010). The likely challenge with colour sorting of spodumene is a
possible overlapping of spodumene colours with those of gangue mi-
nerals.
3.4. Flotation
Froth flotation is the most widely used technique for the bene-
ficiation of lithium bearing minerals such as spodumene. It is a tech-
nique based on surface characteristics of minerals and is used to con-
centrate lithium minerals from pegmatite ores. It is particularly applied
in the treatment of complex or low grade ores where the average par-
ticle size or difference in SG between the target minerals and gangue is
too small for efficient gravity separation. Reverse and direct flotation
techniques have been used for the concentration of lithium minerals
from pegmatite ores. In reverse flotation, gangue minerals are floated
with cationic collectors to produce spodumene concentrate (as tailings)
whereas in direct flotation, spodumene is floated with anionic collec-
tors to reject gangue minerals to the tailings (Redeker, 1979). Flotation
results in a high grade lithium concentrate as compared with other
methods such as DMS (Amarante et al., 1999; Menendez et al., 2004). It
is reported that flotation replaced DMS for beneficiation of spodumene
in pegmatite ores in the early 1960s due its superior performance
(Redeker, 1979). The similarity in mineralogical characteristics be-
tween lithium bearing minerals and gangue minerals presents a chal-
lenge in the selective flotation of lithium minerals such as spodumene
(Moon and Fuerstenau, 2003) and lepidolite (Choi et al., 2012; Vieceli
et al., 2016a). Several factors are known to influence the selective re-
covery of lithium minerals by flotation including the surface chemistry
of minerals, type and concentration of collector, pulp pH, and pre-
treatment methods, and the presence of slimes. These factors will be
reviewed in the next sections.
3.4.1. Mineral surface chemistry
Silicate minerals possess a general similarity with each other be-
cause they consist of (SiO4)4− tetrahedral framework in which a silicon
atom is shared by four oxygen atoms. This suggests that the bonding
potential of oxygen in the SieO bond are not fully utilised. For example,
spodumene and beryl belong to the metasilicate group where each
(SiO4)4− share two oxygen atoms. Lepidolite and muscovite belong to
the mica group of silicates, in which the (SiO4)4− share three oxygen
atoms resulting in two-dimensional sheet structures. When four oxygen
atoms are shared by (SiO4)4−, quartz and microcline are formed as a 3D
network of tetrahedra (Lombe, 1983). Thus, the (SiO4)4− tetrahedral,
based on the number of oxygen atoms shared, can give rise to various
structural modifications which in turn results in silicates with different
chemical and physical properties. Based on the aforementioned struc-
tural properties of silicate minerals, some minerals such as spodumene,
beryl and microcline will have a larger number of Si-O bonds ruptured
during comminution, which may lead to comparable points of zero
charges between them. As electrostatic interaction is the most com-
monly accepted model used to explain the adsorption of collectors on
silicate mineral surfaces, it may be expected that spodumene, beryl and
microcline show similar flotation behaviour due to similarities in sur-
face chemistry. In the same way, lepidolite and muscovite may also
behave similarly in flotation (Lombe, 1983). In general, crystal chem-
istry (e.g., cleavage edges and basal planes) are reported to control the
surface properties of aluminosilicate minerals such as surface charge,
surface hydrophobicity and surface free energy which consequently
influence their flotation (Gupta and Miller, 2010; Yin et al. 2012).
3.4.1.1. Spodumene. The crystal structure of spodumene is found to be
distinctive from other aluminosilicates. The spodumene crystalline
planes of {1 1 0} and {0 0 1} are reported to have varying degree of
175
Minerals Engineering 131 (2019) 170–184
Fig. 5. Correlation between contact angles on {1 1 0} crystal plane and flota-
tion recovery of spodumene with pH in the presence of 10−4 M sodium oleate
solution ().
adapted from Moon and Fuerstenau, 2003
hydrophobicity due to the presence of two unsatisfied coordinations on
{1 1 0} and just one broken Al-O bond on the {0 0 1} crystal plane
(Moon and Fuerstenau, 2003). This was confirmed from the difference
in contact angles between the two planes. Thus, it is to be expected that
surface chemistry plays a key role in the selective flotation of
spodumene. Spodumene shows a high contact angle at the {1 1 0}
cleavage plane and thus collectors such as sodium oleate preferentially
chemisorb onto the surface aluminum sites at the {1 1 0} cleavage plane
of spodumene (Moon and Fuerstenau, 2003). Contact angle
measurements on the {1 1 0} plane correlate very well with the
flotation recovery observed for spodumene. It can be seen from Fig. 5
that the flotation recovery of spodumene with pH shows a primary peak
at pH 8 and a secondary peak at pH 4, similar to contact angle
measurements. The primary peak observed at pH 8 was attributed to
the chemisorption of oleate on the surface Al sites of spodumene while
the secondary peak at pH 4 is ascribed to the presence of ferric iron
impurity (Moon and Fuerstenau, 2003). The above experimental
observations by Moon and Fuerstenau (2003) were confirmed using
computer molecular models that simulated the interactions between
spodumene and oleate as well as interactions between gangue silicates
and oleate (Rai et al. 2011). It was suggested that the {1 1 0} cleavage
plane of spodumene is the most favourable site for oleate molecules
chemisorption. Zhu et al. (2015) conducted flotation studies on wet and
dry ground spodumene samples and found that wet ground spodumene
had more {1 1 0} and {1 0 0} crystal planes while dry ground
spodumene had more {0 1 0} plane exposed on its surface. It was
observed that the oleate adsorption density on wet ground sample was
twice that of dry ground sample which also corresponded to the higher
flotation recovery for wet ground sample than dry ground sample (Zhu
et al., 2015).
3.4.1.2. Lepidolite. Liu et al. (2015b) used quantum mechanics (QM)
and hybrid quantum mechanics/molecular mechanics (MM) methods to
investigate the effect of differences in crystal structures and electron
density distributions on the flotation mechanisms of lepidolite from
muscovite, quartz and albite. They found that although lepidolite and
muscovite have significant differences in chemical formation, they
exhibit similar surface structural properties. Thus, lepidolite and
muscovite showed similarities in their dodecylammonium adsorption
energies suggesting increased difficulty in separating the two minerals
from each other using flotation (Liu et al., 2015b). On the other hand,
the gangue minerals such as albite and quartz showed significant
differences in adsorption energies from lepidolite and muscovite, and
B. Tadesse et al. Minerals Engineering 131 (2019) 170–184

Table 4
Isoelectric points (IEP) of various lithium minerals published in the literature.
Mineral IEP References

Spodumene 2.9 Xu et al. (2016b)

2.5 Jie et al., 2014; Liu et al., 2015a
2.3 Moon and Fuerstenau, 2003
2.8 Lombe, 1983; Tian et al., 2017
2.9 Xu et al., 2016b
2.68 Wang and Yu, 2007
3 Valadao et al., 1984
Lepidolite <2 Choi et al., 2012
< 2.7 Lombe, 1983
2.6 Valadao et al., 1984
1.8 Leja, 1982
Petalite 2.0 Valadao et al., 1984
Amblygonite 5.6 Valadao et al., 1984

thus can be separated under certain pH conditions.

3.4.2. Zeta potential/IEP of lithium minerals
In the flotation of silicate minerals such as spodumene and lepido-
lite which possess similar surface characteristics with those of gangue
silicates, surface charge on minerals plays key role in determining flo-
tation selectivity and recovery. The isoelectric point (IEP) is an im-
portant parameter frequently used in assessing the changes in mineral’s
surface charge with pulp pH via the measurement of zeta potential. IEPs
values reported for spodumene, lepidolite, petalite and amblygonite
reported in the literature are given in Table 4.
It can be seen that most of these lithium minerals have IEP of < 3
which is also generally the case for other silicate gangue minerals such
as quartz (2.5), albite (2.3), feldspar (2.15) and muscovite (1.0) (Choi
et al., 2012; Tian et al., 2017; Fuerstenau and Pradip, 2005). This in-
dicates that the selective flotation of lithium minerals is challenging
particularly using cationic collectors where electrostatic interaction is
the main mechanism for the adsorption of the collector onto the mi-
neral surface.
3.4.3. Effects of chemical pre-treatment and de-sliming
The pre-treatment of lithium ores during flotation is an important
step of the separation process. The objectives of this treatment is to
‘clean’ or modify the surface of minerals before flotation. Early prac-
tices of spodumene surface cleaning may have started in the 1940s and
it was found necessary to clean the surface for its flotation to be se-
lective (Norman and Gieseke, 1940). NaOH, Na2S and NaF are used in
the pre-treatment of lithium pegmatite ores (Moon and Fuerstenau,
2003; Yu et al., 2015a). At the Kings Mountain operations in the US,
cleaning of spodumene was conducted through the addition of 225 g/t
NaOH to the grinding mill before it was fed to the flotation circuit
(Redeker, 1981). Typically, the dosage of NaOH used for pre-treatment
ranges from 0.5 to 2 kg/t and conditioning is conducted for 20–30 mins
(Bulatovic, 2015).
X-ray photoelectron spectrometer (XPS) studies conducted on the
surface of spodumene after cleaning in alkaline solution showed that
the elemental molar ratio of lithium reduced while that of aluminum
slightly increased (Moon and Fuerstenau, 2003). The increase in alu-
minum surface sites was because of the dissolution of silica tetrahedral
framework that exposed more aluminum sites on spodumene. By con-
trast, the dissolution of lithium from spodumene surface decreased its
surface concentration (Moon and Fuerstenau, 2003). The enhanced
flotation of spodumene after sodium hydroxide pre-treatment was as-
cribed to increased interaction of exposed aluminum sites with the
collector (Moon and Fuerstenau, 2003; Xu et al., 2016b). The flotation
recovery of spodumene increased with an increase in dosage of sodium
hydroxide (Yu et al., 2015a).
As shown in Fig. 6, pre-treatment with NaOH (pH 12 leach) appears
to enhance the flotation recovery of spodumene using sodium oleate
Fig. 6. Effects of alkaline leaching at pH 12, aluminum nitrate and ferric nitrate
pre-treatments of spodumene on its flotation recovery at various pH in the
presence of 10−4 M sodium oleate ().
adapted from Moon and Fuerstenau, 2003
collector at pH 4, and over a wide range in alkaline pH conditions.
Moon and Fuerstenau (2003) have attempted to provide an explanation
for these observations by conducting experiments involving spodumene
pre-treatment in ferric or aluminum nitrate solutions. It was shown that
(Fig. 6), after the treatments in aluminum nitrate and ferric nitrate
solutions, the flotation recovery of spodumene is affected only in the
acidic region (secondary peak), with no significant change in the al-
kaline pH region (primary peak). By comparing the peak positions and
their appearances after aluminium nitrate and ferric nitrate pre-treat-
ments, they concluded that the secondary flotation peak at pH 4 is most
likely caused by ferric iron impurities present in the spodumene sample,
while the primary peak at pH 8 is due to oleate chemisorption on Al
sites that originated from spodumene crystal (Moon and Fuerstenau,
2003). It is important to note that the flotation of spodumene with oleic
acid shows only a primary peak at pH 8, thus confirming the conclusion
by Moon and Fuerstenau (2003) that the secondary peak at pH 4 was as
a result of the interaction of oleate ion with iron impurity in the mineral
(Menendez et al., 2004; Yu et al., 2015b).
In many lithium ore beneficiation plants, it is a common practice to
de-slime the ore prior to flotation. De-sliming is typically carried out to
remove the −20 µm size fraction to improve selectivity of separation
because slimes are detrimental to the flotation circuit (Bale and May,
1989). As is the case in many operations, de-sliming is often done using
hydrocyclones. The cut size of the cyclone is dictated by the desired size
distribution and degree of liberation. At Greenbushes spodumene pro-
cessing in Western Australia, cyclones are used for secondary classifi-
cation of the −250 µm size fraction where −20 µm slimes are removed
as tailings (Bale and May, 1989). The underflow from this classification
is fed into flotation circuit. According to Redeker (1981) the separation
of spodumene from feldspar and quartz gangue minerals at Kings
Mountain processing plant involves a de-sliming step that rejects
−15 µm particles to waste during which 7.4 wt% feed assaying 1.43%
Li2O is discarded.
3.4.4. Flotation of spodumene
Anionic collectors such as oleic acid, sodium oleate, sulphonated
and phosphorated fatty acids are widely utilized for the flotation of
spodumene from pegmatite ores (Norman and Gieseke, 1940). Spodu-
mene recoveries in excess of 90% and concentrate grade of 6.52% Li2O
can be achieved with oleic acid (Norman and Gieseke, 1940). A pilot
plant study conducted on the flotation of spodumene from pegmatite of

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Table 5
Typical collectors used in the flotation of lithium pegmatite ores.
Collector type Mineral(s) floated Dosage (g/t) Pulp pH References

Armac T Feldspar, quartz and mica 180–315 Banks et al., 1953

Tallow amine acetate Mica, feldspar 113–180 3.0–3.5 Redeker, 1981
Sodium resinate Iron-bearing minerals 900 Banks et al., 1953
Stearyl trimethyl ammonium chloride Lepidolite 50–200 2–9 Choi et al., 2012
Aeromine 3000C Lepidolite 350 3 Vieceli et al., 2016a
Armeen 12D Lepidolite 500 3 Vieceli et al., 2016a
Tall oil fatty acid Spodumene 680 7 Redeker, 1981
Oleic acid + naphthenic acid Spodumene 500 + 200 8.5–9.5 Amarante et al., 1999
Sodium oleate Spodumene Variable 8 Moon and Fuerstenau, 2003
Oleic acid Spodumene 1400 7.5–9.8 Menendez et al., 2004
Sodium oleate + dodecyl trimethyl ammonium chloride Spodumene 9:1 M ratio 8–9 Tian et al., 2017

Fig. 7. Schematic illustration of the reaction of the single NaOL (a) and mixed NaOL/DTAC (b) collectors with active sites on the spodumene surface (Tian et al.,
2017).

Cleveland County (United States) using oleic acid resulted in 76.7%
spodumene recovery with 6.4% Li2O (McVay and Browning, 1962).
Anionic collectors were principally used for concentrating North Car-
olina spodumene pegmatite ore at industrial scale (Redeker, 1979). A
mixture of fatty acids such as rosin acid, linoleic acid, oleic acid, erucic
acid, and arachidonic acid in fuel oil was found to be effective in spo-
dumene flotation (Knocke et al., 1975). Cationic collectors such as
amine acetate are typically used for the reverse flotation (gangue flo-
tation) of spodumene to remove quartz, feldspar and mica (Banks et al.,
1953). Owing to their inferior flotation performance, cationic collectors
have been replaced by more selective anionic collectors. It was reported
that improved selectivity in spodumene flotation from other gangue
minerals such as feldspar and mica can be achieved by using a mixture
of anionic and cationic collectors (Xu et al., 2016a). Table 5 provides a
summary of common anionic and cationic collectors used for direct or
reverse flotation of lithium pegmatite ores.
The adsorption density of oleic acid and sodium oleate onto spo-
dumene was found to increase with increasing concentration of oleate
ions (Moon and Fuerstenau, 2003; Yu et al., 2015b). Studies on surface
interaction of spodumene with these collectors indicated that adsorp-
tion of oleic acid and sodium oleate onto the spodumene surface was
optimal at pH 8–9 where the flotation of spodumene was maximum
(Moon and Fuerstenau, 2003; Yu et al., 2015b; Zhu et al., 2015).
Maximum adsorption was also observed at pH where significant change
in zeta potential of spodumene-oleate system was observed (Moon and
Fuerstenau, 2003). Also, investigation on surface tension of oleic acid
solutions indicated that the surface tension was minimal at around pH
8–9 which corresponds to maximum flotation of spodumene. The low
surface tension of oleic acid at these pHs was ascribed to strong hy-
drophobicity of the oleic acid collector (Yu et al., 2015b).
Mixed cationic/anionic collectors have prompted research interest
in recent years due to their possible synergistic effect as compared with
single surfactants (Vidyadhar and Rao, 2007). Some studies suggest that
the flotation separation efficiency of minerals could be enhanced using
a mixture of collectors because synergetic effects lead to enhanced
mineral recovery, improved adsorption behaviour of collector on the
target mineral surface, and enhanced selectivity (Rao and Forssberg,
1997; Xu et al., 2013). Cationic collectors such as dodecylamine gen-
erally result in high recoveries but lack selectivity while the opposite is
true for anionic collectors (Wang et al., 2018). For instance, it was
shown that when sodium oleate (NaOL) and dodecyl ammonium
chloride (DTAC) mixed at a molar ratio of 9:1 was used as collector,
high selectivity was achieved for the flotation of spodumene from
feldspar (Xu et al., 2016a, 2016b). Spodumene recovery also increased
from 50% when NaOL alone was used as a collector to 82.15% in the
mixed case. The mechanism for this observation was partly attributed
to the higher surface activity and a denser molecular arrangement in
the mixed NaOL/DTAC case than in single NaOL or DTAC (Tian et al.,
2017). Fourier transform infrared analyses suggested that in the mixed
NaOL/DTAC system, NaOL first reacts with Al sites on the spodumene
surface which is then followed by complexation of DTAC with NaOL
and its co-adsorption on the Stern layer as shown in Fig. 7 (Tian et al.,
2017).
In addition to collectors, several conditioning reagents are used in
the flotation of lithium pegmatite ores (Table 6). The use of gangue
minerals or spodumene depressants is practiced to improve mineral
selectivity during flotation. In the reverse flotation of gangue minerals,
the pulp is conditioned with starch and dextrin to depress spodumene
(Redeker, 1979). Sodium carbonate is reported to depress flotation of
feldspar during flotation of calcium ion-activated spodumene with
mixture of anionic and cationic collectors (Xu et al., 2016a). The ad-
dition of up to 6 × 10−3 mol/L Na2CO3 led to decrease in feldspar

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B. Tadesse et al.
Table 6
Conditioning reagents used in flotation lithium pegmatite ores.
Reagent Purpose
Sodium hydroxide Activator
Ferric chloride Activator
Calcium chloride Activator
Sodium fluoride Activator
Sodium carbonate Depressant
Quebracho extract Depressant
Dextrin or starch Depressant
flotation recovery from 95% to 20% with insignificant effect on the
spodumene recovery (Xu et al., 2016a). The depressing effect of sodium
carbonate in spodumene flotation was also reported by Browning and
McVay (1961). Quebracho extract has been used to depress quartz
during flotation of spodumene with oleate (Browning and McVay,
1961). There is limited literature on the use of depressants in spodu-
mene flotation.
The use of polyvalent metal cations such calcium and ferric ions as
activators during spodumene flotation is extensively reported (Yang,
1978; Wang and Yu, 2007; Jie et al., 2014; Yu et al., 2014). The re-
covery of calcium-activated spodumene was maximum at pH 11.6 when
it was floated with 75% oleic acid and 25% dodecyl amine mixed col-
lector (Wang and Yu, 2007). Liu et al. (2015a) investigated the effect of
calcium and magnesium ions on flotation of spodumene. They found
that the flotation recovery of spodumene increases with increasing
concentration of calcium and magnesium ions. Maximum recoveries of
spodumene were observed at pH 12.5 and 10.0 with Ca2+ and Mg2+
activation, respectively (Liu et al., 2015a). Mineral surface studies
suggested the presence of hydroxy complexes (CaOH(I) and MgOH(I)),
and precipitated metal complexes such as Ca(OH)2 and Mg(OH)2 on
mineral surface which is claimed to have increased sodium oleate ad-
sorption (Liu et al., 2015a). However, it has been reported that calcium
ions may also activate the flotation of other gangue minerals such as
feldspar (Xu et al., 2016a). Similarly, ferric ions are found to enhanced
flotation of spodumene via surface adsorption which leads to increased
interaction with sodium oleate (Moon and Fuerstenau, 2003; Jie et al.,
2014; Xu et al., 2016b). In comparison with calcium ions, ferric ions
were found to be better activators for spodumene flotation (Wang and
Yu, 2007).
3.4.5. Flotation of lepidolite
Lepidolite is often associated with gangue silicate minerals such as
calcite, muscovite, feldspar and quartz. Although the flotation beha-
viour of these gangue minerals is well known, studies aimed at separ-
ating lepidolite from these silicate minerals by flotation are rare.
Cationic collectors (e.g., dodecyl amines) are usually used in the flo-
tation of lepidolite. Choi et al. (2012) investigated the use of stearyl
trimethyl ammonium chloride (STAC) as collector in the flotation of
lepidolite from an ore containing gangue minerals such as feldspar,
quartz, calcite, calcite and muscovite. The flotation was performed in
three stages based on the IEP of the target and gangue minerals which
were found to be < 2, 2.5, 2.3 and 9.7 for lepidolite, quartz, albite and
calcite, respectively (Choi et al., 2012). Firstly, the pulp was floated at
pH 9 with 50–200 g/t of STAC and 40 g/t frother (AF-65) to separate
calcite by depressing its flotation (Choi et al., 2012). Secondly, the
concentrate from the first flotation stage was cleaned in the pH range of
6–8 with 50 g/t of STAC collector and 20 g/t frother to further remove
calcite. Lastly, lepidolite was selectively floated at pH 2 from the second
concentrate because lepidolite was expected to show higher electro-
static interaction with STAC than quartz and albite at this pH. Lepi-
dolite recovery of 76.3% was reported by this procedure with a con-
centrate grade of 3.8 times higher Li2O% than that of the feed. In
another study, Vieceli et al. (2016a) used Aeromine 3000C and Armeen
12D collectors to float lepidolite from lepidolite pegmatite ore. Weak
Minerals Engineering 131 (2019) 170–184
Mineral activated or depressed Reference
Spodumene Moon and Fuerstenau, 2003
Spodumene, quartz Jie et al., 2014; Yu et al., 2014
Spodumene Yu et al., 2014
Spodumene McVay and Browning, 1962
Feldspar Xu et al., 2016a
Quartz McVay and Browning, 1962
Iron-bearing minerals Banks et al., 1953
selectivity of lepidolite from quartz and albite was reported which lead
to only slight enrichment of Li grade in the concentrate. A better se-
lectivity was reported at pH 3 for both collectors; however, Armeen 12D
was suggested to have limited potential for this application due to its
poor solubility in water (Vieceli et al., 2016a). In a separate study, the
same authors conducted a grade-recovery modelling and optimization
of the froth flotation process of a lepidolite ore and showed that at pulp
pH of 2 and collector dosage of 500 g/t, lepidolite recovery of 91.51%
and concentrate with Li content of 1.96% can be achieved (Vieceli
et al., 2016b). He et al. (2013) claimed that the use of mixed cationic
collectors in the flotation of lepidolite from a gravity tailings at the
YiChum tantalum and niobium mine in China led to lepidolite recovery
of 70.37% with Li concentrate grade of 4.12% as compared with 40%
recovery at 3.5% grade when a single amine collector was used. Star-
ches and Na2S are depressants for lepidolite while sodium silicate and
lithium sulphate can be used as a lepidolite activators (Bulatovic,
2015). It should be noted that only a few studies exist on the flotation of
lepidolite and thus further studies on the mechanism of collector ad-
sorption, and the effects of activators and depressants are required for a
better understanding.
3.4.6. Flotation of petalite
Scant studies exist in literature on the flotation behaviour of peta-
lite. On a study conducted on complex petalite ore containing feldspar,
lepidolite, mica, and albite, it was claimed that the use of dodecylamine
as collector at pH varying between 2.0 and 8.0 results in no selective
flotation of petalite (Bulatovic, 2015). However, it was suggested that
when a reagent scheme involving 500 g/t HF, NaCl/KCl brine (1:1) and
380 g/t AMG93 (AkzoNobel) collector was used, 85% petalite recovery
with a concentrate grade of 4.7% Li2O was achieved (Bulatovic, 2015).
Further studies are required to understand the flotation behaviour of
petalite and develop reagent schemes.
3.5. Recovery of valuable by-products
Tantalum commonly occurs as Ta-Nb oxide minerals in pegmatite
ores containing spodumene. Thus, in cases where the tantalum is of
economic amount, it can be recovered as a by-product. Many spodu-
mene deposits in Western Australia (e.g., Greenbushes, Mt Marion and
Bald Hill) are also important sources of tantalum oxide. Gravity se-
paration is typically used to concentrate tantalum oxides from lithium
ores (Bale and May 1989). Feldspar is a common occurrence in spo-
dumene ores, and has applications in glass making. K-feldspar is a key
component in the manufacturing of ceramic materials. Froth flotation is
the main method used for the recovery of feldspar from lithium ores
because its flotation properties are well understood (Fuerstenau and
Pradip, 2005). Beryl, which is a beryllium aluminum silicate, is another
important by-product of lithium hard rock processing. For example, it is
found to occur with spodumene at the Kings Mountain in the US, and
the Bikita deposits in Zimbabwe. Beryl is the commercial source of
beryllium which is used for alloy making in applications such as
springs, electrical contacts, spot-welding electrode, and as a structural
material for high-speed aircraft, missiles, spacecraft, and communica-
tion satellites. Beryl in lithium ores can be recovered from spodumene
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Table 7
Main minerals and typical metallurgical results for some selected lithium processing plants (Bale and May, 1989; Bulatovic, 2015; British Geological Survey, 2016).
Plant Main minerals Main gangue Feed grade Conc. grade
(Li2O wt%) (Li2O wt%)

Greenbushes Spodumene, cassiterite, tantalite Tourmaline 4.0 7.5–7.7

Kings Mountain Spodumene Soda- feldspar, quartz, muscovite 1.4–1.5 6.34
Bernic Lake Spodumene, amblygonite, tantalite Soda-feldspar and quartz 3.22 7.25
Bikita Petalite, lepidolite, and amblygonite 4.2 4.5–7.3
Bald Hill Spodumene, tantalite Muscovite 1.18 6.55

flotation tailings using HF activator and oleic acid collector (Browning
and McVay, 1961).
4. Plant practices in the beneficiation of lithium bearing ores
A number of plants exist around the world that are known or be-
lieved to be producing lithium concentrate from ores including in
Australia (Greenbushes, Mt Cattlin, Mt Marion, and Bald Hill), Brazil
(Mibra), Canada (Bernic lake), China (Sichuan Aba, Maerkang, Jiajika),
the United States (Kings Mountain) and Zimbabwe (Bikita) (Evans,
2014). The beneficiation and treatment options adopted at these plants
largely depend on the mineralogy (both target and gangue) of the ore. A
summary of typical target and gangue minerals and the metallurgical
performance of selected plants is given in Table 7. In the following
sections, beneficiation methods employed at some of the larger cur-
rently operational and non-operational plants in the world will be re-
viewed. While processing at some of these operations (e.g., Kings
Mountain) is not currently undergoing, it is believed that valuable in-
sights can be gained from examination of past practices to adopt some
aspects of the beneficiation methods for similar deposits in the future.
4.1. The Greenbushes, Australia
The Greenbushes Lithium Operations, located in Western Australia,
have been producing lithium for over 25 years and is recognised as the
longest continuously operated lithium mining operation in Western
Australia. It is a major producer of lithium concentrate in the world.
The ore reserves at Greenbushes was estimated to be in excess of 30
million tonnes, with at least 7 million tonnes at 4.0% Li2O (Bale and
May, 1989). The Greenbushes Lithium Operations has two processing
plants; one producing technical-grade lithium concentrate and the
other producing chemical-grade lithium concentrate. The ore is up-
graded using gravity, heavy media, flotation and magnetic separation to
produce these lithium concentrates according to the flowsheet shown in
Fig. 8.
Run of mine spodumene ore is crushed −16 mm by primary and
secondary jaw crushing and tertiary cone crushing which is then fed to
a ball mill. The undersize (−250 μm) fraction from the ball mill dis-
charge is feed to cyclones to remove the slimes (−20 μm) as tailings,
and the cyclone underflow is fed to the flotation circuit (Bale and May,
1989). The oversize (+250 μm) from the ball mill discharge is screened
at 800 μm where the undersize is subjected to a magnetic separation to

Fig. 8. Greenbushes spodumene processing flowsheet similar to one of the processing plants currently in operation (as of May 2018).

179
B. Tadesse et al.
Fig. 9. A simplified flowsheet for spodumene flotation at Kings Mountain, USA (modified from Redeker, 1981).
produce a glass grade spodumene in the non-magnetic fraction. The
screen oversize is recycled to the ball mill. In the flotation circuit, the
first stage involves bulk flotation of spodumene and tourmaline using
fatty acid collector and soda ash. Following roughing, cleaning and re-
cleaning stages, spodumene concentrate assaying about 7.2% Li2O and
0.4% Fe2O3 is produced. Gravity separation is employed on the flota-
tion concentrate to recover heavy minerals such as cassiterite and
tantalite, while magnetic separation is then used to remove the tour-
maline. The final concentrate grade assays 7.5–7.7% Li2O and < 0.1%
Fe2O3 (Bale and May, 1989).
4.2. The Kings Mountain Operations, USA
The pegmatite deposit in the Kings Mountain district in North
Carolina is considered as one of the three largest lithium bearing peg-
matite deposits in the world together with the Manono deposit in the
Democratic Republic of Congo (DRC) and Greenbushes in Australia,
although only the latter produces lithium concentrate at present
(British Geological Survey, 2016). The Kings Mountain was the prin-
cipal producer of glass, ceramic and chemical grade spodumene since
the 1950s before its closure in 1998 due to the commencement of
cheaper brine operations in South America (British Geological Survey,
2016). In addition to spodumene, mica, feldspar and quartz were major
by-products. A simplified flowsheet for spodumene flotation is shown in
Fig. 9. The ore with head grade of 1.64% Li2O is milled to −16 mm by
ball mill grinding to increase degree of liberation. About 400 g/t of
NaOH is added for spodumene surface cleaning during ball milling
which is operated in a closed circuit with cyclone. The cyclone overflow
is re-cycloned to remove the −15 μm slimes. The slimes account for
7.4% wt at 1.43% Li2O. The +15 μm material is conditioned at 55%
solids in neutral pH conditions with 700 g/t of tall oil fatty acid and
glycol-type frother. The conditioned pulp is floated at 30% solids fol-
lowed by cleaning and re-cleaning stages to obtain 6.34% Li2O grade
concentrate at 93.5% recovery.
4.3. Bernic Lake lithium operation, Canada
The Bernic Lake group of pegmatites in Manitoba represent a
complex zoned pegmatites with over 100 different minerals including
spodumene, lepidolite, amblygonite, petalite and eucryptite (British
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Minerals Engineering 131 (2019) 170–184
Geological Survey, 2016). The Bernic Lake mine was originally estab-
lished in 1929 for tin processing. In 1969 the mine started its operations
as a tantalum mine which was followed by spodumene processing in
1984. Over the years, spodumene, together with tantalum, caesium,
and rubidium were the major products at this processing plant. It was
reported that the amblygonite in the ores created a problem in the re-
covery of spodumene due to its phosphorus content which is an im-
purity in production of high-grade spodumene (Bulatovic, 2015). The
beneficiation flowsheet at Bernic Lake involved dense media separa-
tion, pre-flotation of amblygonite, magnetic separation and flotation as
illustrated in Fig. 10. The feed size to the dense media separator was
−12 + 0.5 mm in which a mixture of ferrosilicon and magnetite with
media density of 2.7 was used as a media. The light fraction (K-feldspar)
was rejected while the dense fraction (sinks) was ground to −0.25 mm
and processed further. Iron was removed from the fine fraction by low-
intensity magnetic separation, which was then followed by gravity se-
paration to remove tantalum containing fraction. The next stage was
the removal of amblygonite by flotation. The amblygonite flotation
involved the use of starch as spodumene depressant and tall oil col-
lector. The tailings were then floated to remove the soda-feldspar and
quartz by reverse flotation, and produce a spodumene concentrate
grading 7.25% Li2O (Cerny et al., 1996). During spodumene flotation,
mixtures of petroleum sulfonate and fatty acids (LR19) was used as
collector, and Na2CO3 was used as a pH modifier. The spodumene
rougher and cleaning was performed at pH 9.5.
4.4. The Bikita Operation, Zimbabwe
Bikita pegmatite is one of the world’s largest lithium deposits and
contains most of the major lithium minerals including spodumene,
petalite, lepidolite, eucryptite and amblygonite (Von Knorring and
Condliff, 1987). The Bikita pegmatite area possesses a variety of high
tonnage of lithium minerals (23,000 Mt lithium) as well as tantalum,
tin, beryl and pollucite (Garret, 2004; Jaskula, 2015). In 2014, the
production of lithium minerals concentrate was about 44,000 tonnes at
an average grade of 4.2% Li2O and 0.03% Fe2O3 (British Geological
Survey, 2016). Beneficiation of the lithium minerals was initially done
by hand picking of coarsely crushed run-of-mine but current production
involves DMS. In the first stage of DMS, petalite concentrate is re-
covered in the float fraction. The sinks fraction is reprocessed at a
B. Tadesse et al.
Fig. 10. Simplified schematic flowsheet of the Bernic lake (Tanco) spodumene processing plant (Cerny et al., 1996).
higher media density to yield a spodumene concentrate.
4.5. Bald Hill lithium and tantalum operations, Australia
The Bald Hill lithium-tantalum mine (jointly owned by Tawana
Resources and Alliance Mineral Assets Limited) in the Eastern
Goldfields, Western Australia started production of spodumene con-
centrate in early 2018. The lithium ore reserve at Bald Hill is estimated
to be 18.3 Mt at 1.18% Li2O. Tantalite is also a major by-product.
The processing plant flowsheet employed for spodumene recovery
at Bald Hill is shown in Fig. 11. The run-of-mine ore is first crushed to
−12 mm particle size. Spirals and shaking tables are used to separate
the high grade tantalite bearing ore. The spodumene contain ore is
subjected to screening to remove −1 mm size fraction which is sent to
storage after removal of the tantalum minerals through rougher spirals.
The −12 + 1 mm size fraction is sent to coarse screening which sepa-
rates the feed to a −12 + 5 mm (coarse fraction) and −5 + 1 mm
(fines fraction). The coarse fraction is mixed with Ferrosilicon (FeSi)
medium and pumped to the primary coarse DMS cyclone. The fines
fraction is pumped to a reflux classifier where mica is removed and the
underflow (fine fraction) is sent to primary fine DMS cyclone. The FeSi
is recovered from the underflows and overflows of both the fine and
coarse primary DMS cyclones, the overflows rejected, and the under-
flow coarse and fine fractions mixed with a higher SG FeSi and sent to
the respective secondary coarse and fine DMS cyclones. The underflow
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Minerals Engineering 131 (2019) 170–184
from the secondary cyclones (coarse and fines), after FeSi removal, is
the main spodumene concentrate product.
5. The future of hard rock lithium ore processing
The global production of lithium has seen rapid growth in recent
years, with an estimated production volume increase of 70% in the past
five years (Martin et al., 2017). The lithium production volume is ex-
pected to rise due to the continuous demand for the metal in new en-
ergy technologies. For example, a leading electric car manufacturer is
constructing a lithium-ion battery plant in Nevada capable of producing
up to 500,000 lithium-ion vehicle batteries per year (US Geological
Survey, 2017). The rise in lithium demand prompted supply security to
become a top priority for technology companies around the world. This
has led to the search for diversified supply of lithium to satisfy demand
for battery suppliers and vehicle manufacturers. Although hard rock
pegmatite ores were the predominant source of lithium over many
decades, continental brine operations in Argentina, Bolivia, Chile, and
China have taken a major share in lithium production in recent years. In
addition, several mining operations involving pegmatites and other
minerals have been developed or are in advanced stages of develop-
ment in Australia, Canada, China, Finland, Serbia and Mexico (Fig. 12).
As can be seen from Fig. 12, lithium production from hard rock peg-
matite deposits is concentrated in a few countries while clays, zinn-
waldite and jadarite are evolving as potential lithium sources.
B. Tadesse et al. Minerals Engineering 131 (2019) 170–184

Fig. 11. Simplified process flow diagram for Bald Hill spodumene processing (May 2018).

The emergence of brine operations in the late 1990s as cheap li- main lithium producer (British Geological Survey, 2016). Brine opera-
thium carbonate sources has dramatically changed lithium production tions, however, have their own production bottle-necks as the eva-
around the world. This has led to the closure of pegmatite mines in- poration process typically requires between one and 2 years before the
cluding the Kings Mountain operations in the US, which was once the final product is ready for use. The long timescales required for lithium

Fig. 12. Location of lithium producing mines from hard rock ores and selected advanced-stage lithium projects, excluding lithium production from brines (Evans,
2014; British Geological Survey, 2016).

182
B. Tadesse et al.
production can make brine deposits unsuitable to meet sudden changes
in demand.
Pegmatite deposits are currently the main sources of lithium from
minerals owing to their relatively coarse grain-sized crystals making
processing less complicated. However, extraction of lithium from mi-
neral concentrates remains a costly and challenge due to the require-
ment for high temperature pre-treatment prior to intense leaching.
Spodumene from pegmatite deposits is expected to be the main source
of lithium from ores as suggested by recent expansions of existing mines
at Greenbushes and Bikita as well as new projects in many locations in
Australia (e.g., Mt Cattlin, Mt Marion, Bald Hill) and Canada (e.g.,
Whabouchi). However, future sources would most probably include
other minerals such as jadarite and hectorite. Deposits of hectorite clay
were not considered as a source of lithium in the past. There appears to
be some interest in extracting lithium from hectorite deposits in
Nevada, USA and Sonora, Mexico (British Geological Survey, 2016).
Jadarite is a new mineral that has been recently discovered by Rio Tinto
in the Jadar Basin, Serbia (Evans, 2014). A large deposit has been re-
ported in the area with a weighted average lithium content of 1.8%
Li2O (British Geological Survey, 2016). Pilot-scale studies and research
in processing methods and extraction of lithium from jadarite are un-
dergoing to assess its suitability as lithium resource (Rio Tinto, 2011).
The Cínovec Sn-W-Li deposit, a significant lithium resource in Europe,
which can be upgraded through multi-stage magnetic separation, has
been claimed to be a potentially low cost hard rock lithium source
(European Metals Holdings Limited, 2018).
In order to compete with the low cost brines, operations based on
the extraction of lithium from hard rocks will need to consider a
number of strategies. It is estimated that crushing and grinding, directly
and indirectly, contribute to about 50% of the costs related to the en-
richment of spodumene to a commercial product (Levich, 2009). Given
that many pegmatite deposits contain easy to liberate coarse grained
target minerals (Brandt and Haus, 2010), coarse particle gangue re-
jection has a potential to significantly reduce costs associated with
unnecessary comminution and downstream extraction stages. For in-
stance, coarse gangue rejection can be achieved via dense medium se-
paration, electrodynamic fragmentation and optical sorting (Brandt and
Haus, 2010). The potential benefit of emerging methods such as reflux
classifier for rejection of gangue minerals (e.g., mica) will need to be
investigated. Traditionally, DMS and froth flotation are the two most
common beneficiation methods employed in the enrichment of lithium
minerals, and only a few improvements have been made to these pro-
cesses in the past few decades. Most research in the past has focused on
the flotation behavior of spodumene with very limited data on the
flotation of other lithium minerals. Detailed fundamental studies on the
beneficiation methods of hectorite and jadarite is crucial to determine if
these minerals could be possible sources of lithium in the future. Lastly,
further technological developments in the extraction of lithium from
concentrates is invaluable as the current route involving calcination at
extreme temperatures and leaching using hydrochloric acid (highly
corrosive) is considered unfavorable.
6. Conclusions
The various techniques used in the beneficiation of lithium minerals
from hard rock pegmatite ores containing spodumene, petalite, lepi-
dolite and amblygonite have been reviewed. Dense media separation
and flotation are the main beneficiation methods used in many plants
around the world. The success in separating lithium minerals from ores
using these methods depends significantly on the differences in specific
gravity, and the chemical and physical properties between lithium
minerals and associated gangue. Studies conducted on the use of au-
tomated sorting methods in lithium ore beneficiation are scarce.
However, this technique is expected to have potential use in the future
because lithium minerals such as spodumene are known to exhibit
distinct color spectrum depending on the level of alteration of the
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Minerals Engineering 131 (2019) 170–184
mineral and the presence of impurities. Most published studies in the
literature focussed on the beneficiation of spodumene as it is the main
lithium bearing mineral currently processed. Detailed studies on other
lithium minerals such as petalite, zinnwaldite and lepidolite is required
to optimize their separation from pegmatite ores. Other future lithium
sources would most probably include minerals such as jadarite and
hectorite.
Acknowledgements
The financial assistance of the Western Australian School of Mines,
Curtin University and CRC ORE is gratefully acknowledged.
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