Minerals Engineering 89 (2016) 119–137

Contents lists available at ScienceDirect

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

Advance review on the exploitation of the prominent energy-storage

element: Lithium. Part I: From mineral and brine resources
Pankaj K. Choubey, Min-seuk Kim, Rajiv R. Srivastava, Jae-chun Lee ⇑, Jin-Young Lee
Resources Recycling, Korea University of Science and Technology, Daejeon 305-350, Republic of Korea
Mineral Resources Research Division, Korea Institute of Geoscience and Mineral Resources (KIGAM), Daejeon 305-350, Republic of Korea

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

Article history: Lithium (Li), an exceptional cathode material in rechargeable batteries, is an essential element in modern
Received 16 July 2015 energy production and storage devices. The continuously increasing demand for lithium in these devices,
Revised 19 December 2015 along with their steady production, has led to the high economic importance of lithium, making it one of
Accepted 15 January 2016
the strategically influential elements. The uneven distribution of mineral resources in the earth’s crust
and the unequal concentration in brine and sea water reserves also causes lithium exploitation to be
of critical importance. This situation requires the efficient processing of lithium resources either by the
Keywords:
processing of minerals/brine/sea water or by the recycling of spent lithium-ion batteries. To explore
Lithium minerals
Brine
new routes for the sustainable exploitation of lithium, it is imperative to review the methodologies that
Energy-critical element have already been studied and are currently in industrial practice. In this study, we present an overview
Leaching of the processes investigated for the extraction, separation and recovery of lithium from not only a
Recovery technological perspective but also from a chemical perspective.
In Part I, this state-of-the-art review addresses the processing of lithium resources that currently con-
tributes to the commercial exploitation of this energy-critical element. This review includes lithium
recovery from mineral (spodumene, petalite, lepidolite, zinnwaldite) and brine resources. A deliberation
of the mineralogical aspect along with a review of the extraction process of lithium minerals is sub-
divided according to the chosen media, namely, chloride, sulfate and carbonate, for their conversion into
a leachable form, whereas the division of aqua-based resources is based on the lithium concentration. In
the discussion, the advantages and/or disadvantages, problems and prospects of the processes are also
summarized. We believe this article can contribute to improving the extraction and recovery processes
of lithium toward the sustainability of this critical element and can provide future research directions.
Ó 2016 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
2. Technological developments in lithium extraction by processing mineral resources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
2.1. Processing of spodumene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
2.1.1. Mineralogical aspects of spodumene metallurgy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
2.1.2. Sulfation processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
2.1.3. Carbonation processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
2.1.4. Chlorination processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
2.1.5. Fluorination processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
2.1.6. Lime processing at elevated temperatures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
2.2. Processing of lepidolite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
2.2.1. Mineralogical aspect of lepidolite metallurgy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
2.2.2. Processing via sulfation roasting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
2.2.3. Processing via carbonation roasting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127

⇑ Corresponding author at: Mineral Resources Research Division, Korea Institute

of Geoscience and Mineral Resources (KIGAM), Daejeon 305-350, Republic of Korea.
E-mail address: jclee@kigam.re.kr (J.-c. Lee).

http://dx.doi.org/10.1016/j.mineng.2016.01.010
0892-6875/Ó 2016 Elsevier Ltd. All rights reserved.
120 P.K. Choubey et al. / Minerals Engineering 89 (2016) 119–137

2.2.4. Processing via chlorination roasting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128

2.2.5. Processing via the de-fluorination and lime pressure leaching process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
2.3. Processing of zinnwaldite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
2.3.1. Mineralogical aspect of zinnwaldite metallurgy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
2.3.2. Processing via sulfation roasting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
2.3.3. Processing via carbonation roasting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
2.4. Processing of amblygonite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
2.4.1. Mineralogical aspect of amblygonite metallurgy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
2.4.2. Processing via sulfate roasting. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
2.4.3. Processing via alkali digestion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
2.5. Existing commercial process for lithium recovery from minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
3. Technological improvement for the extraction of lithium from brine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
3.1. Processing of brine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
3.2. Pre-concentration/pre-treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
3.3. Existing commercial processes for lithium recovery from brine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
4. Perspective and recommendations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
5. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135

1. Introduction and supply of Li2CO3, which is often used in battery materials.

Catastrophic climate changes, global warming and energy crises
are substantial global challenges. The dependency on traditional
fossil-based resources is one of the major causes of the energy
crises. There is a consensus that countries cannot rely indefinitely
on fossil-based energy sources; renewable energy must be devel-
oped as an alternative to meet the growing energy demands
(UNDP, 2000; Rajasthan Renewable Energy, 2015). The conserva-
tion, storage and transmission of renewable energy require the
availability of suitable devices. Batteries have been considered
suitable candidates for power sources in large and portable appli-
cations. For any battery, the most critical feature is the capability of
storing a large amount of energy within a given volume-to-mass
ratio in a short period (J.S. Kim et al., 2014; H. Kim et al., 2014).
For this purpose, lithium (Li, with a very low density of
0.534 g/cm3 combined with a high electrochemical standard
potential of
3.04 V) (Hart and Beumel, 1973) has found applica-
tions in rechargeable batteries as an exceptional cathode material.
Currently, lithium ion batteries (LIBs) are the most promising
rechargeable batteries due to their unmatched characteristics to
capture energy compared to the other technologies (Table 1)
(Salil, 2012; Wagner, 2006). Moreover, as a blanket material in
the fuel regeneration of fusion energy reactors, the large amounts
of energy carried by the neutrons would be transferred to the
excess lithium and then recovered by a heat exchanger (Lithium
World Nuclear Association, 2014).
In addition to the major applications in glass and ceramics
(35%), rechargeable batteries (29%), lubricating grease (9%), air
treatment by CO2 capture (5%), continuous casting mold flux pow-
ders (6%) and polymer production (5%) (Jaskula, 2013), the
unprecedented growth in direct plug-in hybrid vehicles is pro-
jected to increase the demand for lithium in LIBs by >30% by
2020 (Ping et al., 2014; Forster and Rutherford, 2011). The role of
lithium in the fulfillment of the global energy demand is vital for
the energy age of tomorrow. Fig. 1 presents the future demand
A shortage is projected to occur around 2020 (Critical Materials
Strategy, 2010). The mitigation of the supply risk in clean energy
requires more than 1.5-fold of Li2CO3 in 2025 than in 2015
(265 kilo tons) (Critical Materials Strategy, 2010; Fox-Davies
Resources Specialist, 2013). This enormous demand projection
indicates the greater economic importance of lithium than of silver
(ECEI-Report, 2010), even though lithium is the 25th most abun-
dant element (20 mg/kg) in the earth’s crust, with total reserves
of 13,000 kilo tons (including brine) worldwide (Jaskula, 2013;
Fox-Davies Resources Specialist, 2013). The high economic
importance and the capability to transform the methods of
production, transmission, storage, or energy conservation have
placed lithium among the strategically influential elements,
called the ‘‘energy-critical elements”, because of the significant
uncertainty related to time delays in the production and utilization
of lithium (Fox-Davies Resources Specialist, 2013; ECEI-Report,
2010; ECEs-Energy Critical Elements, 2011).
The global production and consumption data of lithium from its
resources are shown in Fig. 2 (Polinares EU Policy on Natural
Resource, 2012; USGS, 2014; USGS Mineral Yearbook, 2013;
Mohr et al., 2012). The efficient processing of resources is compli-
cated largely because of the low concentration of lithium in sea
water (as low as 0.1–0.2 ppm) (Brown, 2010; Shahmansouri
et al., 2015) and the need for beneficiation to upgrade the rock-
minerals followed by an energy-consuming heat treatment (usu-
ally at or above 800 °C) prior to lithium dissolution into aqueous
media (Luong et al., 2013). The aqueous solutions always contain
high levels of impurities, which make downstream processing dif-
ficult. In general, the traditional separation technologies are con-
sidered amateurish, unfriendly to the environment and
unsustainable. Therefore, improving the separation and processing
of lithium from primary and secondary resources is necessary.
Hence, to explore new methods of lithium exploitation, both tech-
nologically and economically, it is imperative to review the
methodologies that have already been explored. It has been nearly

Table 1
Application of lithium ion batteries (Salil, 2012; Wagner, 2006).

Battery type Specific energy density (W h/kg) Specific power (W/kg) Life span cycles Major application areas
Li-ion 100–265 250–340 400–1200 Laptop, computers, mobile devices, modern electric vehicles
Ni–Cd 40–60 150 2000 Cordless & wireless telephones, emergency light
Ni–Zn 100 >3000 400–1000 Cordless telephones, digital cameras, battery operated lawn
Pb-acid 33–42 180 500–800 Automotive engine ignition
 P.K. Choubey et al. / Minerals Engineering 89 (2016) 119–137 121

primary resources. Therefore, while reviewing the exploitation of

Fig. 1. Statistics for the supply and demand of lithium carbonate for the projection
of the future status in the commodity market (Adopted and modified from: Critical
Materials Strategy, 2010).
four decades since the first attempt at lithium exploitation was
undertaken by Averill and Olson, and only a few studies had been
published at that time (Averill and Olson, 1978). The review was
focused on reporting the general idea for the exploitation of
lithium from pegmatite sources with limited information about
the processing of brine. Recently, one attempt by Meshram et al.
(2014) was made to comprehensively review the lithium extrac-
tion processes. The study provided information on resource pro-
cessing with an emphasis on the processing of spent LIBs.
However, the mineralogical aspect, structure, and extraction
chemistry have not been addressed in the previous review articles,
which are important parts of any study on lithium recovery from
lithium from various resources, we attempted to underpin the pro-
cess fundamentals involved in the extraction, separation and
recovery of lithium, along with the conception of commercialized
processes. Moreover, a multi-disciplinary aspect that defines the
extraction processes emphasizes the requirement of understand-
ing the overall scenario by elaborating the chemistry involved in
the metallurgical processes (both pyro and hydro). This state-of-
the-art review can further assist the subsequent research to obtain
sustainable technology for lithium extraction and ultimately con-
tributes to the sustainability of clean energy.
We divide the review according to the lithium resources as (i)
being in commercial production to fulfill the market demand in
the current scenario and (ii) having the potential to be exploited
for sustainability in the near future. The commercialized practice
in lithium (salt/s) production includes the processing of minerals
and brines. A large reserve of lithium exists in ocean/sea water,
and the processing of hydrothermal water and end-of-life LIBs
accounts for future reservoirs (yet to be commercialized for
lithium production).
This paper (Part 1) addresses the technological development
and the processes that are in commercial practice for the exploita-
tion of lithium from mineral and brine resources. During the dis-
cussion of the technology and its improvement, knowledge of the
mineralogical aspect and the enrichment of lithium is important
for processing the minerals and brines, respectively. Whenever
required, the thermodynamics and fundamentals of the chemistry
involved in the process are also addressed to better understand the
extraction, separation and recovery of lithium. A subsequent paper
(Part II) will address the extraction and recovery of lithium from its
future resources (including sea water and the recycling of spent
LIBs), which are identified to have the potential to contribute to
the sustainability of this critical element in the commodity market

Fig. 2. Lithium production (from rock minerals and brines) and consumption data on a yearly basis (2008–2013) (Adopted and modified from: Polinares EU Policy on Natural
Resource, 2012; USGS, 2014; USGS Mineral Yearbook, 2013; Mohr et al., 2012).

Table 2
Chemical composition of minerals (Fox-Devies Resources Specialist, 2013; Martine and Sebastian, 1991; Mizota et al., 1986; Lee et al., 1990; Losey and John, 2004).

Minerals Chemical formula Chemical composition of minerals in weight% Crystalline system

Li2O Na2O K2O Rb2O FeO SiO2 Al2O3 F P2O5 Others
Spodumene LiAl(SiO3)2 6–9 0.55 0.48 – – 63.6 28.7 – – – Monoclinic, 2/m
Petalite LiAlSi4O10 4.73 0.17 0.02 – – 77.7 17.1 – – – Monoclinic
Lepidolite K(Li,Al)3(Al,Si,Rb)4O10(F,OH)2 4.19 0.56 8.55 3.39 – 52.3 28.8 5.9 – 0.2 Monoclinic H-M Symbol, 2/m
Zinwalidite KLiFeAl(AlSi3)O10(OH,F)2 2–5 0.19 10.1 0.45 – 42.8 21.7 6.1 – 0.5 Monoclinic-prismatic
Amblygonite LiAl(F,OH)PO4 7.40 5.12 – – – – 33.6 9.4 46.8 – Triclinic
Eucryptite LiAlSiO4 9.70 0.26 0.16 – – 51.7 36.7 – – – Trigonal–Rhombohedral
Triphylite-79 Li(Fe,Mn)PO4 9.47 0.02 – 34.1 – – – 43.8 10.5 Orthorhombic dipyramidal
122 P.K. Choubey et al. / Minerals Engineering 89 (2016) 119–137

Fig. 3a. Typical structure of a-Spodumene (Adopted and modified from: Skinner and Evans, 1960).

Fig. 3b. Typical structure of b-Spodumene (Adopted and modified from: Skinner and Evans, 1960).

and in the fulfillment of the global energy demand by renewable
methods.
2. Technological developments in lithium extraction by
processing mineral resources
Of approximately 131 known minerals of lithium (Mineralogy
database, 2012), a few silicates and phosphate-based minerals
are of economic importance (Table 2) and have been studied to
exploit the lithium values. Among them, triphylite is principally
found in Europe and Africa, but the high consumption of mineral
acids to decompose the phosphates and then precipitate the liber-
ated lithium as LiPO4 is a major problem in processing these min-
erals (Colton, 1957). The presence of PO
4 linking the polyhedral
oxides of the transition metal does not allow proper overlapping
between their electron orbitals, which results in a very low elec-
tronic conductivity. Eucrypite has generally been considered a very
rare mineral whose processing is the same as other silicate miner-
als; therefore, it is not considered in this review (Norton and
Schlegel, 1955). Various methods have been developed to recover
lithium from its minerals by physical beneficiation followed by
chemical treatment (Walter and Bichowsky, 1935; Victor, 1953;
Robinson and Vale, 1961; Wietelmann and Bauer, 2008; Dresler
et al., 1998; Morstadt, 1987). The complex ores are first enriched
to concentrate the metallic values by physical beneficiation pro-
cesses consisting of size reduction, froth flotation, and magnetic
separation (Bale and May, 1989; Amarante et al., 1999). Employing
surface crystal chemistry, selective flotation of spodumene from
aluminosilicates using an oleate collector has been suggested to
enrich the lithium content for subsequent processing (Moon and
Fuerstenau, 2003). Brandt and Haus (2010) reported electrody-
namic fragmentation and optical sorting methods for the selective
liberation and separation of spodumene from quartz and feldspar
crystals of lithium pegmatite minerals. The obtained concentrate
is then used to recover the lithium using a combined heat
 P.K. Choubey et al. / Minerals Engineering 89 (2016) 119–137 123

Table 3
Solubility of lithium salts at different temperatures (g/100 g H2O) (Phillips and Perry,
1995; Dean, 1999).

Li-salts 0 °C 20 °C 40 °C 60 °C 80 °C 100 °C
Li2CO3 1.54 1.33 1.17 1.01 0.85 0.72
LiCl 69.2 83.5 89.2 98.4 112 128
Li2SO4 36.1 34.8 33.7 32.6 31.4 –
LiHCO3 5.80 5.74 – – – –

Fig. 4. Ellingham diagram for the phase transformation of spodumene.
treatment followed by chemical processing methods. Due to the
complexity of the minerals and the crystalline structure (Deer
et al., 1978; Cundy et al., 1963; Lee et al., 1990; Cerny and
London, 1983), the beneficiated minerals undergo heat treatment
using many methods to break the intricate structure and to convert
them into a leachable phase from the unleachable form (Skinner
and Evans, 1960). Therefore, this process will also be discussed in
the following sections on minerals with their corresponding
thermodynamics.
2.1. Processing of spodumene
2.1.1. Mineralogical aspects of spodumene metallurgy
Spodumene is the main mineral source of lithium due to its
high content (Li2O 6–9%) and deposits in earth’s crust (Table 2)
(Fox-Devies Resources Specialist, 2013; Martine and Sebastian,
1991); however, the direct extraction of lithium from naturally
occurring a-spodumene is not feasible due to its crystalline struc-
ture (Fig. 3a). Spodumene is a chain silicate/pyroxene-type min-
eral, with the presence of silica in the tetrahedral form (Skinner
and Evans, 1960). Each silicon atom is surrounded by four oxygen
atoms situated at the corners of a tetrahedron. Two of the oxygen
atoms of each tetrahedron are shared, one with each of the two
adjacent tetrahedra, thereby forming infinite chains. The silica
chains are parallel, with the vertices of the tetrahedra pointing
alternately in opposite directions. In the two directions normal to
their lengths, the chains are held together by oxygen cation bonds,
with the cations of Li+ and Al3+. Spodumene is placed in the mon-
oclinic section of the pyroxene group of minerals.
The use of a heat treatment to convert a to b-spodumene with a
tetragonal structure is necessary to provide a passage (Fig. 3b) to
liberate lithium with the expansion of volume and decrease in
specific gravity (from 3.2 g/cm3 to 2.4 g/cm3) (SGS Minerals
Services, 2010). Thermodynamic data show that the transition of
a to b-spodumene is not feasible at the ambient temperature of
the standard conditions but can be achieved by elevating the tem-
perature, as follows:
DG298 K ¼4:63 kcal
b-Spodumene ƒƒƒƒƒƒƒƒƒƒ a-Spodumene
DG1073 K ¼
0:45 kcal
ƒƒƒƒƒƒƒƒƒƒƒ! b-Spodumene ð1Þ
The Gibbs free energy change vs. temperature diagram (Fig. 4)
reveals the possibility of a phase conversion at P800 °C, but the
investigations performed in this direction have suggested the suit-
ability of a higher temperature to transform the a to the b phase
(HSC Chemistry-6.0), which was confirmed by XRD analysis
(Barbosa et al., 2014). Recently, a microwave furnace was used
for the phase transformation of spodumene to extract lithium
(Peltosaari et al., 2015). During the phase transformation, lithium
atoms introduced into the cavity have a tetragonal structure. The
insertion of the small cavity increases the cell volume with the
lithium content, as described in the crystal chemistry of spo-
dumene (Skinner and Evans, 1960). As a result, the b-spodumene
obtained after heat treatment has cation exchange properties
(strictly for Li+ and H+) and is subject to attack by acid as follows:
DG ¼
375:28 kcal
LiAlSi2 O6 þ H2 SO4 ƒƒƒƒƒƒƒƒƒƒ! Li2 SO4 þ Al2 O3 SiO2 þ H2 O ð2Þ
Spodumene is the mineral employed on the commercial scale
for lithium recovery; the studies of different processing routes
employing various reagents are summarized in Table 4, divided
accordingly, and are discussed below.

Fig. 5a. Eh–pH diagrams in the Li–S–H2O system at 25 °C (HSC Chemistry 6.0). Fig. 5b. Eh–pH diagrams in the Li–C–H2O system at 25 °C (HSC Chemistry 6.0).
124 P.K. Choubey et al. / Minerals Engineering 89 (2016) 119–137
2.1.2. Sulfation processing
The sulfation is one of the most common techniques for pro-
cessing of spodumene to recover lithium due to the high stability
of Li2SO4 in aqueous systems (Eh–pH diagram shown in Fig. 5a)
and its solubility (Table 3). Although the sulfate forms of other
impurities (Al, Na, Mg, and K) that are commonly present with
lithium also form soluble compounds, lithium is slightly soluble
in a carbonate medium (Table 3) (Phillips and Perry, 1995), which
is helpful for precipitating Li2CO3 from water-dissolved Li2SO4 as
follows:
DG ¼
48:88 kcal
Li2 SO4 þ Na2 CO3 ƒƒƒƒƒƒƒƒƒƒ! Li2 CO3 þ Na2 SO4
Sivander et al. (1941) compared the temperature of the roast-
ing of lithium-bearing minerals, particularly spodumene, using
sulfate/potassium sulfate salts. The minerals were crushed and
ground into the desired size and then treated with alkali metal
sulfates (Na2SO4/K2SO4) at 850–1200 °C for the maximum recov-
ery of lithium. During roasting, lithium was replaced by the Na-
atom of the sodium sulfate to form lithium sulfate by an ion
exchange reaction at 1170 °C. K2SO4 required a higher tempera-
ture to replace lithium because of its higher melting point than
Na2SO4. Additionally, at a higher temperature, silica also decom-
poses, causing an adverse reaction on lithium recovery. Therefore,
less expensive Na2SO4 is a suitable reagent for the extraction of
lithium from spodumene. Dwyer and Passaic (1957) used ammo-
nium sulfate for the recovery of lithium from heat treated spo-
dumene at 1040 °C by roasting at 150–370 °C. During the
reaction, Li2SO4 is formed with the evolution of ammonia gas,
which is absorbed in water for the subsequent leaching of lithium
at pH 7, leaving impurities Fe, Al, Mg, and Ca in the residue.
Lithium containing the leached solution was treated with ammo-
nium fluoride to precipitate LiF, which was then treated with
H2SO4 at 300 °C to form Li2SO4 and HF. Li2SO4 was processed at
1150 °C in the presence of reducing gas and hydrolyzed to
lithium hydroxide. Finally, Li2CO3 is produced by passing CO2
gas through LiHCO3 solution. However, this process has the oper-
ational disadvantage of requiring several steps to precipitate
Li2CO3.
Ellestad et al. (1950) and Archarnbault et al. (1962) reported the
extraction of lithium from spodumene by heat treatment at 1100–
1350 °C to convert a to b-spodumene followed by hot digestion
with concentrated sulfuric acid at 250 °C to replace Li+ with H+ ions
from the sulfuric acid to form Li2SO4 and LiHSO4. After hot diges-
tion, water leaching followed by carbonate precipitation was con-
ducted at 90 °C to separate lithium as Li2CO3. Apart from the hot
digestion process, a solid–gas reaction between b-spodumene
and SO3 gas was also performed for the extraction of lithium at
350 °C. In this process, the roasted mass was leached in water to
dissolve Li2SO4 along with impurities. Li2CO3 was precipitated
using soda ash after purification of the solution with respect to
Fe and Al by precipitation at pH 6–7. The process is not economi-
cally viable due to the dissolution of the undesirable impurities
and causes difficulty for the purification process to produce high
purity lithium carbonate.
2.1.3. Carbonation processing
In carbonation processing, spodumene is mixed with Na2CO3
and heated in the range of 525–675 °C to replace the Li-atoms with
Na-atoms of soda ash to form lithium carbonate and sodium alu-
minum silicate (Archarnhault et al., 1968). Then, the roasted pro-
duct is subjected to leaching with water in the presence of CO2
to separate lithium as Li2CO3 precipitates. The reaction occurs as
follows (Amouzegar et al., 2000; Olivier et al., 1978; Kroll et al.,
1953):
DG ¼
450319:8 kcal
2½LiAlSi2 O6  þ Na2 CO3 ƒƒƒƒƒƒƒƒƒƒƒ
ƒ! Li2 CO3
þ Na2 O  Al2  O3  4SiO2  H2 O ð4Þ
DG ¼
8:48 kcal
Li2 CO3 þ CO2 þ H2 O ƒƒƒƒƒƒƒƒƒ! 2½LiHCO3  ð5Þ
The formation of lithium bicarbonate is an important step prior
to yielding the Li2CO3 product because the solubility of Li2CO3 is
very low in water; therefore, the conversion of LiHCO3 of higher
solubility (Phillips and Perry, 1995) is performed by passing
through CO2 gas. The Eh–pH diagram drawn for the Li–C–H2O sys-
tem (Fig. 5b) indicates the existence of lithium bicarbonate in the
pH range of 6–8, which is maintained during the reaction. The sol-
ð3Þ
ubility of LiHCO3 in solution can be enhanced by autoclaving the
system in the presence of CO2 at 250 °C, which improves the pro-
cess efficiency (Chen et al., 2011). Under the optimized leaching
conditions, more than 94% lithium was obtained with a 99.6% pro-
duct purity of Li2CO3, which is higher than that obtained in the sul-
furic acid process (Chen et al., 2011). This difference is attributed to
the absence of sulfate ions in the product. The residue obtained in
this process contained only analcime and quartz because analcime
contains one crystal water (Tu et al., 2003; Yang, 2004).
2.1.4. Chlorination processing
Chlorination is also an effective process because of the high
reactivity with metal oxides and silicates, forming water-soluble
chlorides. The chlorination of lithium-bearing ores has been used
in various chlorination methods to selectively extract lithium as
lithium chloride at elevated temperatures, but the process is com-
plicated and requires highly corrosion-resistant equipment
(Davidson, 1981; Lof and Lewis, 1942). Barbosa et al. (2014) pre-
sented the possibility of the equilibrium composition of the Si–A
l–Li–O–Cl system to form solid or liquid product LiCl and other
solid products of different phases of Al and Si during chlorination.
Further, chlorination of spodumene concentrate (7.25% Li2O and 2%
impurities Fe, Ca and Mg) was performed in a fixed bed reactor
under the following conditions: total flow rate 100 mL/min, Cl2
partial pressures 0.2–1.0 atm, and 1000–1100 °C. In this process,
the kinetics of chlorination showed an apparent activation energy
of 359 kJ/mol (Barbosa et al., 2013). The reaction was non-catalytic,
gas–solid in nature and fits the sequential nucleation and growth
model. The reactions may be represented as given below, forming
the solid products Al6Si2O13 (mullite) and SiO2 (cristobalite) during
the chlorination of b-spodumene.
DG ¼
202 kcal
LiAlSi2 O6 þ 1=2Cl2 ƒƒƒƒƒƒƒ! LiCl þ 1=6Al6 Si2 O13 þ 1=4O2 ð6Þ
Further, the chlorination studies performed with pure Cl2
caused a loss in mass, which increased markedly with an increase
in the chlorine temperature due to the volatilization of lithium
chloride and chlorides formed by the impurities present in the
ore. The conversion of lithium as LiCl was completed after
150 min of chlorination at 1100 °C. The elimination of impurities
from spodumene by chlorination has been applied to industrial
processes by temperature control (Barbosa et al., 2014). It was
found that iron, if present, is removed below 1000 °C, followed
by obtainment of LiCl. LiCl can be further treated to eliminate the
chlorides of the other impurities by distillation using a fractionat-
ing column (Habashi, 1986). To improve the purity of Li2CO3, stud-
ies conducted by different researchers are described below.
2.1.5. Fluorination processing
Recently, Rosales et al. (2014) proposed the leaching of
b-spodumene in hydrofluoric acid for lithium recovery. A maximum
extraction of 90% Li was obtained under the following optimized
leaching conditions: 7 vol.% HF at 75 °C; stirring speed 330 rpm
and reaction time 10 min. Si and Al that were also dissolved in
 P.K. Choubey et al. / Minerals Engineering 89 (2016) 119–137
Fig. 6. Typical structure of lepidolite (M1 = Li0.93(Mg, Mn, Fe2+)2, = M2 = Al0.58, Li0.35) (Adopted and modified from: Swanson and Bailey, 1981).
HF and removed by precipitating as Na2SiF6 and Na3AlF6 using
NaOH. Simultaneously, the fluoride species of lithium were also
converted into the soluble hydroxide form (LiOH), which was sub-
jected to evaporation until the concentration of lithium reached
20 g/L (An et al., 2012). Finally, the solution was heated to 95 °C
for 20 min, leading to the precipitation of lithium as a carbonate
salt. The obtained unwashed precipitate of Li2CO3 has 98% purity
(Jandova et al., 2010). The chemical reactions involved in the pro-
cess are given below with their thermodynamic feasibility (An
et al., 2012; Jandova et al., 2010).
DG ¼
7:25 kcal
LiF þ NaOH ƒƒƒƒƒƒƒƒƒ! LiOH þ NaF
DG ¼
25:1 kcal
2½LiOH þ CO2 ƒƒƒƒƒƒƒƒƒ! Li2 CO3 þ H2 O
DG ¼
8:48 kcal
Li2 CO3 þ CO2 þ H2 O ƒƒƒƒƒƒƒƒƒ! 2½LiHCO3 
2.1.6. Lime processing at elevated temperatures
Autoclaving of b-spodumene with lime has been proposed for
lithium extraction from b-spodumene (Nicholson, 1946). In this
process, the concentrate was treated with lime and water in a tem-
perature range from 100 to 205 °C under pressure to leach out the
lithium as LiOH by the following reaction:
DG ¼
1143742:8 kcal
LiAlSi2 O6 þ CaO þ H2 O ƒƒƒƒƒƒƒƒƒƒƒ
ƒ! LiOH þ CaAl2 Si2 O8
Undissolved impurities of Al, Fe, and Mg were separated by a
simple, solid–liquid separation procedure. Finally, the leached
solution was subjected to evaporation to increase the lithium con-
centration and was further treated with CO2 to precipitate Li2CO3
(similar to Eq. (8)) with a purity of 97.8%, which is not suitable
for battery-grade intermediates.
2.2. Processing of lepidolite
2.2.1. Mineralogical aspect of lepidolite metallurgy
In contrast to spodumene, lepidolite is a sheet silicate (phyl-
losilicate) mineral with a monoclinic crystalline structure (Fig. 6)
in which the position of the lithium atoms is between the sheets
(Swanson and Bailey, 1981). This structure requires roasting prior
to leaching of lepidolite to liberate the lithium from the encapsu-
lated structure. Luong et al. (2013) reported that lepidolite
125
completely breaks down at 850–900 °C (at a Na2SO4–Li molar
ratio of 2:1). The reaction of lepidolite and Na2SO4 forms the
lithium-containing products LiF, NaLiSO4, LiKSO4, Li2OSiO2, and
Li2O2SiO2 with minor amounts of silicates, such as LiAlO2 and
LiAlSiO4, in which only the crystalline LiKSO4 and Li2NaK(SO4)2
were detected by XRD patterns, along with residual Na2SO4. After
leaching at the water–calcine mass ratio of 10:1, Li2NaK(SO4)2
was not detected in the XRD profile of the residue, whereas some
remaining peaks of LiKSO4 are still present, which indicates that
incomplete dissolution of LiKSO4 at a 10:1 water–calcine ratio
would cause a lower extraction (80% Li). However, when the
ð7Þ water–calcine ratio of 15:1 was used, 90% Li was extracted, con-
firming that LiKSO4 plays an important role in determining the
ð8Þ
extraction of lithium.
ð9Þ For lepidolite roasting with FeSO47H2O and CaO mixtures, the
breakdown of lepidolite forms HF, whereas iron sulfate decom-
poses to create SO2 and SO3 (in the presence of oxygen) at temper-
atures of 350–400 °C (Luong et al., 2014). On the other hand, Li2SO4
and LiKSO4 are the main lithium compounds formed (98% of all Li)
from the reaction of lepidolite with iron sulfate at temperatures
>900 °C. The amount of Li2SO4 slightly decreases with the steady
increase of the LiKSO4 quantity as the temperature increases. Both
compounds then start decomposing at >900 °C, whereas other
lithium compounds, such as LiAlSiO4, LiAlO2, and LiFeO2, begin to
ð10Þ
form. It was predicted that the formation of these compounds
could reduce the recovery of lithium during water leaching due
to their potentially low solubility. This was confirmed by a
decrease in lithium extraction during the leaching of the calcined
product at 925 °C. The presence of Li2SO4 in calcine was also veri-
fied by the XRD pattern, which can easily be dissolved in water, as
confirmed by the XRD of the leached residue. Iron sulfate plays a
different role than Na2SO4 in the interaction with lepidolite during
roasting due to its thermal stability and the formation of SO2/SO3
at the high temperatures of 750–800 °C (in the case of iron sulfate,
350–400 °C). Many reagents were used by different researchers for
the processing of lepidolite, as summarized in Table 4.
2.2.2. Processing via sulfation roasting
Because the direct leaching of lithium from lepidolite is not pos-
sible, Botton et al. (1965) reported hot digestion followed by leach-
ing and precipitation to extract lithium containing 1–2 wt.%. The
126 P.K. Choubey et al. / Minerals Engineering 89 (2016) 119–137

Table 4
Summary of the literature survey for different minerals.

Minerals Experimental conditions (heat-treatment, leaching) Salient results Merits Demerits References
Spodumene Heat-treatment at Leaching conditions H2O, Recovery of Li: 86% Commercially viable 8% loss of Li during Ellestad et al.
850–1150 room temperature 99% pure Li2CO3 process processing (1950)
Roasting with CaO at NaCl leaching at elevated Recovery of Li: 90% Electrochemical grade Roasting temp. is very Kroll et al.
1000–1300 °C pressure of 20 bar, Li2CO3 obtained high (1953)
temperature 210 °C
Roasting with Na2CO3 Water leaching at ambient Recovery of Li: 92% 98% Li2CO3 produced 10% loss of lithium Archarnhault
at 550–650 °C for temperature without any purification et al. (1968)
30 min
Heat-treatment at Pressure leaching with Recovery of Li: 94% Li2CO3 suitable for Energy extensive Archarnbault
Temp. 1050 °C Na2CO3 at 225 °C, 60 min battery grade process et al. (1962)
Heat-treatment at 7% HF, temp: 75 °C, Recovery of Li: 90%, Low conc. of HF required Not commercialized yet Rosales et al.
1100 °C reaction time: 20 min 98.2% pure Li2CO3 for leaching (2014)
Chlorination with Cl2 – LiCl extracted at LiCl extracted by Cl2 roasting is very Barbosa et al.
(g) at 1100 °C, 150 min 1100 °C distillation corrosive in nature (2014)
Chlorination (using – 90.2% Li extracted as Commercialized process Corrosive resistant Barbosa et al.
CaCl2) at around LiCl at 900 °C equipment required (2015)
700 °C.
Lepidolite H2SO4 hot-digestion at Water leaching at ambient Recovery: 90% Li Comparatively low Leaching efficiency is Botton et al.
700 °C temperature roasting temperature low (1965)
Roasting with Water leaching at ambient Recovery: 90% Li. CaCl2 lowered the 10% loss of Li Yan et al.
Na2SO4 + CaCl2 at temperature for 30 min Purity of Product: roasting temperature (2012a)
880 °C 99.5% Li2CO3
Na2SO4 roasting with/ Water leaching at ambient Recovery of Li: 91.61%, Purity of lithium Formation of CaF2 may Yan et al.
without CaO, K2SO4 at temperature for 30 min Purity 99.5% Li2CO3 carbonate is  99.5% decrease the leaching. (2012b)
850 °C
Heat-digestion with Pressure leaching with Recovery: 98.9%. Li Electrochemical grade High energy Yan et al.
steam at 880 °C lime-milk at an elevate Purity of product: Li2CO3 obtained consumption (2012d)
temperature 170 °C 99.9% Li2CO3
Roasting with NaCl Water leaching at 60 °C for Recovery: 92.86% Li Roasting temp decreased Leaching temp. is Yan et al.
+ CaCl2 at 880 °C for 30 min duration due to combine effect of comparatively high (2012c)
30 min NaCl + CaCl2
Na2SO4 roasting at Water leaching at 85 °C for Recovery: 90.4%, Li Roasting agent is very Silicate formation Luong et al.
1000 °C for 30 min 3h cheap decrease the Li recovery (2013)
FeSO4 roasting at Water leaching at Recovery: 93/85% Li (in More than 90% recovery Formation of lithium Luong et al.
850 °C temperature of 20 °C closed/open system) of Li achieved at room aluminates decreased (2014)
temperature recovery
Roasting with (FeS)– Water leaching at 50 °C, S/L 81% Li recovery Comparatively less Leaching efficiency is Dinh et al.
CaO, 750 °C ratio 5:1 energy consumption very low (2015)
Zinnwalidite Sintering with CaSO4 Water leaching at 90 °C, Recovery of Li: 87–93% Leaching time is only Leaching efficiency is Kondas and
and Ca(OH)2 at 850– duration 10 min 10 min comparatively low Jandova
975 °C (2006)
Sintering at 950 °C Water leaching at 90 °C for Recovery of Li: 96% Li2CO3 is suitable for Leaching temp. is high Jandova et al.
with CaSO4 and Ca 10 min direct utilization (2009)
(OH)2
Roasting with CaCO3 Water leaching at 85 °C, Recovery of Li: 90%, Purity of product is high Leaching efficiency is Jandova et al.
at 825 °C for 60 min. duration 30 min Selective extraction of suitable for LIB only 90% (2010)
Li at pH  13
Sintering with CaCO3 Water leaching at 95 °C for Recovery of Li: 85% Sintering agent is Formation of glassy Vu et al.
at 835 °C for 60 min. 60 min economically phase decrease the (2013)
leaching efficiency
Amblygonite H2SO4 hot-digestion Water Leaching at room 95% Recovery of Li Have a potential for Energy extensive Siegens and
(100–200 °C) followed temperature commerciazation process Roder (1936)
by roasting
Hot-digestion with Leaching agent: H2SO4 83% Recovery of Li Impurities separated Li recovery is Coleman and
NaOH at 93 °C before Li leaching comparatively low Jaffa (1935)
Heat-treatment at Water leaching 97% recovery of Li More than 95% Li Difficult to Kalenowski
950 °C with gypsum recovered commercialize and Runke
and lime (1952)
Solid gas (SO3) Water leaching at room Only 67% recovery of SO3 formed in situ during Recovery of Li is very Frevel and
reaction at 900 °C temperature Li roasting low Kressley
(1962)

mineral was first treated with concentrated H2SO4 at temperatures
varying from 150 to 170 °C to replace Li+ ions with H+ to form
Li2SO4. The digested slurry of Li2SO4 was then selectively dissolved
in cold water because Al and K have low solubility in cold water.
Subsequently, lithium was precipitated as Li2CO3 at 90 °C using
Na2CO3 as a precipitating agent after removing the dissolved Al
by precipitation using alkali and alkaline earth carbonate. Luong
et al. (2013) studied the extraction of lithium from a lepidolite con-
centrate (2.55% Li) using a 2-stage process based on roasting with
Na2SO4 and water leaching. The study of lepidolite decomposition
roasting was conducted at 850–1000 °C with Na2SO4 to Li molar
ratios of 1:1–3:1 for 0.5–2 h to produce different products to leach.
LiKSO4 was identified as one of the main lithium-containing prod-
ucts formed in calcine, which has a low solubility; therefore, it con-
trols the release of lithium into water during leaching. The low
solubility of LiKSO4 at 25 °C was confirmed during leaching at dif-
ferent water–calcine mass ratios (5:1–15:1). A leach solution con-
centration of only <1.0 g/L Li was obtained, corresponding to
 P.K. Choubey et al. / Minerals Engineering 89 (2016) 119–137
Fig. 7. Generalized process flow sheet for the recovery of Li from lepidolite (Adopted and modified from: Yan et al., 2012a,b).
45–48% recovery. After increasing the temperature to 85 °C, the
leaching recovery increased to 47–90%. Under the optimum condi-
tions (at a water–calcine mass ratio of 15:1, 85 °C and 3 h), 90.4% of
the lithium was extracted from the calcines roasted at 1000 °C for
0.5 h (Na2SO4 to Li molar ratio of 2:1). The sulfate roasting was fol-
lowed by leaching to recover lithium as Li2CO3, as presented in
Fig. 7 (Yan et al., 2012a,b). During roasting, an additive was used
to enhance the extraction efficiency.
Initially, roasting was performed at different temperatures
using sodium sulfate and using potassium sulfate and calcium
oxide as additives. At 850 °C, 91.6% Li was extracted, maintaining
a mass ratio of lepidolite/Na2SO4/K2SO4/CaO of 1.0/0.5/0.1/0.1
(Yan et al., 2012b). The addition of a suitable amount of K2SO4
and CaO prevents the roasted product from fusing, increasing the
lithium extraction efficiency. However, if excess amounts of
K2SO4 and CaO were added, then the extraction decreased, forming
a red brick of roasted product, such as CaAl2Si2O8 and Ca4Si2O7F2,
which encapsulated the lithium ion. Therefore, the additives
should be used in a suitable amount to increase extraction effi-
ciency; otherwise, they will adversely affect lithium extraction.
Yan et al. (2012a) investigated the effect of CaCl2 as an additive
for the extraction of lithium under the same conditions given
above, which enhanced lithium extraction up to 94.8% at a mass
ratio of lepidolite/Na2SO4/CaCl2 of 1/0.5/0.3 and a roasting temper-
ature of 850 °C. Above this temperature, the sample fused, result-
ing in decreased leaching efficiency. Under the optimum
conditions of roasting for 0.5 h at 880 °C, the recovery of metals
was 94.8%, 60.7%, 93.5% and 90.1% for Li, K, Rb and Cs, respectively.
The recovery of lithium was constant from 830 to 930 °C; thus,
temperature control is flexible during industrial applications. After
removal of Na2SO4 salt by crystallization, the solution containing
20–24 g/L Li was precipitated by adding Na2CO3 (Li2CO3 of purity
>99.5%), leaving the solution suitable for recovery of Rb, Cs and
127
K. The process is simple and effective for the extraction of valuable
metals from lepidolite.
Recently, Luong et al. (2014) proposed iron sulfate roasting and
water leaching to extract lithium from lepidolite for a recovery of
85% and 93% for the open and closed systems, respectively, by
leaching lepidolite calcine at a water/calcine mass ratio of 1:1 at
room temperature for 1 h. The step-wise reactions occur as
follows:
DG ¼
153:28 kcal
12½FeSO4  þ 3O2 ƒƒƒƒƒƒƒƒƒƒ! 4½Fe2 ðSO4 Þ3  þ 2½FeSO4  ð11Þ
DG ¼186:71 kcal
Fe2 ðSO4 Þ3 ƒƒƒƒƒƒƒƒƒ! Fe2 O3 þ 3SO3 ð12Þ
DG ¼140:69 kcal
KLi2 AlSi4 O10 ðFOHÞ2 þ SO3 ƒƒƒƒƒƒƒƒƒ! Li2 SO4 þ LiKSO4
þ LiAlSiO4 þ LiAlSO2 þ HF ð13Þ
A suitable proportion of calcium oxide and sulfate are mixed
with ore to enhance the extraction of lithium by minimizing HF
formation.
2.2.3. Processing via carbonation roasting
Calcium carbonate roasting followed by water leaching has also
been used for lithium recovery from its minerals, such as lepidolite
(Rosett et al., 1935; Mazza and Whittier, 1960). In this process,
minerals ground to the desired size were roasted with calcium car-
bonate at 1000 °C until the mass was completely clinkered (Rosett
et al., 1935). The clinker was then treated with hot water to dis-
solve the lithium; however, Na, Rb, Cs and Ca with a trace of Fe
and Mg were also dissolved. Therefore, the impurities were
removed before the precipitation of Li2CO3, and Ca was separated
by sparging carbon dioxide gas in the solution to precipitate CaCO3.
Then the solution was neutralized using HCl to convert into chlo-
ride. Mazza and Whittier (1960) also performed roasting with cal-
cium carbonate from 800 to 1000 °C, followed by water leaching at
128 P.K. Choubey et al. / Minerals Engineering 89 (2016) 119–137
Fig. 8. Generalized process flow sheet for the recovery of Li from lepidolite by
defluorination (Adopted and modified from: Yan et al., 2012d).
100 °C. Impurities, such as Ca and Al, present in the solution were
separated as calcium aluminate. After the separation of impurities,
the solution was evaporated to recover lithium as LiOHH2O.
2.2.4. Processing via chlorination roasting
In addition to the sulfate and carbonate process, chloride roast-
ing followed by leaching was also reported for lithium extraction.
Lithium forms soluble chloride complexes, such as NaCl, CaCl2
and their mixtures, during roasting with sodium and calcium
chloride, as shown below.
DG ¼
1762381:08 kcal
KðLi; AlÞðSi; AlÞ4 O10 ðF; OHÞ2 þ 2NaCl ƒƒƒƒƒƒƒƒƒƒƒƒ
ƒ!
NaAlSi3 O8 þ 2RCl
DG ¼
5553035:1 kcal
KðLi; AlÞðSi; AlÞ4 O10 ðF; OHÞ2 þ CaCl2 ƒƒƒƒƒƒƒƒƒƒƒƒƒ!
CaAl2 Si2 O8 þ 2RCl
where R = Li, Cs, K, Ca, Rb.
NaCl, KCl, NaAlSi3O8, and SiO2 species are formed with NaCl
roasting at a mass ratio of lepidolite to NaCl of 1:2 and 1:1,
whereas NaCl, KCl, NaAlSi2O6, SiO2, CaF2, CaSiO3, and CaAl2Si2O8
species were obtained at a mass ratio of CaCl2 to lepidolite 1:2.
The LiAlSi2O6 phase disappears when the CaCl2 and lepodolite
mass ratio increases to 1:1, as reported by Yan et al. (2012c). The
extraction efficiency was only 62% in both cases due to incomplete
diffusion of chlorine in lepidolite. Further roasting was performed
with a mixture of NaCl and CaCl2, which showed an enhanced
lithium extraction because the melting point of the mixture of NaCl
and CaCl2 is lower than that of NaCl and CaCl2 alone, which
increases the fluidity of the chloride and decreases the viscosity
of the liquid phase. Hence, chlorination roasting diffuses more
easily than NaCl and CaCl2 to the surface of lepidolite, which
results in enhanced extraction up to 92.0% Li at 60 °C in 30 min,
maintaining an S/L ratio of 1:2.5 in water. After leaching,
lithium was recovered as Li2CO3 after solution purification at a
suitable pH.
2.2.5. Processing via the de-fluorination and lime pressure leaching
process
Treatment of lepidolite with steam (H2O) at high temperatures
to form aluminum silicate (LiAl(SiO3)2) and leucite (KAlSi2O6) and
hydrofluoric acid has been performed (Yan et al., 2012d). During
the heat treatment, steam (H2O) dissociates into H+ and OH
. The
proton reacts with fluoride to form HF, and the hydroxyl group
reacts with the Si–O–Si bond of lepidolite to form a Si-OH group.
The Si-OH group may react with OH
to form new phases, such
as H2O, leucite or aluminum silicates. Under the optimum condi-
tions of steam roasting (860 °C, 30 min), 42.3% of fluoride was
removed from lepidolite. The steam-treated lepidolite was then
processed under pressure at 130 °C using sodium carbonate solu-
tion, and  99% Li was obtained during leaching. Then, lithium
hydroxide was recovered as crystallized salt based on the solubil-
ity, which is lower than the other alkali metal hydroxides, as
shown in Table 4. After crystallization, lithium hydroxide was re-
dissolved as LiHCO3 by CO2 gas, followed by lithium precipitation
as Li2CO3 by heating to 90–100 °C, as presented in Fig. 8.
DG ¼
25:1 kcal
2½LiOH þ CO2 ƒƒƒƒƒƒƒƒƒ! Li2 CO3 þ H2 O ð16Þ
DG ¼
8:48 kcal
Li2 CO3 þ H2 O þ CO2 ƒƒƒƒƒƒƒƒƒ! 2½LiHCO3  ð17Þ
2.3. Processing of zinnwaldite
2.3.1. Mineralogical aspect of zinnwaldite metallurgy
Zinnwaldite belongs to the mica group minerals containing
potassium, lithium, iron, aluminum, silicate, hydroxide and fluo-
ride (composition given in Table 2). Zinnwaldite is also a phyllosil-
icate/sheet silicate mineral [KLiFeAl(AlSi3)O10(OH,F)2] similar to
lepidolite, with a monoclinic crystalline structure (Mizota et al.,
1986). Different authors reported the extraction of lithium from
zinnwaldite and other resources, as given in Table 4 (Alex and
Suri 1996; Kondas and Jandova, 2006; Jandova et al., 2007a;
Jandova et al., 2007b). However, the processing of zinnwaldite is
yet to be commercialized because of the lower concentration of
lithium and/or its limited deposition in the earth’s crust.
2.3.2. Processing via sulfation roasting
The gypsum (CaSO4 roasting) process has been used for the
recovery of lithium from zinnwaldite concentrate, providing a suf-
ð14Þ
ficient yield of lithium, whereas rubidium extraction did not
exceed 25% (Kondas and Jandova, 2006; Jandova et al., 2007a). In
ð15Þ this process, the concentrate was sintered with CaSO4 and Ca
(OH)2 at 850–975 °C, forming a soluble Li2SO4 complex, which
was leached with water at 90 °C, maintaining a liquid-to-solid ratio
of 5–15:1. A recovery of 87–93% lithium was obtained from the
sintered product at 900 °C. The leach solution containing 1.4 g/L
Li was suitable for recovering Li2CO3 salt. Further, the gypsum pro-
cess was also investigated for the processing of zinnwaldite con-
centrate (1.40% Li, 0.98% Rb) obtained from Sn–W wastes (0.21%
Li, 0.20% Rb) by dry-magnetic and grain-size separations for the
extraction of lithium in the Czech Republic (Jandova et al., 2009).
The ground sample (<0.1 mm size) was sintered with CaSO4 and
Ca(OH)2 at 950 °C, maintaining a mass ratio of concentrate/CaSO4/
Ca(OH)2 of 6/4.2/2, followed by leaching in water at 90 °C, with a
liquid-to-solid ratio 10:1 for 10 min. Decreasing the liquid-to-solid
 P.K. Choubey et al. / Minerals Engineering 89 (2016) 119–137
ratio from 15:1 to 3:1 did not influence the lithium extraction,
whereas decreasing the leaching temperature from 90 to 20 °C
resulted in 5% lower extraction. The leach liquor containing lithium
along with impurities, such as Ca, K, Rb, Na, and Ca, was purified
with respect to Ca as carbonate precipitates (at 20 °C), followed
by precipitation of Li2CO3 (using potassium carbonate as a
precipitating agent at 90 °C) based on the solubility in H2O,
whereas K and Rb remained in the solution because of their higher
solubility. Thus, 96% of the lithium was obtained with 99% purity
as Li2CO3, which is suitable for direct industrial utilization. The
process is a promising method for the separation of Li2CO3 from
leached solutions of zinnwaldite wastes of Sn–W ores containing
K, Rb, and Ca.
2.3.3. Processing via carbonation roasting
The calcium carbonate roasting process followed by water
leaching process has been studied for lithium recovery from zin-
nwaldite concentrate (1.21% Li and 0.84% Rb). A recovery of 90%
lithium and rubidium was obtained under an optimized roasting
temperature of 825 °C followed by water leaching and solvent
extraction/precipitation. The obtained leach liquor was purified
with respect to Al, Si and Ca by sparging CO2 at pH 6.8, followed
by crystallization of Li2CO3 by evaporation at high temperatures.
In another procedure, lithium was separated by solvent extraction
using LIX54 and TOPO at pH 13. The loaded organic was stripped
by dilute sulfuric acid solution, followed by precipitation of Li2CO3
from the lithium-enriched solution using potassium carbonate. The
precipitated salt was washed with water to produce nearly 99.5%
pure Li2CO3. Mother liquors after Li2CO3 crystallization and/or raf-
finate after lithium extraction were found suitable for the produc-
tion of rubidium compounds, such as Rb2CO3, Rb2SO4 and RbOH
(Jandova et al., 2010). Vu et al. (2013) used CaCO3 powder as the
roasting agent followed by water leaching and an alkali digestion
process to recover lithium and rubidium from zinnwaldite concen-
trate containing 1.29% Li and 0.94% Rb. The sintering process pro-
ceeded in three partially overlapping stages: (i) decomposition of
zinnwaldite up to 800 °C, (ii) formation of new phases between
750 and 835 °C, and (iii) formation of an amorphous glassy phase
above 835 °C. The densification of the reaction mixture occurred
via liquid phase sintering at temperatures above 750 °C, and diffu-
sion of Ca, K, Si and Rb resulted in the formation of the new phases.
The optimal extraction efficiencies of 84% Li and 91% Rb were
achieved by leaching of the sintered mass (sintering temperature
of 825 °C) at 95 °C. The good fit of the hyperbolic and uniform reac-
tion models to the leaching data indicated that the dissolution of
lithium and rubidium proceeded through two stages of diffusion
control. The formation of a layer of Ca(OH)2 on the surface of the
sinters occurred and then terminated the dissolution of lithium
and rubidium in the later stage of leaching.
A comparative study of zinnwalidite concentrate (2.07% Li2O)
obtained by physical beneficiation of the tailings (0.84% Li2O) of
granites was performed using a number of roasting agents, namely,
limestone, gypsum and sodium sulfate, at different temperatures
(Siame and Pascoe, 2011). Limestone was not effective for lithium
extraction due to the formation of eucryptite. A recovery of 84% Li
was obtained by roasting the concentrate with gypsum at 1050 °C.
Sodium sulfate is an effective and energy-efficient reagent because
97% Li was recovered by roasting the concentrate, even at temper-
atures as low as 850 °C. In contrast, roasting with gypsum was
energy intensive because of the requirement of high temperatures
and the lower lithium recovery compared with sodium sulfate,
which may be due to the higher melting point of gypsum than that
of sodium sulfate. In all of the cases, the iron extraction was very
low. The preliminary study showed that Li2CO3 with a purity of
>90% was produced by precipitation with Na2CO3 from the sulfate
leach liquor (Siame and Pascoe, 2011).
129
2.4. Processing of amblygonite
2.4.1. Mineralogical aspect of amblygonite metallurgy
Amblygonite is a fluorophosphate mineral [LiAl(F,OH)PO4] that
geologically occurs in granite pegmatite with a triclinic crystalline
structure and is found in fluorine-rich topaz-bearing granites
(Simonov and Belov, 1958). Amblygonite also forms an isostructure
with istavorite (LiFe3+PO4F) and only occurs as an alteration pro-
duct of primary phosphates in pegmatites; consequently, Al M Fe
substitution in amblygonite–montebrasite is rare to nonexistent.
A typical composition of amblygonite is presented in Table 2,
which shows that it is a fluorine-rich mineral and forms a series
with montebrasite (Lee et al., 1990). Few studies have been con-
ducted on the extraction of lithium from the amblygonite mineral.
2.4.2. Processing via sulfate roasting
Processing of amblygonite is similar to other minerals. Either
hot digestion or roasting is necessary for effective lithium recovery.
Hot digestion with H2SO4 followed by leaching for the lithium
recovery has been reported (Siegens and Roder, 1936). In this pro-
cess, beneficiated amblygonite was treated with H2SO4 at 100–
200 °C followed by heat treatment at 850 °C and water leaching
to extract lithium as Li2SO4 with a leaching efficiency of 95%.
The leach solution was purified, and lithium was precipitated as
Li2CO3 using Na2CO3 as a precipitating agent. Further, Kalenowski
and Runke (1952) used gypsum and lime (at a 1:2 mass ratio) as
roasting agents for the lithium recovery. Amblygonite (8.46%
Li2O) was mixed with gypsum and lime (at a 1:2 mass ratio) at
950 °C for 2 h and was then leached in water while maintaining
a liquid:solid mass ratio of 5:1; 97.3% Li was recovered. In
another method, amblygonite was treated with SO3 gas at 900 °C
to form water-soluble lithium species (Li2SO4) (Frevel and
Kressley, 1962). However, the efficiency of this process is lower
than other processes; only 67.5% lithium was recovered with this
technique, whereas 90% lithium was released from lepidolite using
the same procedure.
2.4.3. Processing via alkali digestion
Caustic soda digestion followed by acid leaching was also
reported for the lithium extraction. In this process (Coleman and
Jaffa, 1935), amblygonite (8.63% Li2O) was mixed with a NaOH
solution and heated to 93 °C for 3 h to dissolve aluminum as alu-
minum phosphate. The aluminum solution was separated by filtra-
tion, and an insoluble, lithium-rich residue obtained. The residue
was washed with either a NaH2PO4 or H3PO4 solution to remove
the entrapped phosphorus as P2O5. Finally, the lithium-rich residue
underwent leaching with H2SO4 to recover lithium as Li2SO4. Dur-
ing the lithium leaching, other metals were leached and removed
as impurities by adding lime or soda ash to the leach liquor. Then,
the purified lithium-bearing solution was concentrated, and the
lithium was precipitated as Li2CO3 using soda ash.
2.5. Existing commercial process for lithium recovery from minerals
After describing the technological developments for processing
lithium minerals, it is easier to understand the commercial opera-
tions in practice. The processing of lithium minerals involves
upgrading the ground ores by beneficiation techniques, such as
flotation and wet magnetic separation (Dresler et al., 1998), optical
sorting (Kondas and Jandova, 2006) or heavy media separation, as
practiced by Galaxy Resources Ltd. in its plants in Australia and
China. Subsequently, concentrates containing 4–6% Li2O can then
be subjected to a 2-stage (roasting and water leaching) treatment
to extract lithium into solution and to recover the metal as lithium
carbonate or lithium chloride. Commercial lithium carbonate (bat-
tery grade) products require a purity of >99.5%; thus, the major
130 P.K. Choubey et al. / Minerals Engineering 89 (2016) 119–137
Fig. 9. Sulfate process flow sheet for the recovery of Li from spodumene (Adopted and modified from: Galaxy Resources Limited, 2011).
Fig. 10. Alkali process flow sheet for the recovery of Li from spodumene (Adopted
and modified from: Galaxy Resources Limited, 2011).
impurities normally leached along with Li, such as Fe, Ca, Mg, K and
Na, must be removed during processing.
Employing the heat treatment, hot digestion route, Galaxy
Resources Limited (2011) has established the sulfation processing
of lithium, as presented in Fig. 9. The concentrate of this processing
plant is produced from spodumene mined from Mt. Catlin and
Greenbushes (in Western Australia), containing 1.05–3% Li2O. Nat-
ural spodumene (of a-phase) is converted to b- spodumene by heat
treatment at 1100 °C. After the phase transformation, b-
spodumene is subjected to treatment with concentrated sulfuric
acid at a high pulp density while maintaining a temperature of
250–300 °C to extract lithium in the sulfate form. The lithium sul-
fate formed under the above conditions is leached out in water at
room temperature. The dissolved impurities of Fe, Al, Ca and Mg
are removed by precipitating the contaminants at various pH val-
ues (Al and Fe at 5.5–6.5; Ca and Mg at 11–13) as metal hydroxides
and gypsum. Finally, the lithium as Li2CO3 is precipitated by adding
sodium carbonate as a precipitating agent at 90 °C for the produc-
tion of 17,000 tpa (second largest in the world) in its China plant.
This process is commercially less viable than soda processing from
an economic point of view and based on the purity of lithium car-
bonate. Therefore, further soda processing is used to produce
battery-grade lithium salt with a purity P99.5%, as shown in
Fig. 10. Initially, spodumene converted from the a to b form is trea-
ted with a sodium carbonate solution under high pressure and
temperature (250–300 °C) to leach out the lithium as bicarbonate
in the neutral pH range of 6–8 by passing through CO2 gas. For
purification, the pressure-leached solution is treated with lime to
precipitate the impurities, such as Fe, Mg and Ca, followed by a
 P.K. Choubey et al. / Minerals Engineering 89 (2016) 119–137 131

Table 5
Compositions of divergent brine deposits of commercial value worldwide (An et al., 2012).

Elements Ocean Dead Sea, Israel Great salt lake, Utah Bonneville Brine, Utah Salton Sea, USA Silver peak brine, Nevada Salar de Atacama
brine, Chile
Na 1.05 3.0 7.0 9.4 5.71 6.2 7.17 5.70
K 0.038 0.6 0.4 0.6 1.42 0.8 1.85 1.71
Mg 0.12 4.0 0.8 0.4 0.028 0.02 0.96 1.37
Li 0.0001 0.002 0.006 0.007 0.022 0.02 0.15 0.193
Ca 0.04 0.05 1.5 0.5 0.0 0.71 1.46 0.043
Cl 1.9 16.0 14.0 16.0 15.06 10.06 16.04 17.07
Br 0.0065 0.4 0.0 0.0 0.0 0.002 0.005 0.005
B 0.0004 0.003 0.007 0.007 0.039 0.005 0.04 0.04

solid–liquid separation procedure. The filtrate solution containing
LiHCO3 is then heated at 90 °C to remove the CO2, which is recircu-
lated for reuse in the leaching stage, resulting in the precipitation
of lithium as Li2CO3 of high-purity battery grade.
The highest lithium values of >4000 ppm are found in an area of
7 km2 in the southernmost part of the basin.
Despite the difference in nature, the concentration and regional
occurrences, the processing routes of brine are similar, as discussed
below.

3. Technological improvement for the extraction of lithium

from brine
3.1. Processing of brine
Brine is one of the most important sources of lithium; neverthe-
less, commercial production started much later than production
from minerals. The contribution of brine is nearly two times that
of minerals (Fig. 2). Lithium production from brine depends on
its composition, volume and accessibility, as well as its amenability
to local processing (Kesler et al., 2012). The lithium concentration
in most brine ranges from 200 to 700 ppm, and the differences are
largely due to either an unusually large surface area or the pres-
ence of brines in deep reservoirs (Kesler et al., 2012). Brines can
be divided into different types based on the nature of the salt ions,
such as sulfate, chloride or carbonate (shown in Table 5 with the
composition), which depends on the geographical climate of the
region of occurrence (Nie et al., 2011; An et al., 2012).
For example, the brine of the Qinghai–Tibet plateau was created
by thrusting and transtensional faulting during the formation of
the Himalayan Lakes, resulting in reduced salinity from north
and northwest to south and southeast, including carbonate,
sodium sulfate, magnesium sulfate and chloride (Nie et al., 2011).
The brine found in Salar de Atacama, Chile is chloride-enriched, of
which the upper part of the salt layer occupies an area of 1400 km2
(Lowenstein and Risacher, 2009). The porosity of the upper salt
layer decreases from 30% near the surface to approximately zero
at depths of 35 m (Garrett, 2004). The brine that fills this porosity
at <50–70 cm of depth has an unusually high lithium concentration
(of several thousand ppm) that shows systematic regional zones.
Fig. 11. Movement of ions (Adopted and modified from: Yu et al., 2015).
3.2. Pre-concentration/pre-treatment
The lithium content in brine is too low to exploit it economi-
cally; therefore, pre-concentration is required, as in the case of
extraction from minerals. Using the naturally available and plenti-
ful solar energy to pre-concentrate lithium in a large volume of
brine is one of the most inexpensive methods to increase the via-
bility of the process. The oldest effective technique in salt produc-
tion is used in areas with warm climates in which the evaporation
rate exceeds the precipitation rate, either annually or for extended
periods, with steady prevailing winds (Calvonico, 1990). During
the salt-making season of 4–5 months, a saturated brine solution
flows continuously through a series of ponds. The water is super-
saturated with salts; therefore, most of the pure salt crystallizes
out of the solution as the water evaporates. The ponds are then
completely drained. This technique works best at low latitudes in
large areas with a small slope, low salt water permeability, low
rainfall rate, high evaporation, dry wind, and long summer seasons
for evaporation. Generally, 70–90% of evaporation occurs during
the months of April to October; thus, the resultant pond composi-
tion has enough brine to service the plant throughout the year to
help smooth the production of lithium (Huang et al., 2010;
Blochi et al., 1951; Smith and Newell, 1991; Ossandon et al.,
2010; Liu et al., 2014; Agha et al., 2002; Xiao et al., 2013).
Carbonate brine is processed using solar evaporation in a pond
that is divided into three zones, namely, the upper convective zone
(UCZ; contains fresh water), the non-convective zone (NCZ; in
which the salinity gradually increases from top to bottom) and
the lower convective zone (LCZ; composed of pre-concentrated
brine). Yu et al. (2015) reported the processing of brine using
lithium extraction by a geothermal salinity gradient solar pond
(G-SGSP). In this technique, lithium was initially concentrated to
2.75 g/L from 0.32 g/L while the concentration and crystallization
of other metals occurred simultaneously. Lithium settled as Li2CO3
at the bottom of the lower zone of the pond, whereas potassium
and sodium migrated upward, according to the diffusion law and
due to the lower hydration energy compared to that of lithium,
which led to higher ionic mobility of sodium and potassium. Thus,
the alkali metals other than lithium shifted to the upper zone, as
presented in Fig. 11, whereas the product obtained at the bottom
contained 90% of lithium as Li2CO3.
For the pre-concentration of lithium via solar evaporation, a
concentration of 6–7 wt.% of lithium in solution has been defined
as the ‘‘end point” or ‘‘drying-up point” (Wilkomirksy, 1999;
Boryta, 2000, 2001, 2002, 2005, 2007, 2008, 2009, 2010, 2011; Galli
and Demetrio, 2011; Brown et al., 1981a; Brown and Jacob, 1981;
Brown et al., 1981b; Brown and Falletta, 1980; Brown and Boryta, 1993);
132 P.K. Choubey et al. / Minerals Engineering 89 (2016) 119–137

Table 6
Recovery of lithium from brines using the precipitation, adsorption and solvent extraction techniques.

Experimental conditions Salient results Merits Demerits References

Solar evaporation: Precipitation of magnesium and calcium with lime at Purity of product: Commercialized process Very slow process Boryta (2002)
pH 8.4–9.1 and 11 respectively. Li2CO3 precipitation at 70–95 °C 99.99% Li2CO3 with high purity of Li2CO3
obtained
Magnesium and calcium precipitation with lime. Extraction of LiCl with More than 90% LiCl Highly pure LiCl produced Cost effective Brown (1990)
20% iso-octyl alcohol. Crystallization of LiCl at 110 °C produced with 99.2% process
purity
1st stage Mg and Ca precipitation at pH below using lime 11.3; 2nd stage  90% Li recovered Ca and Mg oxalate reused Energy extensive An et al. (2012)
precipitation of Mg and Ca using sodium oxalate with 99.55% purity at during the processing process
80–90 °C
Using LimMgxMnIII yMnIVzO4 as an adsorbent, sorption time = 24 h, Adsorption capacity: High selectivity for Li Commercially not Chitrakar et al.
solution pH 6.5 23–25 mg/g adsorption viable (2013)
adsorbent
Using Al(OH)3 as an adsorbent at temp. 30 °C and solution pH 9 Adsorption capacity: Adsorbent capacity is high Yet to be Hawash et al.
123 mg/g adsorbent commercialized (2010)
Using hydrated alumina as an adsorbent, Sorbent-to-LiOH ratio = 2 M, Adsorption: 0.6– High adsorption stability Adsorption Dong et al.
pH 5.8 0.9 mg/g sorbent capacity is low (2007)
Pure butanol as the organic extractant, extraction pH = 7  90% extraction of Li: Extractant is very cheap Loss of 10% Li Gabra (1978)
Purity of LiCl 99% during extraction
Fluorinated b-diketone (HFDMOD) and TOPO as an organic extractant 94% extraction of Li Battery grade Li obtained commercialized Seeley and
not viable Baldwin (1976)
Synergistic extraction using 0.4 M LIX 54 + 0.2 M Cyanex 923 in diluent 97% extraction of Li Extraction efficiency is Cost effective Pranolo et al.
ShellSol D70, A/O ratio = 1:1, temp. 40 °C, pH 11 following HCl high process (2015)
stripping (pH 3.5)
Anion exchange resin containing active group of Al(OH)3, extraction pH Elute a portion of Li+ Alumina can be used for Degradation of Lee and
6.0–7.5 with weak solution of more than 140 cycle resin during Bauman (1978,
LiX processing 1980, 1982)

>11

8.4

Fig. 12. Generalized process flow sheet for the recovery of Li from brine.
 P.K. Choubey et al. / Minerals Engineering 89 (2016) 119–137
Fig. 13. Eh–pH diagram of Mg–H2O system at 25 °C (HSC Chemistry 6.0).
Fig. 14. Eh–pH diagram of Ca–H2O system at 25 °C (HSC Chemistry 6.0).
further enrichment is difficult due to the operational point of the
highly viscous slurry.
Prior to recovering lithium from brine, the maximum possible
pre-concentration is achieved by solar evaporation. In addition to
the solar evaporation process, lithium can also be concentrated
by solvent extraction, ion exchange and adsorption prior to precip-
itation, as shown in Table 6.
The studies reported by Boryta (2000, 2001, 2002, 2005, 2007,
2008, 2009, 2010, 2011) and Galli and Demetrio (2011) for the
recovery of technical and chemical grade LiCl and Li2CO3, as shown
in Fig. 12, using an evaporation-precipitation-crystallization route
have adopted the precipitation of magnesium and calcium for sep-
aration from pre-concentrated brine. They used the inexpensive
and available precipitating agents CaO/Ca(OH)2 to precipitate
impurities as Mg(OH)2/CaSO42H2O at high alkalinity (per the
Eh–pH diagram shown in Figs. 13 and 14, which also shows the
solubility of these compounds). After purification of the solution,
a technical-grade lithium carbonate was separated by precipitation
by adding Na2CO3. Further treatment of the obtained technical-
grade product with CO2 yields 99.97% pure electrochemical-grade
Li2CO3, as presented in Figs. 11 and 14, and the equation is similar
to 3 and 18.
Alternatively, the purity of technical-grade Li2CO3 can be
upgraded to electrochemical-grade Li2CO3, as shown in Fig. 15.
133
Li2CO3 sol
Ca(OH)2 Precipitation CaCO3
LiOH
Crystallization
LIOH.H2O
Recrystallization
LiOH
CO2 Precipitation
Li2CO3
Fig. 15. Process flow sheet for the separation of Li2CO3.
Technical-grade Li2CO3 can be treated with slacked lime to produce
LiOHH2O by vacuum crystallization; subsequently, re-
crystallization yields high-purity LiCl salt after treatment of
LiOHH2O with HCl solution. The reaction occurs as follows:
DG ¼
0:41 kcal
Li2 CO3 þ CaðOHÞ2 ƒƒƒƒƒƒƒƒƒ! 2LiOH þ CaCO3 ð18Þ
DG ¼
12:6 kcal
LiOH þ HCl ƒƒƒƒƒƒƒƒƒ! LiCl þ H2 O ð19Þ
Brown and Falletta (1980), Brown et al. (1981a), Brown and
Jacob (1981), Brown et al. (1981b) and Brown and Boryta (1993)
reported the extraction of lithium from pre-concentrated brine of
7 wt.% Li. After the rejection of Mg 62 ppm in solution by adding
slaked lime, CaCl2 was added to remove calcium and boron as
CaB2O46H2O with low solubility in brine. The remaining boron
(not precipitated) can be removed by solvent extraction using
20% iso-octyl alcohol in a pH range of 1–2 by maintaining an
organic-to-aqueous phase ratio of 4:1, followed by water stripping.
The boron-free LiCl solution is subjected to evaporation under a
pressure of 70–90 mmHg and an elevated temperature of 110 °C
to separate the saturated LiCl by solid–liquid separation at 99%
purity, leaving the impurities of Mg and Ca in the filtrate. To obtain
extra-pure product, LiCl can be washed with isopropanol. This pro-
duct can also be electrolyzed to produce metallic lithium.
A two-stage precipitation process was developed using lime fol-
lowed by sodium oxalate as a precipitant to remove Mg, Ca, B and
sulfate from the brine. Further, residual Ca and Mg were removed
before subjecting the treated brine to carbonation at 80–90 °C
using sodium carbonate for the recovery of high-purity (99.55%),
crystalline lithium as lithium carbonate (Tran et al., 2013;
Hamzaoui et al., 2003). Lithium recovery as sulfate precipitates
(Li2SO4H2O) using the salting-out effect was also reported
(Garrett, 1981).
In addition to solar evaporation, adsorption processes were also
reported for the selective recovery of lithium using different types
of adsorbents. Chitrakar et al. (2013) reported lithium adsorption
using Li0.15H0.76Mg0.40–MnIII IV
0.08Mn1.59O4 adsorbent. The adsorbent
134 P.K. Choubey et al. / Minerals Engineering 89 (2016) 119–137
exhibited a maximum lithium adsorption capacity of 23 mg/g at pH
6.5. After adsorption, lithium can be desorbed with diluted HCl solu-
tion, and the efficiency of the adsorptive capacity of the sample did
not decrease even after 10 cycles. Lithium adsorption using alu-
minum salt as (AlCl36H2O) as an adsorbent was performed by vary-
ing the temperature from 10 to 30 °C, but over 30 °C, the
temperature does not affect lithium uptake on Al(OH)3, which
proved that the process occurs via physical adsorption (Hawash
et al., 2010). Equilibrium isotherms have been determined for the
adsorption of Li+ onto Al(OH)3 as a function of pH (5–9) at 30 °C;
the maximum adsorption capacity at pH 9 was 123 mg/g. Desorption
of Li+ was better when using HF than H2SO4. When using an inor-
ganic adsorbent for the selective recovery of lithium from brine,
magnesium was initially separated as Mg(OH)2, followed by the
selective adsorption of lithium onto manganese oxide. Desorption
and enrichment of lithium were performed using HCl solution. Alu-
minum and manganese oxide were also reported for the adsorption
of lithium, followed by desorption using diluted HCl. The rate of
adsorption of the lithium ion on manganese oxide was higher than
that of aluminum oxide due to the ionic radii of manganese oxide
(J.S. Kim et al., 2014; H. Kim et al., 2014). Dong et al. (2007) also
reported lithium extraction using aluminum salts (with a capacity
of up to 0.6–0.9 mg/g) prepared using Al(OH)3 and LiOH.
For the selective adsorption of lithium, a strong base anion
exchanger (Dowex MSA-I) and a weak base anion exchanger
(Dowex MWA-l) were also used (Lee and Bauman, 1978, 1980,
1982). Prior to contact with the feed solution, changing the active
chloride group into the hydroxyl form is optional and can be used
in the integrated form, whereas the active group of Dowex MWA-l
must be modified into the hydroxyl form. While working with
Dowex MSA-I, the active chloride form of the resins was exchanged
with AlCl3 by treating with a saturated solution of aluminum chlo-
ride. Subsequently, the treatment with ammonia solution converts
Brine
Pre-treatment
Concentrated Brine
Iso-octyl alcohol BORON Extraction Boric acid
Ca(OH)2 Precipitation-I Mg(OH)2
CaCl2 Precipitation-II CaSO4.2H2O
Na2CO3 Precipitation-III
Filtration
Li2CO3
Fig. 16. Technical process flow sheet for the recovery of lithium from brine
(Adopted and modified from: Outotec, 2013).
the AlCl3 into the Al(OH)3 form, which comes into contact with
brine containing LiCl at pH > 6. The use of NaOH instead of a
NH4OH solution has an adverse effect during hydroxylation of
the resin because it caused the formation of the alkali aluminates,
which elute the AlCl3 of the modified resins. The LiCl from the brine
is extracted into the modified resin as a halo lithium aluminate
complex in a temperature range of 40–50 °C. Note that maintain-
ing the extraction temperature within the optimized range
enhances the life-cycle of the active group of resins that can work
for more than 100 cycles. The elution of lithium from the pregnant
resins was successfully achieved with hot water at  50 °C (Lee and
Bauman, 1982).
In addition to the adsorption process, solvent extraction and
ion-exchange studies were also conducted to recover lithium from
brine. The extraction of lithium from a chloride solution containing
Li, K, Na, and Ca has been performed using butanol. At equilibrium
pH 7, 90% lithium was extracted (Gabra, 1978). Pranolo et al.
(2015) reported the extraction of lithium from a sodium chloride
solution using a mixture of LIX 54 and Cyanex 923. At pH 11.2,
97% lithium was extracted with the synergistic solvent extraction
system consisting of 0.4 M LIX 54 and 0.2 M Cyanex 923 in ShellSol
D70 at a unit phase ratio and at 40 °C. Back-extraction of lithium
from the loaded organic was performed at the equilibrium pH
3.5. The extraction behavior of lithium from a neutral alkali metal
solution using different types of b-diketone diluted in various dilu-
ents was investigated (Seeley and Baldwin, 1976). The extraction of
lithium increases as the acidity of the extractant increases, and
94% Li was extracted with a mixture of solvents, such as fluori-
nated b-diketone (HFDMOD) and TOPO, as the extractant diluted
in dodecane. In another work, by mixing b-diketone with neutral
organophosphorus extractants (TOPO, TBPO, TBP, and T2EHP), the
extraction kinetics at the water-heptane interface was studied.
The adsorption constants for organophosphorus compounds were
larger than those of b-diketone. The extraction of lithium was
reported using the chelating extractant dipivaloymethane
(2,2,6,6-tetramethyl 3,5-heptanedione, DPM) in the presence of
ether (Zushi et al., 2003). Dang and Steinberg (1978) also used dip-
ivaloylmethane, a chelating extractant, for the recovery of lithium,
which was subsequently stripped with diluted HCl. The obtained
stripped LiCl solution can be used in the electrolytic production
of lithium metal and Cl2.
Schultze et al. (1986) proposed a process for the separation of
LiCl from brine using tetrahydrofuran. AlCl3 was added to the solu-
tion to form a precipitate at pH 7.5. Then, the precipitate was
treated with hydrochloric acid solution and was sparged with gas-
eous HCl to remove aluminum chloride at pH 2. The solution con-
taining different metal chlorides was dried at 200 °C and then
crushed to –35 mesh size. The mixed chlorides were treated with
tetrahydrofuran in the temperature range of 15–35 °C to selec-
tively extract LiCl due to the covalent bonding in LiCl, whereas
CaCl2 has ionic bonding. The insoluble metal salts were removed.
Then, tetrahydrofuran was evaporated to obtain pure LiCl.
Recently, a US-based company, Symbol, in cooperation with the
South Korean giant, POSCO, has attempted to establish an alternate
process to solar evaporation in lithium extraction. They are treat-
ing the hydrothermal brines of geothermal power plants that oper-
ate in Southern California’s Salton Sea based on reverse osmosis
techniques, which eliminate the need for solar evaporation and
make the operation cost-effective. Solar evaporation has a recovery
rate of 50% or less, but POSCO’s technology has shown >80% recov-
ery with 99.99% purity. In December 2012, POSCO started a pilot
plant operation for the production of Li2CO3 with a capacity of 20
tons per annum, in association with Li3 Energy (OTCBB:LIEG), in
Copiapo, Northern Chile. Considering the brine supply, POSCO also
signed a cooperation agreement with the Bolivian government to
evaluate the application of its technology for lithium brine projects
 P.K. Choubey et al. / Minerals Engineering 89 (2016) 119–137
in the region in addition to its partnership with Li3 Energy (Pistilli,
2015).
3.3. Existing commercial processes for lithium recovery from brine
The commercial processes for lithium exploitation from brine
are not much different from the technologies discussed in the pre-
ceding section. A commercialized process of Outotec Ltd. (Fig. 16)
in Australia and China involves solar evaporation to concentrate
the lithium up to 6–7% from brine solutions (Outotec, 2013). The
concentrated solution contains major impurities of B, Mg, Ca,
SO2– –
4 , and Cl that must be removed prior to recovering the pure
lithium carbonate product. Boron is first removed by solvent
extraction using a fatty alcohol, preferably iso-octyl alcohol, in a
pH range of 1–2 and is recovered as a by-product. Subsequently,
the concentrate is subjected to a 3-stage precipitation to obtain
technical-grade Li2CO3. Mg, Ca and Li are precipitated in a stepwise
process of pH-swinging (Figs. 13, 14 and 5b) using Ca(OH)2, CaCl2
and Na2CO3, respectively, as precipitating agents. To upgrade the
purity to electrochemical grade, the technical-grade Li2CO3 is sub-
jected to carbonation with gaseous CO2 at elevated temperature
and pressure to solubilize the lithium as LiHCO3. Then, LiHCO3 is
heated at 90 °C to precipitate lithium as Li2CO3 with 99.95% purity;
the released CO2 is recycled for reuse as described in Fig. 10.
4. Perspective and recommendations
Energy storage devices will continue to increase the lithium
demand in the commodity market in the near future; therefore,
the efficient processing of the available resources is important.
Many resources, such as spent batteries, sea water and clay, are
yet to be commercialized for lithium production, which places
pressure on the current methodologies for exploitable resources.
In minerals, spodumene is the main source, which has a high
energy requirement to convert lithium to a leachable phase. During
heat treatment, the use of a suitable reagent/additive to directly
leach the spodumene at a lower temperature than that of the hot
digestion process can lower the process cost. Another potential
process involves the carbonation process at a lower temperature
and pressure to avoid the sulfate impurities of the hot digestion
process. In some cases, the impurity profiles of mixed spodumene
with other mineral sources present an obstacle in the processing
route. This obstacle can be overcome by using mature separation
and purification techniques, such as solvent extraction/ion
exchange.
The speed at which brine has contributed to lithium production
(Fig. 2) is not matched by the slow rate of lithium enrichment by
solar evaporation. The energy savings achieved by solar evapora-
tion are restricted to dry and sunny climates. The market projec-
tion for lithium (Fig. 1) and the rapid depletion of ground
resources require improved enrichment processing of brines.
Advanced technologies, such as adsorption, electro-dialysis, and
reverse osmosis, can be applied to selectively enrich/extract the
lithium from brines in less time, subject to the cost-benefit-
analysis of the process employed (Somrani et al., 2013).
5. Conclusions
Lithium reserves in brine and mineral resources face challenges
in terms of process sustainability and reduced operational cost. In
the case of minerals, heat treatment for phase transformation, par-
ticularly of a-spodumene to b-spodumene, is necessary to expand
the volume of spodumene to release the lithium from its crys-
talline structure. Roasting with chemical reagents is required for
minerals, such as lepidolite and zinnwaldite, prior to leaching the
135
lithium into aqueous solutions. The chlorination process requires
well-equipped arrangements to resist corrosion; however, chlori-
nation has the advantage of forming more highly soluble species
(LiCl) than the carbonation and sulfation of minerals. The sulfation
process, with a lower cost, is prominent in leaching, even at ambi-
ent temperature. The high-purity product yield of Li2CO3 using the
carbonation process is in demand for battery production.
Currently, Chilean and Argentinean continental deposits, along
with the Dead Sea in Israel and other brines, are producing large
amounts of lithium. The processing routes are similar to solar
evaporation, the crystallization of impurities and precipitation.
The evaporation techniques used to enrich the lithium contents
in brine depend on the factors of low latitudes in large areas with
small slopes, low salt water permeability, low rainfall rate, dry
winds, and long summer seasons. The currently used brine extrac-
tion techniques are inadequate for the majority of resources; addi-
tional work in this area is essential for lithium recovery.
Acknowledgments
This research was supported by the Basic Research Project of
the Korea Institute of Geoscience and Mineral Resources (KIGAM),
South Korea, funded by the Ministry of Science, ICT and Future
Planning of Korea.
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