Review

Received: 5 February 2016 Revised: 3 March 2016 Accepted article published: 11 March 2016 Published online in Wiley Online Library:

(wileyonlinelibrary.com) DOI 10.1002/jctb.4976

Separation and purification of lithium

by solvent extraction and supported liquid
membrane, analysis of their mechanism:
a review
Basudev Swain*

Abstract
Separation and purification of lithium by solvent extraction and supported liquid membrane using various commercial and
non-commercial extraction has been reviewed. In solvent extraction, extraction by chelating extractants, acidic extractants,
solvation extractants and mechanism involved in the extraction has been discussed. Solvent extraction of lithium by solvation
extractants like; TOPO, DBM, TBP, and LIX and synergism of diketone with various solvation extractant combinations have been
reviewed. Finally, lithium extraction by supported liquid membrane using various extractants has been reviewed. The reported
processes mainly lacking in analysis of chemical mechanism involved in the lithium extraction using all these extractants are
analyzed and discussed.
© 2016 Society of Chemical Industry

Keywords: lithium; solvent extraction; separation and purification; supported liquid membrane

INTRODUCTION following four sectors: cellular, computers, video cameras and

The most important and common uses of lithium include bat- cordless.7 The use of LIB has recently been driven by significant
teries, ceramic glass, enamels, adhesive, lubricant greases, metal growth in transportation. It is estimated that the penetration of
alloy, air-conditioning, and dyeing. Lithium metal is alloyed with plug-in hybrid (PHEV), electric (EV) and hybrid (HEV) vehicles into
aluminum and magnesium to improving their strength and the market in 2020 will be at 20%.8 Exponential growth is esti-
lightness. Magnesium–lithium alloy is used for armor plating; mated for the lithium market as a component of electric and hybrid
aluminum–lithium alloys are used in aircraft, and high-speed vehicle batteries and for alternative energy production. Concern
over the carbon footprint of internal-combustion-powered auto-
trains. Lithium hydroxide is the most widely used thickening
mobiles, the projected future hydrocarbon shortage, and the
agent in multipurpose greases for automotive and industrial lubri-
quest for alternative energy sources is estimated to occupy the
cants. Lithium oxide is used in special glasses and glass ceramics.
LIB market. Electric-powered vehicles are expected to take mar-
Lithium stearate is used as an all-purpose and high-temperature
ket share from internal-combustion-powered vehicles in the near
lubricant; lithium-hydrides are used as a means of storing hydro-
future. Large LIBs are and will continue to be needed for power-
gen for use as a fuel.1 – 3 Highly purified lithium carbonate has
ing all-electric and hybrid vehicles and also for load leveling within
been successfully used in the chemotherapeutic treatment of solar- and wind-powered electric generation systems. Future light
manic depression. Some lithium, in the form of lithium carbonate vehicles will potentially be powered by electric motors with large,
or lithium citrate, is used as medicine to treat gout (an inflamma- lightweight batteries, and lithium is a particularly desirable metal
tion of joints) and to treat serious mental illness. Lithium also has for use in these batteries because of its high charge-to-weight
significant potential as absorption blankets in nuclear fusion reac- ratio.9 – 11 From energy security to carbon footprint, from daily life
tors and as a component in high-energy, long shelf-life batteries. to industrial growth, from environmental safety to mental health,
Among all these uses the most valuable application of lithium is lithium is a very important commodity. Thus, it is essential to deter-
as a component of high energy-density rechargeable lithium-ion mine rapid and accurate methods for separation, purification and
batteries (LIB). Lithium is also used in some non-rechargeable recovery of lithium, and this is currently receiving great attention
batteries in heart pacemakers, toys, and clocks. from scientists, engineers, and industrialists.1 – 3
Lithium primary cells have been on the market for about 40
years, while lithium secondary batteries or storage batteries have
become commercially dominating during the current decade.4 – 6 ∗ Correspondence to: B Swain, Institute for Advanced Engineering, Advanced
LIBs represents about 37% of the rechargeable battery world mar- Materials & Processing Center, Yongin, 449-863, Korea.
E-mail: [email protected], [email protected]
ket, powering laptop computers, cordless heavy-duty power tools,
and hand-held electronic devices, and their uses are increasing. Institute for Advanced Engineering, Advanced Materials & Processing Center,
The small rechargeable LIB market is steadily increasing in the Yongin, 449-863, Korea

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 www.soci.org B Swain

Solvent extraction of base metals, rare earth metals, and precious (a)
metals has been reviewed in the literature. The review regarding Agrochemicals, alloys,
separation and purification of lithium by solvent extraction and cement and concrete additives,
dyes and pigment 9%
supported liquid membrane (SLM), and analysis of their mecha- Lubricating greases
Rechargeable batteries 8%
nism has never been reported. The mechanism of solvent extrac-
29% Casting mold flux
tion of lithium is seldom discussed in the literature. In this paper powders 6%
the solvent extraction mechanism has been discussed thoroughly. Air treatment 5%
Polymer production 5%

REVIEW OF LITHIUM PRODUCTION, Primary battery 2%

DEMANDS, AND PROCESSES Primary aluminum
High electrochemical reactivity, the highest redox potential value, production 1%
the high specific heat capacity of any solid element, low atomic Ceramics and glass
mass, and low coefficient of thermal expansion properties have 35%
resulted in many commercial applications of lithium products. (b)
Lithium products are used in ceramics and the special glass 40000
industry, in the primary aluminum production industry, rocket

World lithium production, t

propellants industry, nuclear industry, pharmaceutical industry, Lithiun production
in the manufacture of lubricants and greases, synthesis of vita- 30000
min A, synthesis of organic compounds, silver solders, underwater
buoyancy devices, and batteries. The most important lithium com-
pounds produced commercially are lithium carbonate, lithium 20000
hydroxide, lithium chloride, lithium bromide, and butyl lithium.
Figure 1 shows the estimated global market for lithium in various
sectors for the year 2013. Global markets for lithium products 10000
were estimated to be ceramics and glass, 35%; rechargeable bat-
teries, 29%; lubricating greases, 8%; continuous casting mold flux
powders, 6%; air treatment, 5%; polymer production, 5%; primary 0
2009 2010 2011 2012 2013
batteries, 2%; primary aluminum production, 1%; and other uses, Year
9%. Total global lithium consumption increased by an average of
7% per year from 2003 through 2013. The lithium consumption Figure 1. (a) Estimated global market for lithium in various sectors for the
for rechargeable batteries increased at an average rate of 25% year 2013, and (b) worldwide lithium production for the years 2009 to 2013.
per year during the same period. Figure 1(b) shows worldwide
lithium production for the year 2009 to 2013. The figure shows reported as being above 85%. Considering energy costs, both the
that worldwide lithium production was almost the same for the processes are beneficial only for lithium-rich mineral resources, but
year 2012/2013. The British geological survey places the lithium at these processes are non-commercial and non-economical from
relative supply risk index of 6.7 out of 10. Supply, production and low-grade ores.16,17 From the environmental perspective, these
estimated future technological trends definitely raise concerns processes are not favorable industrial processes.
over lithium production. Figure 3 shows a typical flow sheet for lithium recovery from
Commercial lithium is produced as lithium carbonate, lithium brine. In general, lithium recovery from brine water involves solar
chloride and lithium hydroxide from various resources like brines evaporation of raw brine water to ≈ 1 g L−1 Li followed by removal
and high-grade lithium ores. Basically, two different processes; of magnesium, calcium, boron and sulfate in a number of precipi-
(i) mineral beneficiation followed by chlorination, leaching, and tation steps using lime and sodium carbonate.18 After magnesium,
carbonation, and (ii) mineral beneficiation followed by roast- calcium, boron and sulfate precipitation, lithium enrichment is fol-
ing/calcination, leaching, and carbonation are used for commer- lowed by lithium precipitation in the common process for lithium
cial production of lithium from lithium ores.2,12 – 15 Figure 2(a) and production. The production process from either resource uses a
(b) show the lithium recovery from ores by: (i) mineral beneficiation precipitation process, which is associated with inherent drawbacks
followed by chlorination, leaching, and carbonation; and (ii) min- like co-precipitation of other metals, compromised high purity,
eral beneficiation followed by roasting/calcination, leaching and and slow kinetics.
carbonation, respectively. In the chlorination route as shown in Considering thermal stability of lithium, which limits lithium
Fig. 2(a), the ore is mixed with limonite, heated to 700∘ C in a fur- recycling and recovery through the pyrometallurgical process.
nace, and after volatilizing, the ore is leached with 20% HCl. Then Hence, separation and purification of lithium by solvent extraction
water is introduced with HCl, which is necessary for selective chlo- should be a potential opportunity for industrial production of high
rination of lithium and eliminates undesirable components. Finally, purity lithium metal/compounds. The solvent extraction tech-
the Li2 CO3 is precipitated out through carbonation by adding soda nique is one of the most versatile methods used for the removal,
ash, which yields up to 80%. After precipitation the precipitated separation and concentration of metallic species from mixed metal
Li2 CO3 is separated through solid/liquid separation, followed by aqueous media. The solvent extraction technique also has been
drying and the pure Li2 CO3 is recovered. In the roasting route as used commercially for the production of different metals either
shown in Fig. 2(b) the ore is mixed with limestone and gypsum from primary resources or from secondary resources. Industrial sol-
in a kiln and the mixture is heated to 700–800∘ C. Then the solids vent extraction of lithium is rare. Literature investigation suggests
are leached and separated. The lithium salt is leached out along that no solvent extraction process has been reported for lithium
with some sodium, potassium, and calcium. Recovery of lithium is recovery at an industrial scale. Considering LIB current market,

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Separation and purification of lithium www.soci.org

(a) Brine
Clay
Lime Stone
Solar Evaporation
Palletization

Pretreatment
20% HCl Chlorination
Boric acid by
Solvent Extraction
Leaching product
Tails of Boron

Purification CaCO3 Calcium and Magnesium Calcium and Magnesium

Precipitation Purification

Na2CO3 Carbonation
Lithium Carbonate Calcium and Magnesium
Precipitation Precipitate by Product
Separation

Lithium Carbonate Flotation

Lithium Carbonate
Filtration
Production

(b) Lithium Carbonate Potassium and Sodium Salt

Clay Production by Product

Lime Stone, Figure 3. Flow sheet for lithium recovery from brine
Gypsum
Palletization
for extraction of lithium by several investigators. Lithium extrac-
tion by the polydentate structure of crown ether is governed
Roasting
by Pearson’s hard–soft acid-base (HSAB) principle. The principle
states that hard acids prefer to bind to hard bases and soft acids
Leaching Tails prefer to bind to soft bases. The hard acids have small, highly
charged and non-polarizable acceptor atoms and soft acids are
larger and not so highly charged. The bonding between hard acids
Purification Mg(OH)3 and hard bases is dominated by electrostatic interactions, whereas
CaCO3
the bonding between soft acids and soft bases is primarily cova-
lent. Crown ethers utilizing ether oxygens as donor atoms, which
Na2CO3 Carbonation
are ‘hard base’ species, coordinate well with the hard acid, alkali
metal cations.21,22 Figure 4(a) shows possible conformations of
Separation Glauber Recovery alkali cations with crown ether; Fig. 4(b) shows the X-ray struc-
ture of alkali cations with crown ether, and Fig. 4(c) shows lithium
complexation with crown ether. Crown ethers showed various con-
formations after complexation according to the cation size, that is,
Lithium Carbonate Na2SO4
Production guest cations are generally located in the center of crown ethers;
by Product
however, the sandwich structure is formed if the cation size is too
Figure 2. (a) Lithium recovery by chlorination of clay; (b) lithium recovery large for the cavity size. Crown ethers have often been selected as
by roasting of clay ligands to form complexes with lithium ion because the oxygen
atom which is a hard base and preferably binds to the lithium ion
end-of-life of LIB, and expected overall world market future evo- as shown in Fig. 4(c).22,23
lution, recovery of lithium from various waste resources should be Bartsch and coworkers synthesized a series of novel crown-ether
a panacea for environment, economy and energy securities. Thus compounds in which the crown ether ring size systematically var-
achieving lithium recovery through recycling technology for these ied from 13 to 16 atoms. The bonding/extraction ability of syn-
waste materials is a challenge and an opportunity, too.19,20 Several thesized crown ethers towards Li+ extraction was investigated,
authors have reported solvent extraction (SX), and SLM for lithium and the extraction ability of crown ether decreased as the crown
extraction and purification is reviewed in this paper. ring size was varied as 14-crown-4 > 13-crown-4 ≥ 15-crown-5
> > 16-crown-4.24 – 26 This order was rationalized in terms of the
size fit concept.26 Based on cavity size, the diameter of cations, and
SOLVENT EXTRACTION OF LITHIUM binding constant, the appropriate crown ether can be chosen for
Solvent extraction of lithium by chelating extractants the selected alkali metal and its mixture (Table 1).
The polydentate structure of crown ether and crown ether deriva- Crown ethers with ionizable pendant arms are known to form
tive has a special reactivity toward lithium, and has been used stronger complexes with cations than their neutral counterparts

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 www.soci.org B Swain

Table 1. Comparison of cation diameter, cavity size and binding constant crown ether interaction constants with alkali metal cations

Binding constant (log Ks )

Cations Cations diameter, Å Crown ethers Cavity size,Å Li+ Na+ K+ Rb+ Cs+

Li+ 1.48 12-crown-4 1.20 ∼ 1.50 -- 1.7 1.74 -- --

Na+ 2.04 15-crown-5 1.70 ∼ 2.20 1.20 3.48 3.35 2.81 2.18
K+ 2.76 18-crown-6 2.60 ∼ 3.20 1.00 4.35 6.08 5.32 4.79
Rb+ 2.98 21-crown-7 3.40 ∼ 4.30 0.50 2.54 4.35 4.86 5.20
Cs+ 3.40 24-crown-8 4.00 -- 2.35 3.53 -- 4.15

because the anion provides an internal counter ion for a com- phosphoric acid moiety as an additional binding site of a pen-
plexed cation, as shown in Fig. 5(a)–(b). Ionizable armed crown dant arm was measured by solvent extraction and transport exper-
ethers introduce guest-ligating side arms to the crown rings iment. It was observed that the introduction of the pendant group
to form dynamic and three-dimensional complexes to extract to the dibenzo-14-crown-4 provided significant enhancement of
cations. Similarly, crown ethers with pendant arms with a donor the extractability and the transport rate of only Li+ ion rather
electron pair moiety form complex ionophores with cations along than other alkali metals.29 The mechanism for extraction of lithium
with main chain crown as shown in Fig. 5(c). The same is also true using dibenzo-14-crown-4 possessing an ionizable phosphoric
with aza crown ether with pendant arms, and a possible mecha- acid moiety is explained in Fig. 6(a).
nism is shown in Fig. 5(d). The various derivatives of crown ethers, Binding properties of ten different benzo-13-crown-4 com-
particularly armed crown ethers, are effective for the separation pounds and a series of 15 14-crown-4 derivatives to Li+ and Na+
and extraction of lithium, as has been reported in the literature. have been assessed by picrate extraction and the response of
Basically, two main groups of armed crown ether (side chain crown polymeric membrane electrodes. Variation in cation selectivity
ethers, and side chain aza crown ethers) have been reported for was observed as a function of the group that attached to the cen-
extraction of lithium, and are reviewed below. In the side chain tral carbon atom. Of the different groups, those attached to the
crown or aza crown ether, basically, three main groups of side central carbon atom of the three-carbon bridges in the ionophores
chains, i.e. carboxylic acid, aromatic carboxylic acid, and phospho- play the vital role in lithium extraction. For the benzo-13-crown-4
ric acid have been reported. Figure 5 shows the general mecha- series, only weak cation binding and low selectivity were observed.
nism for side chain crown ether and side chain aza crown ether. For the 14-crown-4 series, the 6,13-dimethylenyl-14-crown-4
Katayama et al. reported the synthesis of crown ethers carry- exhibited the highest Li+ selectivity in picrate extraction.
ing a pendant phenolic chromophore for recovery of lithium.27 In polymeric membrane electrodes, considerably higher Li+
The phenolic protons of these crown ethers after dissociation selectivity was observed with 6,6,13-tribenzyl-14-crown-4 and
provide lipophilic anions which can extract alkali metal cations 6,6,13,13-tetraethyl-14-crown-4 than with the commercially avail-
into 1,2-dichloroethane by forming highly-colored neutral metal able Li+ ionophore 6,6-dibenzyl-14-crown-4. The 14-crown-4
complexes. 15-crown-5 or smaller ring-sized reagents favored the compounds lacked Li+ selectivity but the matrix on ionophore
extraction of lithium ion, whence the 15-crown-5 type reagents selectivity had a profound influence on lithium.25
are sodium-selective but 18-crown-6 type reagents were generally Tsukube et al. reported that amine-armed aza-12-crown-4 is a
potassium-selective. Alkali metal selectivity depends on structural, suitable extractant for Li+ , which forms Li+ ion-specific ionophore
steric, and conformational parameters, and all play a very impor- via three-dimensional complexation for extraction.30 The extrac-
tant role.27 Katayama et al. reported that the following factors are tion mechanism of lithium using amine-armed aza-12-crown-4 is
very important for alkali metal/lithium ion extractability: (i) nature explained in Fig. 6(b). Similarly, Sakai et al. also synthesized a chro-
of the crown ether ring; (ii) nature of the pendant phenolic group; mogenic crown ether, i.e. 1-(2-hydroxy-5-nitrobenzyl)-1-aza-4,7,10
and (iii) geometry between the crown ether center and pendant trioxacyclododecane, chromogenic aza-12-crown-4 has a sig-
phenolic group. 15-crown-5 or smaller ring-sized reagents favored nificant for lithium ion extraction. The extractant constants
the extraction of lithium ion. The 15-crown-5 type reagents are for this aza-12-crown-4 were pK a1 = 5.77, pK a2 = 10.31, pK ex
sodium-selective whereas the 18-crown-6 type reagents were gen- (Li) = 10.18, and pK ex (Na) = 12.50, indicating significant selectivity
erally potassium-selective. However, these selectivities were not and extractability of lithium.31
absolute, and other structural parameters, steric and conforma- From the above study it is reasonably inferred that the ring
tional, must be considered to explain in detail the selectivity of the size of the crown ether, aza-crown ether, the derivative of the
individual reagents.27 crown ether and their ability to form ionophore, ring type plays
Synthesis and extraction behavior of (2-sym-dibenzo-14-crown- an important role for selective extraction of alkali metal in general
4-oxy)-acetic acid and hexanoic acid, which is an improved synthe- and lithium in particular. Similarly, the cation size of alkali metals
sis of carboxylic acid derivatives of dibenzo-14-crown-4 has been and their ratio in the aqueous solution also affect the selectivity of
reported. The (2-sym-dibenzo-14-crown-4-oxy) hexanoic acid is a extraction. Competitive solvent extraction of lithium from aque-
very good extractant for lithium as well as alkaline earth metal ous chloride solution of Li, Na, K, Rb, and Cs using 0.25 mol L−1
ions.28 As commonly observed in the solvent extraction pro- each with 0.05 mol L−1 of crown ether and crown ether carboxylic
cess, dependence of the metal distribution on pH and ligand acid has been compared.32 Competitive and selective extrac-
concentration has been observed.28 Habata et al. synthesized tion alkali metals as the different ratio of Li+ /Na+ , which has been
dibenzo-14-crown-4 possessing an ionizable phosphoric acid moi- reported by Bartsch et al. has been reproduced in Table 2.32 Table 1
ety as an additional binding site of a pendant arm. The com- and Table 2 clearly show the possibility of lithium extraction and
plexing ability of dibenzo-14-crown-4 possessing an ionizable extraction efficiency depends on the cavity size of crown ether

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(a) (a) Complexation of proton ionizable side chain crown ether with metal ions

X----H -
X

O O - H+ O O
+ M+ M+
O O
(b) Complexation of proton ionizable side chain aza crown ether with metal
ions

-
X----H X
(b)
N N N N
+ M+ - H+ M+
O O
(c) Complexation of side chain crown ether with metal ions

Y Y

O O O O
+ M+ M+
O O
(d) Complexation of side chain aza crown ether with metal ions

Y Y

N N N N
+ M+ M+
O O

Figure 5. Representative figure for complexation of (a) proton-ionizable

side chain crown ether, (b) proton-ionizable side chain aza crown ether,
(c) side chain crown ether, (d) side chain aza crown ether with the metal
ion.
(C)
15-crown-5, and the following separation factors 1.06, 1.04,
O O 1.04 and 1.03 were obtained for 12-crown-4, benzo15-crown-5,
O O lauryloxge- metylene-15-crown-5 and dicyclohexane18-crown-6,
+ Li + Li +
respectively. All the separation factors depend on the ring diam-
O O O O eter of the respective crown.33 Extractive separation of lithium
isotope was also studied with benzo15-crown-5, which suggests
12-Crown-4 12-Crown-4-LI+ that the separation factor of lithium isotope will be 1.045 at
200 C.34 Even for selective extraction of lithium isotope, the above
Figure 4. (a) Possible conformations of alkali cations with crown ether; (b) conclusion, i.e. cavity size of crown ether/crown ether deriva-
possible X-ray structure of alkali cations with crown ether; and (c) show
lithium complexation with crown ether. tive compatibility plays an important role selective extraction of
lithium isotopes.
Figure 6 shows two typical representative cases for a lithium
or crown ether derivative. The cavity size of crown ether/crown extraction mechanism through the side chain ionizable crown
ether derivative compatibility plays an important role in selective ether and side chain aza crown ether. As shown in Fig. 6(a) the
extraction of lithium even in the competitive atmosphere of other lithium replaces the proton in the ionizable side chain crown ether
alkaline metals. subsequently lithium bound through polydentate cavities of the
Various derivatives of crown ether are also effective for the crown to form a complex for extraction. Figure 6(b) shows lithium
separation and extraction of lithium isotope, as has been reported ion entering the cavity of aza crown ether and donor electrons to
in the literature. The abilities of crown ethers to separate lithium form a side chain and chelation to extract lithium.
isotope were investigated for the number of oxygen atoms Although several crown ethers, aza crown ethers, and
composing the crown ring and for the constituent groups to their derivatives have been reported in the literature, from

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 www.soci.org B Swain

(a)
Lithium extraction mechanism using ionizable phosphoric acid side chain
O
O
CH3
O P O CH3 O P O
O
H O

O -H + O O
O
Li
+Li+ O O
O O

(b)
Lithium extraction mechanism using side chain aza 12-crown-4
CH3
CH3
CH3
CH3
N N N N

N O +Li+ N O N O +Li+ O
+ N +
Li Li
O O O O O O O O

Figure 6. Representative figure for (a) complexation of proton-ionizable crown ether, (9) complexation of side chain aza crown ether with lithium ion.

(MEHPA) as the extractant. Extraction equilibrium constants and

Table 2. Selectivity order of alkali metal cations with respect to
various crown ether. the composition of each metal complex in the organic phase were
determined; Li-D2EPHA has solvation number 3. From equilib-
Compound Selectivity order Li+ /Na+ ratio rium data, it has been concluded that lithium has high selectivity
over other monovalent cations. Divalent metal cations, however,
Benzo-12-crown-4 Li+ > Na+ > K+ > Rb+ > Cs+ 1.8
have much stronger affinity for these extractants compared with
Benzo-14-crown-4 Li+ > Na+ > K+ > Rb+ (no Cs+ ) 4.7
monovalent metal ions. Hence, the separation between monova-
Dibenzo-14-crown-4 Na+ > Li+ > K+ > Rb+ > Cs+ 0.6
lent and divalent cations is possible in the stripping stage.35 The
12-crown-4 Li+ > Na+ > K+ > Rb+ ≥ Cs+ 1.7
synergistic effect of tributyl phosphate (TBP) or trioctylphosphine
13-crown-4 Li+ > Na+ > K+ > Rb+ > Cs+ 2.3
oxide (TOPO) along with organophosphoric acid was also studied,
14-crown-4 Li+ > > Na+ (no K+ , Rb+ , Cs+ ) 20
from which it was concluded that the addition of TOPO did not
15-crown-4 Li+ > Na+ > K+ > Cs+ > Rb+ 3.5
affect extraction behavior, but the addition of TBP increases the
extraction rate in contrast to only phosphoric acid extractant. The
metal extraction order was Ca2+ > Mg2+ > Li+ > Na+ > K+ as a func-
the commercial perspective, lithium extraction using crown tion of the synergistic effect of D2EHPA with TBP. TBP alone could
ether is very limited. Commercialization of lithium extrac-
not extract the lithium, hence TBP was found to be a promising
tion using crown ether or its derivative is limited by two
synergistic reagent for lithium extraction along with D2EHPA and
important drawbacks, i.e., (i) crown ethers are expensive in
MEHPA.35
contrast to lithium; (ii) unlikely base metal extraction pro-
Swain et al. investigated separation of cobalt and lithium using
cess using Bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex
Cyanex 272, where the affinity of Cyanex 272 towards extraction
272), 2-Ethylhexyl 2-ethylhexyphosphonic acid (PC 88A) and
of lithium was not observed in the acidic ranges of the sulfate
Di-2-ethyl-hexyl phosphoric acid (D2EPHA). The commercial pro-
solution.36 Rejection of lithium by commercially available acidic
duction process using crown ether for lithium is not available. This
extractant Cyanex 272,37 – 40 D2EHPA,41 PC 88A,42 Ionquest 80143
section of the review clearly indicates that extensive research and
during solvent extraction of other base metals has been reported
thorough investigation of cheaper crown ethers for extraction of
in the acidic pH range of the aqueous phase. In the literature
lithium is needed.
the solvent extraction of lithium using acidic extractant is lim-
ited because commonly used acidic commercial extractants is not
Solvent extraction of lithium by acidic extractants suitable for extraction of lithium. Because the options for extrac-
Hano et al. reported solvent extraction of alkali and alkaline tion of lithium using these extractants are limited, these acidic
earth metals using organo-phosphors acidic compounds such extractants cannot be used for extraction of lithium from aqueous
as D2EHPA or 2-ethylhexyl-phosphonic acid 2-ethylhexyl ester solution.

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Table 3. Summary of 𝛽-diketone and solvation extractants for lithium extraction

𝛽-diketone Solvation extractant Extracted species Reference

N/A TOPO [Li(TOPO)3+ (ClO4 − )] Kusakabe et al.44

TTA TOPO Li(TTA)(TOPO)2 Healy46
TTA TOPO Li(TTA)(TOPO)2 Kim et al.47
TTA TOPO Li(TTA)(TOPO)2 Harvianto et al.48
TTA PHEN [Li(TTA)(PHEN)] Ishimori et al.49
TTA DMP [Li(TTA)(DMP)] Ishimori et al.50
TTA PHEN [Li(TTA)(PHEN)] Ishimori et al.50
DBM TOPO Li(TTA)(TOPO)2 Healy51
DBM TOPO Li(DBM)2 TOPO or Li2 (DBM)2 · 2HDBM · 4TOPO Lee et al.52
1-tolyl-3-methyl-4-perfluoroacyl-5-pyrazolone (HA) TOPO LiA(TOPO)2 Umetani et al.53
1-phenyl-3-methyl-4-acyl-pyrazol-5-one (HA) TOPO LiA(TOPO)2 Umetani et al.54
1-Phenyl-3-methyl-4-benzoylpyrazol-5-one(HA) TOPO LiA(TOPO)2 Bukowsky et al.55
4-acyl-5-pyrazolones(HA) TOPO LiA(TOPO)2 Mukai et al.56
LIX 51 TOPO Li(LIX 51)(TOPO)1.3 Kinugita et al.58
LIX 54 TOPO Li(LIX 54)(TOPO)1.3 Kinugita et al.58
LIX 54 TOPO Li(LIX 54)(TOPO)1.3 Kunugita et al.59
LIX 54 Cyanex 923 Li(LIX 54)(Cyanex 923) Pranolo et al.60

Solvent extraction of lithium by solvating extractants solvent extraction based on various combinations of 𝛽-diketone
Several authors have reported extraction of lithium using solvating as chelate and a solvation as the ligand is reviewed below.
extractants, as summarized in Table 3. Solvent extraction of alkali Healy developed a formula for the alkali metal extracted species
ions in sodium perchlorate (NaClO4 ) ionic media with TOPO or as M(TTA)S2 (M = Li, Na, K or Cs), where S may be a phosphine
(Oct)3 PO in hexane was studied. The order of extraction follows the oxide, a phosphate, an alcohol, a ketone or an amide. The alkali
order Li+ > Na+ > K+ > Rb+ > Cs+ ; i.e. the smaller the alkali cation metal-organic species forms due to the synergistic effect of TTA
the higher the ability of salvation with TOPO. In the above pro- and TOPO mixture as [M(TTA)(TOPO)2 ].46 Kim et al. reported the
cess, the logKex for Li, Na, K, Rb, Cs was calculated to be 2.29 ± 0.13, synergism of solvent extraction of trace lithium (5.76 × 10−4 mol
1.01 ± 0.14, 0.57 ± 0.22, 0.06 ± 0.1, –0.17 ± 0.21, respectively. The L−1 ) with TTA in the presence of TOPO. The species extracted was
extracted species for Li was [Li(TOPO)3 + (ClO4 )− ]. It is most proba- also determined to be Li(TTA)(TOPO)2 .47 Though the possibility of
ble that the interactions between the TOPO and the alkali metal Li(TTA)(TOPO) adduct cannot be ignored, the stability constant for
ion and perchlorate ion in the organic phase are electrostatic in Li-TTA/2TOPO was 150 times higher than for Li-TTA/TOPO and from
nature.44 The possibility of commercial use of the diketone, dip- the log–log analysis, species formation for extraction of lithium
ivaloylmethane (2,2,6,6-tetramethyl-3,5-heptanedione) has been was concluded to be Li(TTA)(TOPO)2. The diluents used for stud-
proposed.45 The possible chemical reaction of alkali metals in per- ies follow the order m-Xylene > Benzene > MIBK (methyl-isobutyl
chlorate media using TOPO can be explained using Equation (1): ketone) > n-hexane and chloroform for Li(TTA)(TOPO)2 formation.
[ ] The lithium was quantitatively extracted from basic solutions
M+ + ClO−4 + n (TOPO)Org ⇌ M (TOPO)+n ClO−4 Org (1) higher than pH 9 as an adduct Li(TTA)(TOPO)2 into m-xylene. The
logarithmic extraction constant (log Kex ) was 6.76.47 Harvianto
For solvent extraction of lithium, the synergism of a 𝛽-diketone et al. applied the TTA–TOPO mixture for extraction of lithium
as chelate and a solvation ligand like TOPO are very proficient seawater.48 Using TTA–TOPO 93% of lithium could be extracted.
in comparison with only a solvating extractant. 𝛽-diketone, like Lithium ion could be easily stripped by acidic solutions, the strip-
Thenoyltrifluoroacetone (TTA) (commonly known as 2-Thenoyltri- ping efficiency decreases with pH of acidic solutions, and the kind
fluoroacetone, Alpha-Thenoyltrifluoroacetone, 4,4,4-Trifluoro-1-(2- of acid does not affect the stripping efficiency. By the same pro-
thienyl)-1,3-butanedione, TTB, or TTFA), and dibenzoylmethane cess, 65% of lithium can be extracted from seawater by this solvent
(DBM) (otherwise known as 1,3-Propanedione, 1,3-diphenyl-; extraction unless magnesium ion is precipitated prior to the sol-
𝜔-Benzoylacetophenone; Phenyl phenacyl ketone; 1,3- vent extraction process. Other metallic ions in seawater negate the
Diphenyl-1,3-propanedione; 2-Benzoylacetophenone; 1,3-Diphe- extraction efficiency of lithium ion.48
nylpropane-1,3-dione; omega-Benzoylacetophenone; Karenzu Ishimori et al. reported the extraction of lithium with TTA in
DK 2; Rhodiastab 83; NSC 6266) are frequently used for extrac- the presence of PHEN in various organic solvents. The extraction
tion of lithium. Similarly, salvation extractant TOPO, 1,10- equilibrium of alkali metals; Li+ , Na+ , and K+ in the presence
phenanthroline (PHEN) (commonly known as ortho-phenan- or absence of PHEN in chlorobenzene has been discussed. A
throline, 𝛽-phenanthroline, 1, 10-o-phenanthroline, 4, 5-diazaphe- remarkable synergistic effect which enhances the extraction of
nanthrene), 2,9-dimethyl-1,10- phenanthroline (DMP) (oth- lithium was observed in the presence of PHEN. High extractability
erwise named as 2,9-dimethyl-; Neo-Cuproin; 2,9-dimethyl- of lithium was attained in toluene, benzene, chlorobenzene and
o-phenanthroline; 2,9-dimethyl-1,10-phenanthroline; 2,9- o-dichlorobenzene. In the presence of PHEN, TTA extracted lithium
Dimethylphenanthroline are used for synergistic solvent extrac- as [Li(TTA)(PHEN)] over a wide concentration range of PHEN in the
tion of lithium. These combinations are also used for separation organic phase, whereas Na+ and K+ extracted as [Na(TTA)(PHEN)2 ]
of lithium from virtually inseparable alkali metals. Synergistic and [K(TTA)(PHEN)2 ] in the high concentration region. Metal

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 www.soci.org B Swain

adducts formation, such as Li(TTA)(PHEN), Na(TTA)(PHEN)2 and DBM–TOPO studied above can be summarized as in Figure 7. As
K(TTA)(PHEN)2 were confirmed formed in the organic solu- the first step of the reaction, the 𝛽-diketones (TTA, DBM) ionize by
tion using slope analysis. Separation of lithium over sodium displacing protons and the ionized 𝛽-diketones form a chelating
and potassium in chloride solution in TTA and PHEN with complex with lithium. Finally, lithium 𝛽-diketone chelates form an
a solvent extraction system containing various diluents has adduct with solvation ligands like TOPO, PHEN, and DMP.
been reported. The maximum value of the separation factor of Umetani et al. investigated the synergistic solvent extrac-
lithium over sodium and potassium from chloride solution in tion of lithium and sodium into benzene or cyclohexane with
TTA and PHEN was observed, and was larger than that in the 4-benzoyl or 4-perfluoroacyl-5-pyrazolone and TOPO.53 Quanti-
TTA–TOPO–benzene system reported previously.49 Ishimori et al. tative extraction of lithium was achieved with 1-tolyl-3-methyl-
also reported synergistic selective Li+ extraction with TTA and 4-perfluoroacyl-5-pyrazolone and TOPO, where poorer extrac-
PHEN as well as TTA and DMP.50 High lithium extraction and tion of sodium was observed under the same conditions. The
selectivity over sodium and potassium using TTA with PHEN, and perfluoroacyl group at the 4-position of the pyrazolone ring
TTA with DMP has been reported. From the extraction equilibrium enhances maximum percentage extraction of lithium. Diluents
analysis formation of adduct complexes, such as Li(TTA)(DMP), have a significant effect on extraction. Cyclohexane as diluent
Na(TTA)(DMP), K(TTA)(DMP), and K(TTA)(DMP)2 in the DMP extract quantitatively but it depends upon the solubility of the
system, and Li(TTA)(PHEN), Na(TTA)(PHEN), Na(TTA)(PHEN)2 , extractant, whereas improved separation of lithium and sodium
K(TTA)(PHEN), and K(TTA)(PHEN)2 in the PHEN system has been could be achieved when benzene was used as a diluent.53 The
observed. The maximum value of the separation factor (104) same group reported solvent extraction of lithium and alka-
between Li+ and Na+ was found in the TTA-DMP system, which line earth metals with 1-phenyl-3-methyl-4-acyl-pyrazol-5-ones
was much higher than that in the TTA-PHEN system. However, the and TOPO. The synergistic extraction of magnesium, calcium,
application of all these reagents is difficult on a large scale due to strontium, barium, and lithium into cyclohexane or benzene con-
their high toxicity, possibly high price, high water solubility and taining 1-phenyl-3-methyl-4-acyl-pyrazol-5-one(HA) and TOPO
poor solubility in conventional diluents.50 was investigated as a function of pH, HA, and TOPO concentra-
In an another report, Healy reported synergism for extraction of tion by Umetani et al.54 The extracted species were MA2 (TOPO)2
lithium from a mixture of dibenzoylmethane (DBM) and neutral (M = Mg, Ca, Sr), BaA2 (TOPO)3 and LiA(TOPO)2 when 4-benzoyl
donor solvents like phosphine oxide, a phosphate, an alcohol or compound was used as extractant. When the 4-trifluoro-acetyl
an amide. A large synergistic effect was observed in the extraction derivative was used, the extracted species were the same
of lithium and sodium by dibenzoylmethane (DBM) with neutral except for SrA2 (TOPO)3 .54 The extraction of calcium, magne-
donor solvents (S).The formulae of the synergistically-extracted sium, and lithium with 1-phenyl-3-methyl-4-stearoylpyrazol-
species are Li(DBM)S2 , Na(DBM)S2 , and UO2 (DBM)2 S where S may 5-one and with 1-phenyl-3-methyl-4-lauroylpyrazol-5-one was
be a phosphine oxide, a phosphate, an alcohol or an amide.51 studied and separation factors were determined. 1-Phenyl-3-
Quantitative and selective extraction of lithium from aqueous methyl-4-benzoylpyrazol-5-one in the presence of TOPO is also
solutions of alkali metal salts by TOPO and dibenzoylmethane suitable as an extractant for lithium whereas other alkali metals are
(DBM) has been reported. Lithium was readily extracted from extracted to only a limited extent.55 The synergistic liquid–liquid
aqueous solutions of alkali metal salts by forming a TOPO extraction of lithium and sodium with 4-acyl-5-pyrazolones hav-
adduct of lithium dibenzoylmethane (LiDBM) into dodecane ing bulky substituents and TOPO was investigated by Mukai
or p-xylene. In the presence of Na+ or NH4 + , lithium was extracted et al. Enhancement of the extraction of lithium with a mixture of
as LiDBM · 2TOPO species but in the presence of K+ , Rb+ or Cs+ 4-acyl-5-pyrazolones and TOPO was achieved, which was much
ions lithium was extracted as Li2 (DBM)2 · 2HDBM · 4TOPO.52 more than with only TOPO. Quantitative extraction of lithium was
The possible chemical reaction of lithium when using TTA with achieved by adduct formation with TOPO. A significant effect of
TOPO, TTA with PHEN, and TTA with DMP can be explained using organic diluents on the extraction of lithium was observed and
Equation (3), (4) and (5), respectively. The DBM with TOPO can be followed the order cyclohexane > > benzene > > chloroform. The
explained using Equation (7), as given below. maximum percentage extraction and the separation of lithium
and sodium were enhanced by introducing bulky substituents.56
TTA ⇌ TTA− + H+ (2) Umetani et al., Bukowsky et al., and Mukai et al. used
5-pyrazolone derivatives as chelating reagent with lithium
and the solvation extractant TOPO to obtain synergism.54 – 56
Li+ + nTTA− + m (TOPO)Org ⇌ [(Li (TTA)n (TOPO)m ]Org (3) Figure 8 shows a possible generalized extraction mechanism
using 5-pyrazolone derivatives as studied by Umetani et al.,
Bukowsky et al., and Mukai et al.54 – 56 As explained in Fig. 8,
Li+ + nTTA− + m (PHEN)Org ⇌ [(Li (TTA)n (PHEN)m ]Org (4)
4-perfluoroacyl, or 4-acyl or 4-benzoyl derivative of 5-pyrazolone
undergoes protonation, followed by lithium form bond substi-
Li+ + nTTA− + m (DMP)Org ⇌ [(Li (TTA)n (DMP)m ]Org (5) tuted to H+ . Lithium intra-molecular chelation with ketonic O.
Finally, the Li− 5-pyrazolone chelation forms an adduct with TOPO,
which synergies the lithium for better extraction.
DBM ⇌ DBM− + H+ (6) Seeley et al. reported extraction of lithium from neutral salt
solutions with fluorinated 𝛽-diketones.57 Lithium was selectively
extracted from near-neutral aqueous solutions of alkali metal salts.
Li+ + nDBM− + m (TOPO)Org ⇌ [(Li (DBM)n (TOPO)m ]Org (7) The selectivity of the fluorinated 𝛽-diketones for lithium over the
alkaline earth was found to be poor.57 For better extraction TOPO
The chemical reaction mechanism for the synergistic solvent was used along with fluorinated 𝛽-diketone and high separation
extraction of lithium using TTA–TOPO, TTA–PHEN, TTA–DMP and factors were obtained from sodium, potassium, rubidium, and

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(a) Li-TTA-TOPO Senergistic Reaction Mechanism

(CH2)7CH3

S S S S
O O O O
+ Li + + TOPO
Li Li O P (CH2)7CH3
-H+ O
O OH O
F F F F
F F F F F F (CH2)7CH3
F F

TTA 2
Li-TTA Complex Li-TTA-TOPO Adduct

(b) Li-TTA-PHEN Senergistic Reaction Mechanism

S S S S N
O O O O
+ Li + + PHEN
Li Li
-H+ O O
O OH N
F F F F
F F F F F F
F F

TTA Li-TTA Complex Li-TTA-PHEN Adduct

(c) Li-TTA-DMP Senergistic Reaction Mechanism

S S S S N
O O + Li + O O
+ DMP
Li Li
-H+
O OH O O N
F F F F
F F F F F F
F F
TTA Li-TTA Complex Li-TTA-DMP Adduct

(d) Li-DBM-TOPO Senergistic Reaction Mechanism

(CH2)7CH3

+
O OH + Li O + TOPO O

-H +
Li Li O P (CH2)7CH3
O O O O

(CH2)7CH3
2

DBM Li-DBM Complex Li-DBM-TOPO Adduct

Figure 7. Synergistic reaction mechanism for (a) Li-TTA-TOPO, (b) Li-TTA-PHEN, (c) Li-TTA-DMP, and (d) Li-DBM-TOPO.

cesium. The mechanism by which this was achieved involves for- and its separation from sodium with the LIX 54–TOPO system were
mation of the trioctylphosphine oxide adduct of a lithium chelate further studied by Kinugasa et al. and LIX 54-TOPO system con-
of a fluorinated 𝛽-diketone, which is then readily extractable into sidered as the best system.59 Among all reported extractants, LIX
an organic diluent.57 Kunugita et al. studied the extraction of 51–TOPO and LIX 54–TOPO are the most effective extractant for
lithium and its separation from sodium in a sulfate system using extraction of lithium. Figure 9(a) shows Li-LIX 54-TOPO reaction
LIX 51 (𝛼- perflouroalkanoyl-m-dodecylacetophenone) and LIX 54 mechanism and Fig. 9(b) shows Li-LIX 51-TOPO reaction mecha-
(𝛼-acetyl-m- dodecylacetophenone).58 Either LIX 51 or LIX 54 alone nism. The reaction mechanism explained in Fig. 9 is very similar to
could not extract lithium. The extracted species of lithium and the mechanism explained in Figs 7 and 8.
sodium with the LIX 51–TOPO and LIX 54–TOPO systems were Recovery and separation of lithium from sodium in chloride solu-
Li(A(TOPO)1.3 ) and Na(A(TOPO)1.3 ), respectively, where A repre- tions using synergistic solvent extraction systems with LIX 54 and
sents the deprotonated LIX reagent.58 The extraction of lithium Cyanex 923 in ShellSol D70 has been studied by Pranolo et al.60 The

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 www.soci.org B Swain

3 3
2 R 2 R 3 3
R R 2 R 2 R
R R (CH2)7CH3

O O O
-H+ O + TOPO
N N H
+Li N Li N
Li O P (CH2)7CH3
N O N O N
N O O

1 1
R R
R
1
R
1 (CH2)7CH3
2

R1 = tolyl, R2 = methyl, and R3 = perfluoroacyl, Umetani et al. [53]

R1 = phenyl, R2 = methyl, and R3 = acyl, Umetani et al. [54]

R1 = phenyl, R2 = methyl, and R3 = benzoyl, Bukowsky et al. [55]

R1 = H, R2 = H, and R3 = acyl, Mukai et al. [56]

Figure 8. Synergistic reaction mechanism for (a) Li-(1-tolyl-3-methyl-4-perfluoroacyl-5-pyrazolone)-TOPO, (b) Li-(1-phenyl-3-methyl-4-acyl-pyrazol-

5-one)-TOPO, (c) Li-(1-Phenyl-3-methyl-4-benzoylpyrazol-5-one)-DMP, and (d) Li-(4-acyl-5-pyrazolones)-TOPO.

(a)
Li-LIX 54-TOPO Senergistic Reaction Mechanism

(CH 2 ) 7 CH3

O + Li+ O O
O + TOPO
-H+
Li Li O P (CH 2)7CH3
OH O O
O
H3C(H 2C) 6 H3C(H 2C) 6
H3C(H 2C) 6 H3C(H 2C) 6 (CH 2 ) 7 CH3
1.3
LIX 54 Li- LIX 54 Chelate Li- LIX 54 -TOPO Adduct

(b)
Li-LIX 51-TOPO Senergistic Reaction Mechanism
(CH 2)10CH3 (CH ) CH (CH 2)10CH3 (CH 2)10CH3
2 10 3

(CH 2 ) 7 CH3

O + Li+ O O
O + TOPO
Li Li O P (CH 2 ) 7 CH3
-H+
OH O O
O

F 3C F 3C F 3C
F 3C (CH 2 ) 7 CH3
1.3
LIX 51 Li- LIX 51 Chelate Li- LIX 51-TOPO Adduct

Figure 9. Synergistic reaction mechanism for (a) Li-LIX 54-TOPO, and (b) Li-LIX 51-TOPO.

Cyanex 923 extractant is a mixture of four trialkylphosphine oxides From the species shown on Table 3, Figs 7–9 and 10, synergis-
as follows: R3 P(O) R2 R’P(O) RR’2 P(O) R’3 P(O) where R = [CH3 (CH2 )7 ] tic extraction can be generalized as a combination of two com-
- normal octyl R’ = [CH3 (CH2 )5 ] - normal hexyl. Over 97% of lithium ponents. Of the two components, one is a solvating extract (S) as
was extracted at pH 11 from a synthetic solution with almost no the ligand and the other is an ionizable species like 𝛽-diketone or
extraction of sodium with synergistic solvent extraction systems pyrazolone derivative (HA) which form an Li–A chelate for solva-
with LIX 54 and Cyanex 923. In the synergistic solvent extraction tion reaction. The generalized chemical reaction for lithium using
system, a separation factor of 1560 was achieved for lithium over A–S can be explained using Equation (8) and Equation (9), where
sodium. The coextracted sodium was scrubbed from the loaded A stands for TAA or a DBM or a pyrazolone derivative and S is TOPO
organic solution using water, and lithium was readily stripped with or PHEN or DMP or Cyanex 923:
an acidic solution and complete stripping was achieved at an equi-
librium of 3.5.60 Figure 10 explains the lithium extraction mecha-
nism using LIX 54 and Cyanex 923. HA ⇌ A− + H+ (8)

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Li-LIX 54-Cyanex 923 Senergistic Reaction Mechanism

(CH2)5CH3
(CH2)7CH3
O
O
Li O P (CH2)5CH3 Li O P (CH2)7CH3
O
O
H 3C(H 2C) 6
(CH2)5CH3 H 3C(H 2C) 6
m (CH2)7CH3
m
+
Cy
an
ex

23
92

x9
3

ne
ya
+C
O O O
+ Li+
Li
-H+
O OH O

+
Cy
H3C(H 2C) 6 H3C(H 2C) 6
H3C(H 2C) 6

an
ex9
Li- LIX 54 Chelate

23
3
92

LIX 54
ex
an
Cy
+

(CH2)5CH3
(CH2)7CH3
O
O
Li O P (CH2)7CH3 Li O P (CH2)5CH3
O
O
H 3C(H 2C) 6
(CH2)5CH3 H 3C(H 2C) 6
m (CH2)7CH3
m

Figure 10. Synergistic reaction mechanism for Li-LIX 54-Cyanex 923.

extraction media are not suitable for industrial application based

Li+ + nA− + m (S)Org ⇌ [(Li (A)n (S)m ]Org (9)
on environment and cost aspects. The possibility of using com-
An equilibrium extraction constant for Equation (9) can be mon industrially used organic media like Shellshol, Escaid, and
expressed as: Kerosene has hardly been reported in the literature. Recently, Shi
[(Li (A)n (S)m ]Org et al. reported lithium extraction using room temperature ionic
Kex = (10) liquid 1-butyl-3-methyl-imidazolium hexafluorophosphate as an
[Li+ ] [A− ]n [S]m
Org organic medium using TBP as an extractant. Sodium perchlo-
rate ionic media (NaClO4 ) was used as the aqueous medium in
Equation (10) can be simplified using distribution ratio as
the solvent extraction. The effects of solution pH value, phase
D ratio, ClO4 − amount and other factors on lithium extraction effi-
Kex = (11) ciency have been investigated. Quantitative extraction of lithium
[A− ]n [S]m
Org
was observed.61 Shi et al. also applied room temperature ionic liq-
where D is given by uid (RTIL), 1-butyl-3-methylimidazolium hexafluorophosphate, in
the extraction of lithium ion from salt lake brine using TBP as
[(Li (A)n (S)m ]Org extractant.62 Preliminary results indicated that the use of room
D= temperature ionic liquid 1-butyl-3-methyl-imidazolium hexafluo-
[Li+ ]
rophosphat as an alternate solvent to replace traditional organic
Taking logarithm Equation (11) are expressed as solvents in the solvent extraction of lithium is promising, and
[ ] needs more extensive research.
log Kex = log D − n log [A− ] + m log (S)Org (12)
Solvent extraction of lithium by other extractants
Solvent extraction of lithium by ionic liquid Sholl et al. synthesized aza phenol cryptand and the extractabil-
As discussed, not only the extractant but also the organic medium ity of Li+ using the aza phenol cryptand were studied. It was
used for lithium solvent extraction plays a vital role in selective reported that Li+ extracted from aqueous solutions into chloro-
extraction/separation of lithium. Most organic solvents used for form with a very high selectivity of Li+ /Na+ = 400.63 However, a

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Li-TTA-12 Crwon 4 ether Senergistic Reaction Mechanism

S S
S
O
S
O + Li + O
+ 12 Crwon 4 O O O
Li Ether Li
-H+
O OH O O O O
F F F F
F F F F F F
F F
2
TTA Li-TTA Complex Li-TTA- 12 Crwon 4 Ether Adduct

Figure 11. Synergistic reaction mechanism for (a) Li-TTA-12 Crown 4 ether.

much higher selectivity method is required for separation and geothermal water, using a SLM of LIX54 and TOPO in kerosene.
determination of lithium in sea water which contains Na+ of 0.5 The model is based on fundamental mass transfer and kinetics
mol L−1 .63 Solvent extraction of lithium using different n-butanol mechanisms that account for all possible transport resistances.
has been reported.64 Lithium chloride extraction with n-butanol The model is used to investigate the effect of various extraction
has been studied using different concentrations of Li, Na, K and Ca conditions and membrane support characteristics. Reasonable
in chloride medium. Based on different process parameter opti- agreement is found between the predicted and the experimental
mizations a laboratory scale lithium recovery process has been results reported in the literature.68
proposed, where 99% pure lithium chloride recovery is indicated.64 New types of lipophilic phthalocyanine derivatives, hexadeca
Extraction of lithium halides including alkali halides by isopentyl (2,2,2-trifluoro-ethoxy) phthalocyanine and hexadeca(2,2,3,3,3-
alcohol has been studied. The extraction of metal halides follow pentafluoro- propoxy) phthalocyanine (abbreviated H2 Pc(TFE)16
the order Li > Cs > Na ≈ K which also depends upon extraction and H2 Pc(PFP)16 , respectively), has been prepared by Kondo et al.
in the anion order Cl < Br < I.65 Itoh et al. reported separation of and evaluated for lithium extraction by SLM.69,70 The extraction
trace lithium with 12-crown-4 ether and TTA. Though the report equilibria of alkali metals with H2 Pc(TFE)16 and H2 Pc(PFP)16 were
is about the determination of lithium at a ppb-ppm level, but investigated, and the extracted complexes and extraction equilib-
the same process can be used for lithium purification. Lithium rium constants of the metals were estimated. The extraction rate
extraction using TTA and 12-crown-4 ether in the various organic of lithium with extractant H2 Pc(TFE)16 was measured. The perme-
medium like benzene, cyclohexane, and o-dichlorobenzene has ation rates of alkali metals through a SLM containing H2 Pc(TFE)16
been investigated, among them o-dichlorobenzene was the best were measured. The transport selectivity of lithium was enhanced
∘
medium for synergistic extraction of lithium. The TTA and the with increase temperature and showed a value of 1.61 at 318 K
12-crown-4 combination have a higher synergistic effect over against potassium. Sodium permeation is limited by the reaction
TTA and TBP. On the basis of these results, the extraction behav- process at the interface. For lithium and potassium permeation
ior of TTA chelate of lithium in o-dichlorobenzene followed by the diffusion of a complex in the membrane accompanying the
adduct formation with 12-crown-4 was indicated.66 Figure 11 reaction is considered to be the rate-controlling step. The extrac-
shows the mechanism of TTA–Li chelation followed by adduct for- tion process is considered to be limited by the diffusion of the
mation. extractant.70

EXTRACTION OF LITHIUM BY SUPPORTED CONCLUSION

LIQUID MEMBRANE (SLM) The consumption of the energy metal lithium is increasing rapidly
This review of lithium solvent extraction revealed that most stud- and estimated to grow exponentially. To meet the lithium require-
ies reported are fundamental studies lacking advanced applica- ment it is essential to find alternatives for the efficient recovery
tion in industry for lithium production. Most authors have used of lithium from secondary resources such as from lithium-ion bat-
very expensive extractant (crown ether) for lithium extraction. teries (LIB). To favor a clean environment and to support environ-
Considering the important drawbacks of solvent extraction, such mental regulation and lithium metal economy, it is also essential to
as high solvent inventory, flooding and solvent loss during extrac- recover the metals from waste LIB. Our thorough literature investi-
tion, then SLM should be an important alternative for extraction gation suggests that lithium extraction using SLM is severely lim-
of high purity lithium. Hence, lithium extraction by SLM has been ited. Considering the drawbacks of solvent extraction and lack of
reviewed.67 – 70 research into SLM for lithium extraction, systematic fundamental
Ma et al. reported a SLM extraction process using a carrier and advanced research needs to be conducted. Although SX is a
combination of LIX54 and TOPO.67 This carrier combination has a versatile method for industrial production of lithium and SLM is
synergistic effect on lithium extraction and was found to be most an advanced technology to recover metals, in the case of lithium
effective. Variables considered were pH, carrier concentrations, both the processes have severe limitations. For lithium extraction
initial lithium concentration, type of organic solvent and stripping by SX, most of the reported extractants are non-commercial or
phase, and the presence of sodium and potassium ions in the feed, expensive. For lithium extraction by SLM, research and develop-
and flow rates of both aqueous phases. The optimal extraction ment reports are very limited. Hence, research and development
efficiency of the system was greater than 95% for a model feed of lithium extraction by SX and SLM using cheaper extractants,
solution containing Na+ , K+ , and Li+ at pH greater than 12.5.67 research into the commercial production of cheaper extractant
Bansal et al. reported a mathematical transport model for the and a commercial process for recovery of lithium from secondary
extraction of lithium from dilute synthetic solution, simulating resources are essential.

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ACKNOWLEDGEMENTS 27 Katayama Y, Nita K, Ueda M, Nakamura H, Takagi M and Ueno K, Syn-

thesis of chromogenic crown ethers and liquid–liquid extraction of
Lovingly dedicated to my most loving mother, Mrs. Ahalya Swain alkali metal ions. Analyt Chim Acta 173:193–209 (1985).
On her II death anniversary 16th May 2016. ‘May God grant her a 28 Uhlemann E, Geyer H, Gloe K and Mühl P, Synthese und extrak-
place in the heaven’. tionseigenschaften von 2-(sym-dibenzo-14-krone-4-oxy)essigsäure
bzw. -n-hexansäure. Analyt Chim Acta 185:279–285 (1986).
29 Habata Y, Ikeda M and Akabori S, Lithium ion selective
dibenzo-14-crown-4 possessing a phosphoric acid functional
REFERENCES group as a pendant. Tetrahed Lett 33:3157–3160 (1992).
1 Bach RO, Lithium, current applications in science, medicine, and tech- 30 Tsukube H, Hori K and Inoue T, Amine-armed aza-12-crown-4 as a new
nology. Wiley, American Chemical Society, Southeastern Regional Li+ ion-specific ionophore. Tetrahedron Lett 34:6749–6752 (1993).
Meeting (1985). 31 Sasaki K and Pacey G, The synthesis and analytical capabilities of
2 Chagnes A and Swiatowska J, Lithium Process Chemistry: Resources, chromogenic aza-12-crown-4 as a selective reagent for lithium ion.
Extraction, Batteries, and Recycling. Elsevier Science (2015). Analyt Chim Acta 174:141–149 (1985).
3 Sapse AM and Von R. Schleyer P, lithium chemistry: a theoretical and 32 Bartsch RA, Czech BP, Kang SI, Stewart LE, Walkowiak W, Charewicz
experimental overview. Wiley (1995). WA, Heo GS and Son B, High lithium selectivity in competitive alkali
4 Nishi Y, Lithium ion secondary batteries; past 10 years and the future. metal solvent extraction by lipophilic crown carboxylic acids. J Am
J Power Sources 100:101–106 (2001). Chem Soc 107:4997–4998 (1985).
5 Vincent C, Lithium Batteries. http://digital-library.theiet.org/content/ 33 Nishizawa K, Takano T, Ikeda I and Okahara M, Extractive separation
journals/10.1049/ir_19990205 [1999]. of lithium isotopes by crown ethers. Sep Sci Technol 23:333–345
6 Vincent CA, Lithium batteries: a 50-year perspective, 1959–2009. Solid (1988).
State Ionics 134:159–167 (2000). 34 Nishizawa K and Takano T, Extractive separation of lithium isotopes
7 http://batteryuniversity.com/, BU-103: Global Battery Markets (2015). using benzo-15-crown-5. Effect of salt concentration. Sep Sci Technol
8 Resea MA, Lithium Demand, Pricing, and Supply Forecast Considered 23:751–757 (1988).
as Li-ion in Automotive Use to Surge (2009). 35 Hano T, Matsumoto M, Ohtake T, Egashir N and Hori F, Recovery of
9 Brenner A, Electrodeposition of Alloys: Principles and Practice. Academic lithium from geothermal water by solvent extraction technique.
Press, London,(1963). Solvent Extract Ion Exchange 10:195–206 (1992).
10 Hamzaoui AH, M’Nif A, Hammi H and Rokbani R, Contribution to the 36 Swain B, Jeong J, Lee J and Lee G-H, Separation of cobalt and lithium
lithium recovery from brine. Desalination 158:221–224 (2003). from mixed sulphate solution using Na-Cyanex 272. Hydrometal-
11 Goonan TG, Lithium use in batteries: US Geological Survey Circular lurgy 84:130–138 (2006).
1371, US Geological Survey, Reston, Virginia (2012). 37 Kang J, Senanayake G, Sohn J and Shin SM, Recovery of cobalt
12 Garrett DE, Handbook of Lithium and Natural Calcium Chloride. Elsevier sulfate from spent lithium ion batteries by reductive leaching and
Science (2004). solvent extraction with Cyanex 272. Hydrometallurgy 100:168–171
13 Bohner HO, Metallurgical Society of A and Light Metals C, Light metals, (2010).
1985: Proceedings of the technical sessions sponsored by the TMS 38 Swain B, Jeong J, Lee J-c and Lee G-H, Development of process flow
Light Metals Committee at the 114th annual meeting, New York, sheet for recovery of high pure cobalt from sulfate leach liquor
New York, February 24–28, 1985. Metallurgical Society of AIME, of LIB industry waste: a mathematical model correlation to pre-
Warrendale, PA. dict optimum operational conditions. Sep Purif Technol 63:360–369
14 Margarido F, Vieceli N, Durão F, Guimarães C and Nogueira CA, (2008).
Minero-metallurgical processes for lithium recovery from peg- 39 Swain B, Jeong J, Lee J-c, Lee G-H and Sohn J-S, Hydrometallurgical
matitic ores. Comunicações Geológicas 101:795–798 (2014). process for recovery of cobalt from waste cathodic active material
15 Medina L and El-Naggar MAA, An alternative method for the recovery generated during manufacturing of lithium ion batteries. J Power
of lithium from spodumene. MTB 15:725–726 (1984). Sources 167:536–544 (2007).
16 May JT, Witkowsky DS, Seidel DC and Mines USBo, Extracting lithium 40 Mantuano DP, Dorella G, Elias RCA and Mansur MB, Analysis of
from clays by roast-leach treatment. Department of the Interior, a hydrometallurgical route to recover base metals from spent
Bureau of Mines (1980). rechargeable batteries by liquid–liquid extraction with Cyanex 272.
17 Davidson CF and Mines USBo, Recovery of lithium from clay by J Power Sources 159:1510–1518 (2006).
selective chlorination. US Department of the Interior, Bureau of 41 Zhang P, Yokoyama T, Itabashi O, Suzuki TM and Inoue K, Hydrometal-
Mines (1981). lurgical process for recovery of metal values from spent lithium-ion
18 An JW, Kang DJ, Tran KT, Kim MJ, Lim T and Tran T, Recovery of lithium secondary batteries. Hydrometallurgy 47:259–271 (1998).
from Uyuni salar brine. Hydrometallurgy 117–118:64–70 (2012). 42 Zhao JM, Shen XY, Deng FL, Wang FC, Wu Y and Liu HZ, Synergistic
19 Contestabile M, Panero S and Scrosati B, A laboratory-scale lithium extraction and separation of valuable metals from waste cathodic
battery recycling process 1. J Power Sources 83:75–78 (1999). material of lithium ion batteries using Cyanex 272 and PC-88A. Sep
20 Xu J, Thomas HR, Francis RW, Lum KR, Wang J and Liang B, A review Purif Technol 78:345–351 (2011).
of processes and technologies for the recycling of lithium-ion sec- 43 Pranolo Y, Zhang W and Cheng CY, Recovery of metals from spent
ondary batteries. J Power Sources 177:512–527 (2008). lithium-ion battery leach solutions with a mixed solvent extractant
21 Lowry TH and Richardson KS, Mechanism and Theory in Organic Chem- system. Hydrometallurgy 102:37–42 (2010).
istry. Harper and Row (1987). 44 Kusakabe S and Sekine T, Studies on the solvent extraction of metal
22 Pearson RG, Hard and Soft Acids and Bases. Dowden, Hutchinson and perchlorates. II. Extraction of alkali metal perchlorates with tri-
Ross, Stroudsburg, PA (1973). octylphosphine oxide. Bull Chem Soc Japan 53:2087–2088 (1980).
23 Izatt RM, Pawlak K, Bradshaw JS and Bruening RL, Thermodynamic and 45 Dang V-D and Steinberg M, Preliminary design and analysis of recovery
kinetic data for macrocycle interactions with cations and anions. of lithium from brine with the use of a selective extractant. Energy
Chem Rev 91:1721–2085 (1991). 3:325–336 (1978).
24 Czech BP, Babb DA, Son B and Bartsch RA, Functionalized 13-crown-4, 46 Healy TV, Synergism in the solvent extraction of alkali metal ions
14-crown-4, 15-crown-4, and 16-crown-4 compounds: synthesis by thenoyl trifluoracetone. J Inorgan Nuclear Chem 30:1025–1036
and lithium ion complexation. J Organic Chem 49:4805–4810 (1968).
(1984). 47 Kim Y-S, In G and Choi J-M, Chemical equilibrium and synergism
25 Bartsch RA, Goo M-J, Christian GD, Wen X, Czech BP, Chapoteau for solvent extraction of trace lithium with thenoyltrifluoroacetone
E and Kumar A, Influence of ring substituents and matrix in the presence of trioctylphosphine oxide. Bull Korean Chem Soc
on lithium/sodium selectivity of 14-crown-4 and benzo-13- 24:1495–1500 (2003).
crown-4-compounds. Anal Chim Acta 272:285–292 48 Harvianto G, Kim S-H and Ju C-S, Solvent extraction and stripping of
(1993). lithium ion from aqueous solution and its application to seawater.
26 Boulatov R, Du B, Meyers EA and Shore SG, Two novel lithium − Rare Met DOI: 10.1007/s12598-015-0453-1 (2015).
15-crown-5 complexes: an extended LiCl chain stabilized by crown 49 Ishimori K, Imura H and Ohashi K, Effect of 1,10-phenanthroline on the
ether and a dimeric complex stabilized by hydrogen bonding with extraction and separation of lithium(I), sodium(I) and potassium(I)
water. Inorganic Chem 38:4554–4558 (1999). with thenoyltrifluoroacetone. Anal Chim Acta 454:241–247 (2002).

J Chem Technol Biotechnol (2016) © 2016 Society of Chemical Industry wileyonlinelibrary.com/jctb

 www.soci.org B Swain

50 Ishimori K-I, Imura, H, The synergistic selective extraction of 60 Pranolo Y, Zhu Z and Cheng CY, Separation of lithium from sodium in
lithium(I) with 2-thenoyltrifluoroacetone and 1,10-phenanthroline chloride solutions using SSX systems with LIX 54 and Cyanex 923.
derivatives. Solvent Extract Res Develop Japan 9:13–25 Hydrometallurgy 154:33–39 (2015).
(2002). 61 Shi C, Duan D, Jia Y and Jing Y, A highly efficient solvent system con-
51 Healy TV, Synergism in the solvent extraction of metal ions by diben- taining ionic liquid in tributyl phosphate for lithium ion extraction.
zoylmethane. J Inorg Nuclear Chem 31:499–511 (1969). J Moc Liquids 200B: 91–195 (2014).
52 Lee DA, Taylor WL, McDowell WJ and Drury JS, Solvent extraction of 62 Shi C, Jia Y, Zhang C, Liu H and Jing Y, Extraction of lithium from
lithium. J Inorg Nuclear Chem 30:2807–2821 (1968). salt lake brine using room temperature ionic liquid in tributyl
53 Umetani S, Maeda K, Kihara S and Matsui M, Solvent extraction of phosphate. Fusion Eng Design 90:1–6 (2015).
lithium and sodium with 4-benzoyl or 4-perfluoroacyl-5-pyrazolone 63 Sholl AF and Sutherland IO, Selective chromogenic reagents based
and TOPO. Talanta 34:779–782 (1987). upon phenolic cryptands. Chem Soc Chem Commun 1716–1718
54 Umetani S, Sasayama K and Matsui M, Solvent extraction of (1992).
alkaline earth metals, and lithium with 1-phenyl-3-methyl-4- 64 Gabra GG and Torma AE, Lithium chloride extraction by n-butanol.
acylpyrazol-5-ones and trioctylphosphine oxide. Anal Chim Acta Hydrometallurgy 3:23–33 (1978).
134:327–331 (1982). 65 Rozen AM and MIkhailichenko AI, Extraction alkali metal halides by
55 Bukowsky H, Uhlemann E, Gloe K and Mühl P, Liquid–liquid extraction isopentyle alcohol. Russian J Inorg Chem 12:380–387 (1967).
of alkaline earth and alkali metal ions with acylpyrazolones. Anal 66 Tatsuo Itoh MB, Takaharu Honjo, Kikuo Terada, Separation and deter-
Chim Acta 257:105–108 (1992). mination of a trace amount of lithium as its thenoyltrifluoroace-
56 Mukai H, Miyazaki S, Umetani S, Kihara S and Matsui M, Synergic tone complex with 12-crown-4 by means of synergic extraction and
liquid/liquid extraction of lithium and sodium with 4-acyl-5- flame photometry. Anal Sci 7:47–50 (1991).
pyrazolones with bulky substituents and tri-n-octylphosphine 67 Ma P, Chen XD and Hossain MM, Lithium extraction from a multicom-
oxide. Anal Chim Acta 220:111–117 (1989). ponent mixture using supported liquid membranes. Sep Sci Technol
57 Seeley FG and Baldwin WH, Extraction of lithium from neutral salt 35:2513–2533 (2000).
solutions with fluorinated 𝛽-diketones. J Inorg Nuclear Chem 68 Bansal B, Chen XD and Hossain MM, Transport of lithium through a
38:1049–1052 (1976). supported liquid membrane of LIX54 and TOPO in kerosene. Chem
58 Kunugita E, Kim JH and Komsawa I, Extraction and separation of Eng Process: Process Intens 44:1327–1336 (2005).
lithium and sodium by solvent extraction with .BETA.-diketone and 69 Kondo K, Matsumoto M, Yoshida T and Sonoda T, Extraction of
neutral ligand. Kagaku Kogaku Ronbunshu (Japanese) 15:504–510 lithium ion with novel lipophilic phthalocyanine derivatives. Kagaku
(1889). Kogaku Ronbunshu (Japanese) 26:542–547 (2000).
59 Kinugasa T, Nishibara H, Murao Y, Kawamura Y, Watanabe K and 70 Kazuo K, Selective Extraction of Lithium Ion with Novel Lipophilic
Takeuchi H, Equilibrium and kinetics of lithium extraction by Phthalocyanine Derivatives and Its Permeation through Supported
a mixture of LIX54 and TOPO. J Chem Eng Japan 27:815–818 Liquid Membrane, in Proceedings of the International Solvent
(1994). Extraction Conference 2002, 706–711.

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