**4.3 Ion-exchange method of lithium recovery from brine**

Through the use of a specially made resin/aluminates composite/inorganic ion exchanger, from brine lithium can be recovered productively. Bukowski et al. reported through a process of carbocation and ion exchange an extract of pure LiCl from brines containing higher levels of CaCl2 and MgCl2 [77]. Three different ion exchange resins Y80-N Chemie AG (Chemie AG Bitterfeld-Wolfen)), TP207 resin (Bayer AG), (MC50 resin, (Chemie AG Bitterfeld-Wolfen) for lithium extraction from synthetic brine were investigated. As a result of the conducted researches, it is established that it is possible to clean LiCl solutions with Y 80 resin at room temperature and with TP 207 resin at 50°C [77]. Hui et al. synthesis of H2TiO3 ion exchanger and extraction of lithium from the brine of natural gas wells have been reported [76]. Ion exchanger H2TiO3 was synthesized from Li2CO3 and TiO2 or precipitation of LiOH and TiO2 followed by calcination at 400–800°C. Ion exchanger H2TiO3 provided high selectivity for Li+ at an exchange capacity of Li+ 25.34 mg g<sup>−</sup><sup>1</sup> in mixtures

**193**

**Resources** End brine and Dead Sea brine

Dead Sea brine Dead Sea brine Salar de Uyini, Bolivia Dead Sea brine From other alkali metal Seawater, hydrothermal water

Column chromatography

Synthetic brine

Brine of natural gas

Inorganic ion

H TiO 2

3 ion exchanger

exchanger

Inorganic ion

H TiO 2

3 ion exchanger

exchanger

wells

Salt Lake brine Synthetic brine

Synthetic brine

Brine Brine

Liquid-liquid

2-Ethyle-1,3-hexanediol, isoamyle alcohol, di-isopropyl ether, diethyl ether

extraction

Liquid-liquid

With tributyl phosphate (TBP)

HeptofIuorodimethyloctunedione, peniafluorodimeihylhepiunedione,

trifluorodimethylhexanedione, dibenzoylmethane and tetrameihylheptonedione

extraction

Liquid-liquid

extraction

Liquid-liquid

n-Butanol

extraction

Chelating resins

MC50 resin, TP207 resin, Y80-N Chemie AG

Reversed phase chromatography

Gel permeation chromatography

Polyacrymidegel, Bio-Gel P-2 and Blue Dextran 2000

Polytetrafluroethylene tribytyle phosphase (TBP), dibenzoylmethane (DBM) and trioctylephosphine oxide (TOPO)

Titanium (IV) antimonate cation exchanger (TiSbA)

Precipitation Precipitation Precipitation

Lithium aluminate

Lithium aluminate

Precipitation

**Process**

**Reagents** Lithium aluminate

**Mechanism** Precipitaion Precipitaion Precipitaion Precipitaion Column chromatography

[77]

Column chromatography

[76]

Column chromatography

[78]

Ion exchange Ion exchange Ion exchange

[81]

[82]

[83]

[84]

[85]

[80]

[79]

[76]

[75]

[74]

[73]

**Reference**

*Lithium Recovery from Brines Including Seawater, Salt Lake Brine, Underground Water…*

*DOI: http://dx.doi.org/10.5772/intechopen.90371*


*Lithium Recovery from Brines Including Seawater, Salt Lake Brine, Underground Water… DOI: http://dx.doi.org/10.5772/intechopen.90371*

*Thermodynamics and Energy Engineering*

As a result of precipitation processes with a high content of pure (99.55%) and

*Outotec lithium production technology from brine. Reproduced with permission from Outotec.*

Through the use of a specially made resin/aluminates composite/inorganic ion exchanger, from brine lithium can be recovered productively. Bukowski et al. reported through a process of carbocation and ion exchange an extract of pure LiCl from brines containing higher levels of CaCl2 and MgCl2 [77]. Three different ion exchange resins Y80-N Chemie AG (Chemie AG Bitterfeld-Wolfen)), TP207 resin (Bayer AG), (MC50 resin, (Chemie AG Bitterfeld-Wolfen) for lithium extraction from synthetic brine were investigated. As a result of the conducted researches, it is established that it is possible to clean LiCl solutions with Y 80 resin at room temperature and with TP 207 resin at 50°C [77]. Hui et al. synthesis of H2TiO3 ion exchanger and extraction of lithium from the brine of natural gas wells have been reported [76]. Ion exchanger H2TiO3 was synthesized from Li2CO3 and TiO2 or precipitation of LiOH and TiO2 followed by calcination at 400–800°C. Ion exchanger H2TiO3 pro-

at an exchange capacity of Li+

25.34 mg g<sup>−</sup><sup>1</sup>

in mixtures

**4.3 Ion-exchange method of lithium recovery from brine**

crystalline Li2CO3 were reduced [93].

vided high selectivity for Li+

**192**

**Figure 2.**


**Table 1.**

**195**

**from brine**

lation efficiency was 85.61% at 1.0 mol L<sup>−</sup><sup>1</sup>

*Lithium Recovery from Brines Including Seawater, Salt Lake Brine, Underground Water…*

of alkaline earth metal and an alkali metal. From brine ion exchanger H2TiO3 showed

Many studies have provided my traditional liquid-liquid extraction and liquidliquid extraction by ionic liquids (ILs) have been reported for lithium extraction from brine. Gabra et al. using synthetic solutions of nbutanol containing different amounts of lithium, potassium, calcium and sodium chloride, a laboratory-scale of LiCl extraction process were developed. A method for lithium reduction for separation and LiCl reduction is proposed, derived from distribution coefficients, separation coefficients and the presentation of McCabe-Thiel results. According to this method, 99.6% purity of LiCl can be restored [78]. Liquid-liquid extraction of lithium from brines by alcohol such as isoamyl alcohol and n-butanol, combined with precipitation of the lithium-aluminum complex reported by Bukowski et al. The amount of LiCl extraction from brine at pH 5.4 with different alcohol follow the order: 2-ethyl-1,3-hexanediol > isoamyl alcohol > di-isopropyl ether > diethyl ether and can extract 32.8, 25.2, 11.4, 9.1% lithium, respectively, along with Na, Mg and Ca. Lithium extraction was also studied using a binary mixture of the above compounds in a 1:1 ratio at a pH of 5.4. 2-ethyl-1,3-hexanediol mixed with isoamyl alcohol is suitable for 90% LiCl reduction as well as suppression of metal co-extraction [79]. Zhou et al. reported the extraction of lithium from brine sources using tributyl phosphate (TBP) in three different diluents [55]. Three salt solutions (ZnCl2, FeCl3 and CrCl3) were selected as co-extractors to investigate the possibility of extracting lithium metal from brine sources. The method of liquid-liquid extraction equilibrium of lithium with tributyl phosphate (TBP) in methylisobutyl ketone (MIBC), TBP in kerosene and TBP in 2-octanol was analyzed. In liquid–liquid extraction, lithium equilibrium is investigated by FeCl3 solution as a co-extractor. The results showed that the extraction efficiency followed the sequence: TBP/2 octanol < TBP/kerosene < TBP/MIBK. It was significantly larger than the TBP/2 octanol system than the TBP/MIBK and TBP/kerosene systems for lithium recovery [55]. A method for extracting lithium from neutral brines using beta-diketone and trioctyl phosphine oxide in benzene was patented by Baldwin and Seeley [80]. The

mechanism of extraction was discussed in more detail with scientists [81].

**4.5 Liquid-liquid extraction using ionic liquid method to extract lithium** 

Unlike traditional liquid-liquid extraction, ionic liquid extraction is considered not only as a solvent but also as a co-extraction reagent. Gao et al. reported the extraction of lithium from salt lake brine using tri-isobutyl phosphate in ionic liquid and kerosene [82]. Three ionic liquids (ILs) have been reported, that is, 1-ethyl-3-methyl-imidazolium-bis[(trifluoromethyl)-sulfonyl]-imide, 1-butyl-3-methylimidazolium-bis[(trifluoromethyl)-sulfonyl]-imide and 1-butyl-3-methylimidazolium-hexafluorophosphate with triisobutyl phosphate (TIBP) and kerosene for ion recovery lithium from salt lake brine. The results show that the best selective lithium extraction was obtained using IL 1-ethyl-3-methylimidazole bis[(trifluoromethyl)-sulfonyl] imide. Under optimal extraction conditions, the one-stage efficiency of lithium ion extraction was 83.71% and the one-stage distil-

HCl in 1.0 mol L<sup>−</sup><sup>1</sup>

NaCl as a stripping

at pH 6.5 from brine was reported [53].

the same H2TiO3 ion exchanger extract lithium from Salt lake brine. Adsorption of lithium ions by H2TiO3 ion exchanger according to Langmuir model having exchange

[76]. Chitrakar et al. reported with

*DOI: http://dx.doi.org/10.5772/intechopen.90371*

capacity for Li+

97% exchange rate and 98% elution rate for Li+

25.34, 32.6 mg g<sup>−</sup><sup>1</sup>

**4.4 Liquid-liquid method of lithium recovery from brine**

*Recovery of lithium from brines by various processes.* *Lithium Recovery from Brines Including Seawater, Salt Lake Brine, Underground Water… DOI: http://dx.doi.org/10.5772/intechopen.90371*

of alkaline earth metal and an alkali metal. From brine ion exchanger H2TiO3 showed 97% exchange rate and 98% elution rate for Li+ [76]. Chitrakar et al. reported with the same H2TiO3 ion exchanger extract lithium from Salt lake brine. Adsorption of lithium ions by H2TiO3 ion exchanger according to Langmuir model having exchange capacity for Li+ 25.34, 32.6 mg g<sup>−</sup><sup>1</sup> at pH 6.5 from brine was reported [53].
