Hydrophobic organic liquid composition for the selective extraction of a lithium salt.

Abstract

------ Hydrophobic Organic Liquid Composition for the Selective Extraction of a Lithium Salt The present invention relates to a hydrophobic organic liquid composition for the selective extraction of a diionic lithium salt comprising a lithium cation and an anion complementary to the lithium cation selected in particular from Cl-, I-, Br-, CN-, NO3-, HCO3- from a lithium-rich brine to be treated, said composition comprising (A) at least one compound extracting lithium cation, selected from compounds of formula: in which R1, R2, R3, R4, R5 and R6 are as defined in the description; (B) at least one organic, protic and hydrophobic compound solvating the anion complementary to the lithium cation; and (C) at least one hydrophobic polar organic diluent having a flash point at atmospheric pressure above 60°C, preferably above 75°C, more preferably above 90°C.

Description

Title of the invention: Hydrophobic organic liquid composition for the selective extraction of a lithium salt.

[0001] The present invention relates to a hydrophobic organic liquid composition for the selective extraction of a lithium salt.

[0002] In the context of the energy transition, global objectives to replace vehicles emitting 20% ​​of global CO2 with electric vehicles lead to the need to multiply the global production of metals such as lithium, nickel, cobalt, copper, manganese... Thus, in particular, lithium, essential for the construction of lithium-ion batteries, should see its production multiplied by four between 2020 (990 kt lithium carbonate equivalent (LCE)) and 2030 (3,700 kt LCE) for the construction of sixteen times more electric vehicles and to supply more than three hundred new battery factory projects.

[0003] Due to this very strong demand which exceeds supply, the price of Lithium has risen from US$16,750 / tonne LCE in 2018 to US$71,750 / tonne LCE in 2022. However, this excess demand is not likely to diminish quickly due to lithium mining production capacity which is unable to keep up with demand.

[0004] Indeed, although lithium is widely available on earth, either in the form of mineral rock (Spodumene, Lepidolite, Petalite...), or in the form of salt (LiCl, Li2SO4...) dissolved or undissolved in water, its extraction (186 kt Li) is still relatively modest today compared to other metals of the energy transition which are counted in millions of tonnes (Iron: 1,500 Mt; Aluminium: 65 Mt; Copper: 20 Mt; Manganese: 19 Mt; Zinc: 12 Mt; Chromium: 12 Mt; Titanium: 8 Mt; Lead: 4.7 Mt; Nickel: 2.5 Mt).

[0005] In particular, lithium-rich brines are generally taken from the natural environment as continental brines from Andean or Tibetan endorheic basins, brines from petroleum production waters, geothermal brines and others.

[0006] In current applications, high-concentration LiCl salt mines use salt marshes to evaporate water from brines extracted from the subsoil and allow the reconcentration of lithium from 200-2000 mg / L to over 50 g / L, or even up to 80 g / L. This phase is carried out on hundreds of hectares of evaporation ponds, which take a long time to construct (3 to 4 years) and require ongoing maintenance to prevent leaks and seepage. Furthermore, this natural evaporation is dependent on sunshine and the general climate, with a reconcentration phase ranging from 12 to 24 months from the well to the production of this concentrate, generating variability in production, both in volume and quality, associated with millions of tons of crystallized salt (NaCl, Na2SO4, K3Na(SO4)2, KC1, Na2Mg(SO4)2.4H2O...) to be regularly removed to maintain an evaporation-crystallization capacity.

[0007] After this initial phase, a lithium concentrate is obtained that can incorporate all the ions from the starting brine. This currently necessitates the implementation of numerous downstream brine treatment steps to remove mineral impurities other than lithium in order to ultimately obtain the desired lithium, generally in the form of Li2CO3 after carbonation. Thus, it is common practice to operate several units in series after these solar evaporation ponds to extract boron by liquid-liquid extraction, then to chemically precipitate calcium, magnesium, and sulfates, followed by a KCl crystallizer, then ion-exchange resins, and finally the carbonation unit. This unit ensures the separation of residual sodium (Na+) and lithium (Li+) via precipitation at 80°C of lithium carbonate (Li2CO3) by the addition of sodium carbonate (Na2CO3).

[0008] LiCl(aq) + Na2CO3(S)=> Li2CO3(S)+ NaCl(aq).

[0009] The presence of sodium in the concentrated LiCl brine obtained also makes it impossible to directly produce battery-grade LiOH·H2O. Therefore, it is used after a first carbonation of the LiCl to Li2CO3, and a second carbonation after redissolving the latter to achieve a sufficient level of Li2CO3 purity before its chemical conversion by electrolysis to LiOH or by the addition of Ca(OH)2 via:

[0010] Ca(OH)2(aq) + Li2CO3(s)=> 2 LiOH(aq)+ CaCO3(s).

[0011] Being able to achieve a direct conversion of LiCl into LiOH.H2O would reduce operating expenses (OPEX) by at least US$2500 / tonne LiOH.H2O, making this sector much more competitive.

[0012] This production route is forced to progress in productivity, lithium yield and purity, and in cost in order to keep up with the strong demand for lithium while presenting top-notch Environmental, Social and Governance (ESG) results.

[0013] Thus, for example, due to the high consumption of water by evaporation of the brine, there are increasingly more restrictions in producing countries, Chile in particular, regarding the maintenance of solar evaporators considered potentially unsustainable on very arid Andean plateaus (15 to 100 mm of precipitation / year).

[0014] Other historical problems with lithium production from brines are also known in China, Bolivia, and to a lesser extent in Argentina, due to brine compositions that are too rich in magnesium and / or sulfate. Indeed, for example, when a Mg / Li mass ratio > 6 is reached, lithium can co-precipitate with magnesium due to similar physical and chemical properties, making their Difficult separation (precipitates of Camalite (MgCl2.KCl1.6H2O), bischofite (MgCl2.6H2O), Lithium camalite (LiCl.MgCl2.7H2O)...). Thus, in China, in the Qinghai Tibetan Plateau region, Mg / Li ratios of 10 to 40 are common, even up to 100. Moreover, in the presence of high sulfate, other combined salts can incorporate lithium and generate its loss by co-precipitation (precipitates of Astrakanite (Na2Mg(SO4)2.4H2O), Schoenite (K2Mg(SO4)2.6H2O), Leonite (K2Mg(SO4)2.4H2O), Kainite (MgSO4.KCl1.3H2O), Epsomite (MgSO4.7H2O)...). Thus, this solar reconcentration step can generate 40% to more than 70% lithium losses through co-precipitation and the removal of lithium-rich brine, which can generate such a significant lithium loss on some brines that this implementation becomes uneconomical and unecological.

[0015] However, the lithium present in brines would represent 75 to 80% of the world's lithium resource, far ahead of Pegmatite mines.

[0016] The object of the invention aims to resolve all these difficulties by implementing a solution for the selective extraction of LiCl from brines in the presence of many other salts, in particular NaCl, KCl, CaCl2, MgCl2, SrCl2, Na2SO4, K2SO4, NaH2BO3, KH2BO3... Thus, rather than treating all the impurities of the brine, which are very numerous, the object of the invention is to extract only the desired salt, namely LiCl, and therefore to significantly improve all the technical and economic parameters presented in Table 1.

[0017] [Tables] Parameter considered Unit State of the art Lithium extraction yield % 30 - 50% Extracted brine consumption m3 / t Li2CO3 125 - 900 Fresh water consumption m3 / t Li2CO3 16 - 100 Process floor area hectare 400 - 2,000 Displaced salts (NaCl, MgCl2, CaSO4...) tonne / t Li2CO3 50 - 500 Chemical reagents (HCl, H2SO4, CaO) kg / t Li2CO3 100 - 4,000 Heat (NG or Diesel) kWh / t Li2CO3 3,000 - 8,500 Electricity kWh / t Li2CO3 500 - 1,200 CO2 emissions tonne / t Li2CO3 4-5 Time to market for new capacity years 5-6 (minimum) Investment costs, CAPEX: US$ k / (t Li2CO3 / year) 16-28 Operating costs, OPEX: US$ / t Li2CO3 3,050 - 4,600

[0018] To achieve this, the invention aims to implement a liquid-liquid extraction solution by presenting an organic formulation allowing the selective extraction of di-ionic lithium salts (salts with one anion and one monovalent cation) in the presence of many other dissolved inorganic compounds, chosen, at least, from among alkalis, alkaline earths, halogens, sulfates, carbonates and other borates.

[0019] The use of liquid-liquid extraction for the selective extraction of lithium from natural or artificial brines has been studied for many years.

[0020] Thus, US patent 3,306,712 describes the use of alcohols or ketones for the selective extraction of LiCl, LiBr or Lil from CaCl2 brine with regeneration of the solvent with water in the presence of urea to extract the co-extracted CaCl2.

[0021] Gabra and Torma [1] studied the extraction of LiCl, NaCl, KCl and CaCl2 by Many alcohols exhibit separation coefficients (Li, Na), (Li, K), and (Li, Ca) below 3.21, 2.9, and 9.17, respectively. The best-performing alcohol is n-butanol, despite relatively high co-absorption of CaCl2. Overall, the solubility of LiCl increases with a decrease in the alcohol's molar mass, but this molar mass must be increased to reduce the solubility of the alkaline earth chlorides, MgCl2 and CaCl2.

[0022] Bukowsky and Uhlemann [2] proposed the use of solvent mixtures of isopentyl alcohol associated with 2-ethyl-1,3-hexane, diisopropyl ether or diethyl ether in order to greatly reduce the co-extraction of alkaline earth chlorides, but this is done at the expense of the extraction of LiCl with products which are ultimately far too soluble in water.

[0023] US patent 3,793,433 proposed the solvent extraction of lithium using [3-halogenated diketone and trioctylphosphine oxide (TOPO)] in benzene with acid regeneration (0.15 N HCl). Separation factors (SF) greater than 1000 are given with respect to the other alkali metals Na+, K+, Rb+ and Cs+, but this extractant extracts the alkaline earth metals Mg2+ and Ca2+ much more favorably than lithium (SF < 0.07), making the selective extraction of lithium impossible from any natural brine, which always contains alkaline earth metals.

[0024] The use of acidic extractants of the 2-ethylhexylphosphonic acid (D2EHPA) type encounters this same difficulty because, although experimental data indicate that the Li-D2EPHA complex has high selectivity compared to other monovalent metal ions and that the addition of tributyl phosphate (TBP) has a synergistic effect in increasing lithium extraction, these acidic extractants preferentially extract alkaline earth metals compared to alkali metals ([3]). Thus, commercial acidic extractants such as MEHPA, D2EHPA, Cyanex 272, PC88A, Ionquest 801, or others are not suitable for the selective extraction of lithium in the presence of alkaline earth metals.

[0025] Gao et al. [4] investigated the use of imidazolium-based ionic liquids with carbon chains of 4 to 9 carbons in the presence of triisobutyl phosphate (TIBP). The formation of the [Li.2TIBP]+org complex was established with acid regeneration by H+ / Li+ cation exchange, but the lithium extraction phase is carried out by cation exchange of the ionic liquid (C4min+) / Li+, which does not allow for the maintenance of extraction performance over time due to decomposition of the ionic liquid.

[0026] Patent CN106498184 proposes the use of A-methyl-A-(A'-2-ethylcarbonyl-ethylpyrrole hexafluorophosphate as an ionic liquid. The patent does not provide any information on the extraction and desorption conditions of LiCl.

[0027] Another approach consisted of studying neutral organophosphate extractants in the presence of the co-extraction agent Iron(III). Thus, the TBP / methylisobutyl system The ketone (MIBK) / FeCl3 ([5]) has attracted attention due to the extractability of the Li+FeCl4 pair in the presence of neutral extractants with oxygen donors. The implementation of a liquid-liquid extraction process with this lithium extraction ternary was thus evaluated ([6]). It appears that its implementation is complex due to the need to prevent the loss of hydrophilic Fe3+ by maintaining an aqueous environment with a high concentration of chloride anion (Cl) and acid (to prevent the precipitation of Fe(OH)3(s)) during the washing and deextraction phases (11 HCl / t LiCl). In addition, NaOH is used for formulation regeneration before extraction (2 t NaOH / t LiCl). As a replacement for TBP, other neutral extradants have been studied, such as A,A-bis(2-ethylhexyl)acetamide (N523) ([7]).

[0028] To avoid the use of iron(III), Zhou et al. ([8]) proposed using sodium phosphomolybdate, a heteropolyacid structure, as a co-extraction agent in combination with TBP / MIBK. This approach allows for Na+ / Li+ exchange during the extraction phase. A washing step is then carried out using a 2M LiCl + NaCl (10 / 90) mixture to remove K+ and Mg2+ impurities by cation exchange. The deextraction step is then performed with 0.24 M HCl to obtain an acidic LiCl effluent. Finally, the organic phase must be neutralized with 0.26 M NaOH to allow its regeneration before reuse.This new liquid-liquid extraction process using cation exchange across its four phases of extraction, washing, de-extraction and regeneration appears to be theoretically functional but requires excellent operational control of the potential release of various forms of potentially toxic molybdenum and presents high chemical reagent costs.

[0029] US2022 / 274956A1 proposes the use of three-dimensional calixpyrroles for The ability to encapsulate a salt, particularly LiCl, in the presence of NaCl and KCl is demonstrated for both solid-liquid and liquid-liquid extraction applications. Information is lacking regarding the impact of alkali metals on this extraction process, making it unclear whether this solution is truly selective for lithium.

[0030] Thus, no liquid-liquid extraction solution is described in the literature which is both selective with respect to lithium in the presence of alkali and alkaline earth metals, without the use of chemical reagents and industrializable in the short term (non-toxic, inexpensive products, sufficiently insoluble in water...).

[0031] The present invention therefore relates to a hydrophobic organic liquid composition for the selective extraction of a diionic lithium salt comprising a lithium cation and an anion complementary to the lithium cation, chosen in particular from Cl, I, Br, CN, NO3, HCO3, from a lithium-rich brine to be treated, said composition comprising:

[0032] (A) at least one lithium cation-extracting compound, selected from the compounds of formula:

[0033] in which: • RI and R2, whether identical or different, are, regardless of their position on a nitrogen atom, independently chosen from linear or branched C1-C12 alkyl, aryl, or C4-C8 cycloalkyl; or • RI and R2, taken together with the nitrogen atom that bears them, form a ring with five, six, seven or eight links; • R3 is chosen from hydrogen, linear or branched CrC8 alkyl, C4-C8 cycloalkyl, C2-C6 alkoxyalkyl and alkoxyalkylaryl; • R4 is chosen from hydrogen, alkyl in linear or branched Ci-C3; • R5 is chosen from hydrogen, alkyl in linear or branched Ci-C3; • R6 is chosen from hydrogen, alkyl in linear or branched CrC3;

[0034] (B) at least one organic, protic and hydrophobic compound, solvating the anion com complementary to the lithium cation; and

[0035] (C) at least one hydrophobic polar organic diluent having a flash point at atmospheric pressure above 60°C, preferably above 75°C, more preferably above 90°C.

[0036] By di-ionic lithium salt, we mean a lithium salt comprising a lithium cation Li+, carrying a single positive charge, and a mono- or polyatomic anion carrying a single negative charge, such as for example the monatomic anion Cl or the polyatomic anion NO3.

[0037] The lithium cation-extracting compound may have a molar mass of at least 450 g / mol, preferably of at least 550 g / mol.

[0038] The lithium cation-extracting compound may have a Log K complexation constant for this cation in methanol at 25°C, at least equal to 1, preferably greater than 2.

[0039] The lithium cation-extracting compound may exhibit a negative enthalpy change upon complexation of the lithium cation, AH, associated with an absolute value of the ratio of the enthalpy change upon complexation of the lithium cation AH to the variation of entropy during the complexation of the lithium cation, AS, at the temperature T=298K, IAH / (TAS)I greater than 2, preferably greater than 5.

[0040] These values ​​for the change in enthalpy and entropy during the complexation of the lithium cation allow us to obtain a value for the change in free energy AG that is more influenced by the enthalpy component than by its entropic component. This makes it possible to have a lithium cation extracting compound that can extract the lithium cation at low temperatures and be regenerated at high temperatures.

[0041] The lithium cation extracting compound may have a melting point below 200°C, preferably below 50°C and more preferably below 25°C.

[0042] In a particular embodiment: • RI and R2 can be, regardless of their position on a nitrogen atom, independently chosen from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, 2-methylbutyl, 2-ethylpropyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, 2-ethylhexyl, phenyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl; or, • RI and R2, taken together with the nitrogen atom that bears them, can form a pyrrolidine, piperidine, azepane or azocane ring; • R3 can be selected from hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, 2-methylbutyl, 2-ethylpropyl, n-hexyl, cyclohexyl, methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl and -CH2-O-CH2-Phenyl; and • R4, R5 and R6 can be hydrogen or methyl,

[0043] RI and R2 being advantageously chosen from butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl or phenyl in the case where the brine to be treated has a calcium concentration greater than 10 g / L and / or where Li+ / Ca2+ selectivity is preferred; and

[0044] RI and R2 being advantageously chosen from iso-propyl, iso-butyl, sec-butyl, tert-butyl, iso-pentyl, 2-methylbutyl, 2-ethylpropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or RI and R2, taken together with the nitrogen atom which bears them, form a pyrrolidine, piperidine, azepane or azocane ring in the case where the brine to be treated has a calcium concentration of less than 10 g / L and / or where Li+ / Na+ selectivity is preferred.

[0045] The lithium cation extracting compound can be chosen from: / i A \ \ . / ( y—N c-—y ) b— -v )-—'' 4 .S ' g x>"'b * °4 A / \ X ’ X ' / .••'■ x.--’' X?-'-' X Xy' X. •••' O''r 7-o CEOO CE01 CE02 HoO----, X b \ / \ \ < y—ix o—-' > b—-x y— / \— / \— / < / O \ O >•—y 0””<’ x ( \ y~\ / ^--- X \ / < efy z.....y G G—' > ü—-> )——' x\ / / \ \ ' \ / ' X f >•—n ; g} < Vy oy / \ ( / b--\ / . x l. À ,.X y. b'-''' ’X.-''’ CE03 CE04 CE05 ÿ b y-. / A-. Cl "b y ’ A _ / / .....v / -' / -4^ y "x / \ ÆA \ / 9. s / —J y-—• / 7 b-’N <•’ 'V-hf > y--.., v / \ / / '.....' ).....% G::::C r""\ 7 ‘f ( .) >""< ) \.....y ?.....y \..... / 7 7 ,CH’ x«}— -N, C-— ■ i>— y .......4 A O X, J CE06 CE07 CE08 \....., / P : ■■■-:. AC., ( l \—4 Q—J y o--v 9---7, .-----.\-----; q r--.^ N—-< ) \ '......' y \ •... .■.•>. CE09 CE10 CE11 . ÿ < XX 1 - ,.••■ x . , / x, - 'X ----. / ... ..--'xy' CE12 CE13 CE14 .....”x { ■ " • xs,.--vx .,.'x . y..... £ X •■' \ •' \ ' XX ..•• y. / CE15 CE16 CE17 >••• X CE18 CE19 CE20 / \ \ CH-, . M-.C CHi •• X 7 ■ / \ \ - x / • p- / > O -A >.....' P d ? Ô' )—¢1¼ pH3. .( Hr£ H—Z CH-, ÇHÿ r—•■ ? x r--Co. V / -4 / \A / ' a-—' Q}.— s: N—, X—-0H} HC— / / / '----N CHs yy 4 CH? .....\ oo H- / C-M → ^\ \----N CHS VO / CHî H^C---Ç H?C CH? \______ ap— / ) Ky csh,3 HssCs'X ' 6' GsH<;i <% O-""< ^"“CsHts \ yTM / y y- m' ) df. X 1X. ç, O—-X ? b—X b yx™t< K .' . > * '■XXX; '^'js CE24 CE25 CE26 < :•.••••:■; v--; ----;■ y y... x X-'-'-d . CE27 CE28 CE29 PH3 { \ \--y \ / '' \ V '—ht 0-----•■ 7 0—v / ------y ----- / Q / d' ) o '—' O \ N— / X \ \ / o O i ° °—\ ! r" \ ^ch* / 1 f''' 0 —\j CE30 CE31 CE32 ÇH3; ■—H Ô-..... ; 0-—s Cft, \ / \ / / \ ' V—J Y--JQ X---NG 0 \ / CH y x 9 X ' '— 0'Â X~X K..c,y ) d" Xhs O» 0:~<' CE33 CE34 CE35

[0046] The organic, protic and hydrophobic compound, solvating the complementary anion of the lithium cation, may have a pKa in water at 25°C of at least 9, preferably of at least 10.5 and preferably less than the pKa of water at 25°C, or at least less than 15 at 25°C and whose solubility in water at 25°C is less than 0.01 mol / 1.

[0047] The organic, protic, and hydrophobic compound that solvates the complementary anion of the lithium cation can be a compound of formula (B): x

[0048]

[0049] (B) in which: at least one of the radicals RB, Rc and RD, identical or different, is a halogen atom or an electron-withdrawing group chosen from the following group: F, Cl, Br; CmF2m+i with m < 4, where m is a non-zero integer; CF2CF2CpH2p+i with p < 4, where p is an integer; CF2CpH2p+i with p < 4, where p is an integer; CH2CpF2p+i with p < 4, where p is an integer; OCH2CF3; C(=O)CF3; CmHnFpClqBrs with m < 4, where n, p, q, s are integers of which at least p, q or s is non-zero; C(=O)OCmH2m+i with m < 4, where m is an integer; and C(=O)CmH2m+i with m < 4, where m is an integer; The remaining radicals RA, RB, Rc, Rd, and RE are chosen, identical or different, from among the following non-electro-withdrawing radicals: H; CH3; CH2; CH3; CH2CH2CpF2p+i with p < 4, where p is an integer; CmH2m_i with m < 10, where m is an integer greater than 1; and CmH2m+i with m < 10, where m is a non-zero integer; where only one of the radicals RA to RE can be one of these last two radicals, CmH2m_i and CmH2m+1; and X is chosen from the following radicals: OH; qH' / .C—R' \ R"

[0050]

[0051] where R' and R”, identical or different, are chosen from the following radicals: H; C nH2n i with n < 4, where n is an integer greater than 1; CnH2n+i with n < 4, where n is a non-zero integer; CH2CH2CpF2p+i with p < 4, where p is an integer; CH2CpF2p+i with p < 4, where p is an integer; CF2CpH2p+i with p < 4, where p is an integer; CF2CF2CpH2p+i with p < 4, where p is an integer; CmF2m+i with m < 4, where m is a non-zero integer; CmHnFpClqBrs with m < 4, where n, p, q, s are integers of which at least p, q or s is non-zero; and where R'” is chosen from the following radicals: CmH2m+i with m < 20, where m is an integer; CmH2m → with m < 20, where m is an integer greater than 1; CmHnFpClqBrs with m < 10, where n, p, q, s are integers of which at least p, q, or s is non-zero; CH2CH2CpF2p+i with p < 4, where p is an integer; CH2CpF2p+i with p < 4, where p is an integer; CF2CpH2p+i with p < 4, where p is an integer; CF2CF2CpH2p+i with p < 4, where p is an integer; CmF2m+i with m < 4, where m is a non-zero integer; and an aryl radical of formula (b):

[0052]

[0053]

[0054]

[0055]

[0056] where Ra, Rb, Rc, Rd and Re, identical or different, are such as previously defined in formula (B). In particular, in the compound of formula (B) X can represent: Compound (B) can be represented by the formula: or (D): Ry in which R”' is chosen from the following radicals: CmH2m+i with m < 20, preferably < 15 where m is an integer; CmH2m_i with m < 20, where m is an integer greater than 1; CmHnFpClqBrs with m < 10, where n, p, q, s are integers of which at least p, q or s is non-zero; and an aryl radical of formula (b):

[0057] where Ra, Rb, Rc, Rd and RE, identical or different, are as defined in formula (B) above.

[0058] In a particular embodiment, the radical R'” can be n-C7Hi5, n-CgH^, n-C11H23 or n-Ci3H27.

[0059] At least one lithium cation extracting compound may be present in the composition at a concentration of 0.15 to 1 mol / L, preferably 0.3 to 1 mol / L, more preferably 0.45 to 1 mol / L.

[0060] The ratio of the molar concentration of at least one organic, protic and hydrophobic compound, solvating the complementary anion of the lithium cation to the molar concentration of at least one compound extracting the lithium cation can be from 1 to 10, preferably from 1.5 to 5 and more preferably from 2 to 4.

[0061] The hydrophobic polar organic diluent may have a viscosity at 20°C of less than 5 mPa.s, preferably less than 2 mPa.s.

[0062] Preferably, the hydrophobic polar organic diluent is an aromatic diluent. This aromatic diluent can be chosen from 2-chlorobromobenzene, 1,2-dibromobenzene, 2-bromotoluene or 3,4-dibromotoluene.

[0063] The hydrophobic organic liquid composition may have a density at 20°C greater than 1.20 kg / L, preferably greater than 1.25 kg / L, more preferably greater than 1.30 kg / L, for a viscosity at 20°C less than 50 mPa.s, preferably less than 25 mPa.s, for a brine to be treated with a density at 20°C at least 0.05 kg / L less.

[0064] The hydrophobic organic liquid composition may have a density at 20°C greater than 1.25 kg / L, preferably greater than 1.30 kg / L, more preferably greater than 1.35 kg / L, for a viscosity at 20°C less than 30 mPa.s, preferably less than 15 mPa.s, for a brine to be treated with a density at 20°C at least 0.15 kg / L less.

[0065] The viscosity of the diluent and the hydrophobic organic liquid composition is measured using an Anton Paar Lovis 2000 viscometer. The sample is introduced into a capillary of known diameter. The measurement is performed using a steel ball that circulates at varying speeds within the capillary depending on the sample's viscosity. The instrument detects the ball and measures the time it takes to travel through the capillary at a specific angle of inclination. Having been previously calibrated using certified liquids, the instrument then provides the viscosity measurement in mPa·s.

[0066] The density is measured using an Anton Paar DMA 4100M electronic densitometer over a temperature range of 0 to 100°C. The points considered here are those at 20°C. This device is described, for example, in patents EP3012612 and EP3101409.

[0067] The sample is introduced into a glass tube of a specific volume. The tube vibrates. The period of the entire system (tube + liquid) is determined. The instrument subtracts this period from the reference period of the empty glass tube to determine the period of the liquid present in this glass tube. A nomogram translating the period into a function of density allows the density of said liquid to be determined.

[0068] The present invention also relates to a compound selected from compounds of formula: Y . .' XY' ''y' Yy X •••., .Z v: j \ y • 'Y. YY y" r\ \ X / “Y<cY xx> ô H.;C— p X / / X i NQ— / > b—- y—>" \ ' X ------' X----- Q ----Y û / O / '""y X / X '' / Ai—y > k—”zy \ CE01 CE02 CE02 CE03 / y > y.—X y / Xy y '.... Y '.... N >" Y..U ' S s ' X.. / ' â— / .• XX b ...... 0=” / / ---. ( ? { ) _n—< ; X—y X X.___J CE04 CE05 CE06 f Yy p.—z' Y—, Y^.z' \ . / X—•• b à—N .... £ / x Y i / ■ y 1 1 ' '?"T ■- 'x-.-.-. Z' • Y. Y. A'?J. l Y X >: 'YY'' CE08 CE09 CE11 ÿ < XX r; .'-"'X y......; CE12 CE13 CE14 X,- £ Â X. ..•••' l? \ < .- X.-” '-v-- q X y..... £ X \ •' X CE15 CE16 CE17 >••• X <• ; X CE18 CE19 CE20 CH5 CHj / \ CH-, . M-.C CHi ' X / ■ / x \ - x / ' 0 - / > O - y >.....' d ? Ô' )—GH:: pH3. .( Hr£ N:—Z CH-, x--( '--CH* ÇHÿ £i'!5 X o; 0---^ ) 'b-.-x psK3 y & yN' ) 0 CsxHv. ^nCe S'”X ^XZS f~' \ y…..-■■ ù Hx-yy-y \ 0' '8^^ CE21 CE24 CE25

[0069] The present invention also relates to the use of the hydrophobic organic liquid composition described above in a lithium salt extraction process, said process comprising a mixing step, at a first temperature, between the hydrophobic organic liquid composition and the brine to be treated, a separation step of the hydrophobic organic liquid composition loaded with lithium salt and the treated brine, and a regeneration step of the hydrophobic organic liquid composition by treating the hydrophobic organic liquid composition loaded with lithium salt with treatment water, said regeneration step being carried out at a second temperature, higher than the first temperature, the difference between the first temperature and the second temperature being from 30 to 150°C, preferably of

[0070]

[0071] 50 to 100°C, preferably 60 to 80°C. One of the objectives of the invention is to be able to selectively extract LiCl from lithium-rich continental brines found in the Andean highlands of Chile, Argentina, and Bolivia, or in the Tibetan Plateau in China. Figure 1 shows the compositions, measured in mmol / L, of about twenty of these natural brines with an average density of 1.22 kg / L. Based on these compositions, the Li / Na selectivity appears to be the primary determining factor, followed by the Mg / Li, Ca / Li, and SO4 / Li selectivities. The compositions according to the invention can also treat these brines after reconcentration by solar evaporation or other means. Ion-selective electrodes (ISEs) based on a poly(vinyl chloride) (PVC) membrane exist that are selective for lithium for measuring lithium concentration in aqueous solutions or in blood. In particular, the series of ionophores I to VIII is presented by Kamenica et al. ([9]). , S^x^x, s' 4^^ v: s 4 O xO » «S .-S , x '"X,' 4"'' < SX <x>V §.4 x xXX-XxX XX' V < ''W" 4 XX. 4^ ■<,' I' 4. 'Xx, 4' XXX^*^ ''"i S 4X' <■ ​​4'^4

[0072] Lithium ionophore I: V,Vz-dihcptyl-V,Vz,5,5-tetramethyl-5,7-dioxanonanediamide, or 2,2'-[(2,2-dimethyl-1,3-propanediyl)bis(oxy)]bis[N-heptyl-N-methyl-acetamide, ETH 149, CAS: 58821-96-8

[0073] Lithium ionophore II: V,V,V',Vz-tctraisobutyl-cis-cyclohcxanc- / ,2-dicarboxamidc, ETH 1644, CAS: 80547-18-8

[0074] Lithium ionophore III: VV-dicyclohcxyl-V'.V'-diisobutyl-cis-cyclohcxanc- / ^ -dicarboxamide, ETH 1810, CAS: 99281-50-2

[0075] Lithium ionophore IV: V,V,Vz,V'-lélracyclohcxyl-5-clhyl-5-bulyl-5,7-dioxanonanediamide, or 2,2'-[(2-butyl-2-ethyl-1,3-propanediyl)bis(oxy)]bis[N,N-dicyclohexylacetamide], ETH 2137, CAS: 108083-23-4

[0076] Lithium ionophore V: 7,4,7,70-tetracyclododecane, or

[0077] 12-crown-4, CAS: 294-93-9

[0078] Lithium ionophore VI: 6,6-dibenzyl-1,4,8,11-tetraoxa-cyclotetradecane, CAS: 106868-21-7

[0079] Lithium ionophore VII: 2-(6-dodecyl-1,4,8,1-tetraoxacyclotetradec-6-yl)ethyl diethyl phosphate,

[0080] CAS: 106868-29-5

[0081] Lithium ionophore VIII: 2,2'-[[2-[[2-(Dicyclohexylamino)-2-oxoethoxy]methyl]-2-ethyl-l,3-propanediyl]bis(ox y)]-bis[N,N-dicyclohexyl-acetamide], CAS: 133338-85-9

[0082] Lithium ionophore 2,2'-[(2,2-Dimethyl-1,3-propanediyl)bis(oxy)]bis[N,N-dicyclohexylacetamide], ETH 2015, CAS: 108444-70-8

[0083] Experimental Part

[0084] A volume of organic formulation is brought into contact with a volume of salt water (O / Aext=l), then stirred at 800 rpm at 23°C for 30 minutes. After stirring is stopped, the two phases are allowed to settle for 5 to 30 minutes at 23°C, and then the aqueous and organic phases are collected. The organic phase then undergoes a deextraction phase at 80 or 90°C with demineralized water (A / Odesext=5) via stirring for 35 minutes at 800 rpm. After stirring is stopped, the two phases are allowed to settle for 10 to 15 minutes at 80 or 90°C, and then the two resulting liquids are analyzed by ion chromatography.

[0085] The extraction and de-extraction (regeneration) parameters are presented in Table 2.

[0086] [Tables2] Parameters Extraction Phase Regeneration Phase Equipment Dragon SK-0330 Pro Hettich lab technology MKR 13 Hettich lab technology MKR 13 Ratio A / OA / O = 1 A / O < 5.2 Volumes Used A = 1.5 mL A = 5 mL Temperature 22.8°C - TA 91-93.7°C Stirring Time 30 min - 1h 35 min Stirring Speed ​​500-800 rpm 800 rpm Settling Time 5-30 min < 15 min

[0087] Depending on the available equipment, the orbital shaking plate or the shaker are used for extraction tests. Conversely, only the shaker is used for the re generation because it is the only device capable of heating up.

[0088] The results are processed after recalculating the analytical values, corrected by the A / O ratio and overshoot (calculated relative to magnesium). For more information To be precise, only de-extraction measures are taken into account.

[0089] Analytical equipment: Metrohm ion chromatograph,

[0090] Cation column: Metrosep C6-150 / 4.0 (ref 6.1051.420)

[0091] Anion column: Metrosep A supp S 250 / 4.0 (Ref 6.1006.530)

[0092] Some definitions necessary for the characterization of the are presented below. results of the following experimental designs.

[0093] The extraction yields (Ew) and deextraction yields ^E^, the distribution coefficients (DM), and the separation factors (SF(Li / M)) for the extraction of lithium Li+ relative to the metal Mn+ and the extractant utilization rate (%Use(M)) are given by equations (1), (2), (3), (4) and (5) respectively: Or, (1) x 100

[0094]

[0095] [jH -[AfX or, CVo ), x[mX (2) em(%) = .....W x 100 =--^.1........x 100 7 [ M X t^X?

[0096] 100971 SFtIJIM) = ^OuSF(LilMi =

[0098]

[0099] %Use(M) = 100 (5) Or [M n+ f ' urV LLL ^de. and [Lfn+1^ represent respectively the initial and final concentrations in aqueous phase of extraction and de-extraction, and in organic phase for the Mn+ ion.

[0100] (o / A ) and (o / A ) are the volume ratios between the organic phases and aqueous respectively in extraction and de-extraction phases.

[0101] Moreover, since a temperature-modulated liquid-liquid extraction solution is sought, the equilibrium constant Keq(T) must be strongly dependent on the operating temperature and therefore predominantly enthalpic (AH) as explained by the Arrhenius equation (5).

[0102] Keq(T) = Kq x exp() = Ko x exp() (5)

[0103] Which can be presented in its linear form:

[0104] Ln(Ke.q) = x (~) + Ln(K0)

[0105] Experimental plan no. 1: Extraction of salts by the ionophores of Lithium II, IV, V, VIII and X.

[0106] This involves carrying out duplicate extraction tests of aqueous solutions of pure LiCl, NaCl, KCl, and CaCl2, respectively, in the presence of an excess of MgCl2, for several ionophores using a liquid organic formulation composed of [(Jp V œ 45 mmol / L of ionophore (CE Cationic Extractant) per 10 LJ equivalents or g of anionic solvator (AS), i.e. 450 mmol / L of N-(3,5-bis(trifluoro-methyl)phenyl)octanamide (Ci6Hi9F6NO, CAS 1974318-14-3), all dissolved in 1,2-dichlorobenzene (2DCB) (C6H4C12, CAS 95-50-1).

[0107] The aqueous phases / brines to be tested in extraction were created in the laboratory from demineralized water and pure salts (> 99.9%). They are defined in Table 3.

[0108] [Tables3] Ions Li+ Na+ K+ Ca2+ Mg2+ Cl- Salinity Test 1.1 0.2 mol / L (1388 mg / L) / / / 1.50 mol / L (36.46 g / L) 3.2 mol / L (113 g / L) 151 g / L Test 1.2 / 1 mol / L (23 g / L) / / 1.50 mol / L (36.46 g / L) 4 mol / L (142 g / L) 201 g / L Test 1.3 / / 1 mol / L (39.1 g / L) / 1.50 mol / L (36.46 g / L) 4 mol / L (142 g / L) 217 ​​g / L Test 1.4 / / / 1 mol / L (40 g / L) 1.50 mol / L (36.46 g / L) 5 mol / L (177 g / L) 254 g / L

[0109] This choice of high salinities and chloride doping was considered in order to be able to push the extractability of salts by ionophores to their maximum and potentially reduce the uncertainty related to the analysis of ions of extracts for these products chosen for their potentially low capacity to extract chloride salts of Na, K and Ca.

[0110] The extraction and de-extraction protocol previously presented is maintained for each of these tests.

[0111] The extraction results are given in Table 4.

[0112] [Tables4]

[0113] It appears that the tripod Li VIII allows a much higher salt extraction than extradants II, IV and X, and that lithium extraction is very low for extradants II and V, which are considered as lithium ionophores for ion-selective electrodes.

[0114] These results show that: 1. Just because an ionophore is used in a cation exchange selective electrode does not mean it can also be used in liquid-liquid salt extraction. For example, the Li II ionophore (ETH 1644) achieves a very low salt extraction rate, ranging from 0.25 to 1.10 mmol / L, which is always less than 2.6% of the extractant usage rate. 2. Just because an ionophore is selective for a cation in electrode-selective application does not mean it will also be selective for that cation in liquid-liquid extraction. Thus, the Li₃V ionophore, even though it is presented as a lithium ionophore, actually much prefers to extract NaCl compared to LiCl, with an extraction rate 205 times higher for NaCl. 3. The Li IV and Li X ionophores, which have very similar structural compositions, exhibit comparable performance, with extractant utilization rates of 19.2% for lithium and 15% for sodium, respectively, and 5.37% and 7.09% for sodium. In contrast, the Li VIII ionophore shows high extractant utilization rates of 83% (Li), 62.6% (Na), and 76% (Ca) in the extraction of pure salts. 4. The Li VIII ionophore, which is the "tripodant" version of the Li IV and Li X ionophores, which are "dipodant", allows 4.33 times greater use of the extractant for the extraction of LiCl compared to the latter.

[0115] Experimental Plan #2: Multi-salt extraction by 14-crown-4 ether

[0116] This involves carrying out multi-salt extraction tests of chloride Li, Na, K, Mg, and CaCl2 with a water composition that can approximate continental salt flat water, i.e., here with an excess of sodium, for several ionophores via a liquid organic formulation composed of [ ]z ~ 80 mmol / L of ionophore LJ wg (CE Cationic Extractant) for 3 equivalents of anionic solvator (AS), i.e. 240 mmol / L of V-(3,4-dichlorophenyl)-octanamide (Ci4HiçCi2NO, CAS 730-25-6), all dissolved in 2-chlorobromobenzene (2CBB) (C6H4BrCl, CAS 694-80-4).

[0117] The brine to be tested by extraction was created in the laboratory from demineralized water and pure salts (> 99.9%). The composition of the measured water (ES-001) is shown in Table 5.

[0118] [Tables5] Ions Li+ Na+ K+ Ca2+ Mg2+ Cl- Salinity Test 2 0.143 mol / L (991 mg / L) 4.071 mol / L (93.64 g / L) 0.023mol / L (911 mg / L) 0.246 mol / L (9867 mg / L) 0.287 mol / L (6.985 g / L) 5.304mol / L (188 g / L) 300 g / L

[0119] It is representative of a brine at the well outlet for the implementation of a direct lithium extraction (DLE) solution, or rather, direct lithium salt extraction (DLSE).

[0120] The previously presented extraction and de-extraction protocol is maintained.

[0121] In view of the level of extraction of Li V, based on a crown ether, we focused the study on 14-crown-4 base crown ethers. In addition to Li VI and Li VII, the two ionophores below were tested, and also characterized in Lithium selective electrodes.

[0122] Dibenzo-14-crown-4 (DB14C4), CAS: 14174-06-2

[0123] 6-[2-(benzyloxy)ethyl]-6-dodecyl-14-crown-4 (BzO Li VII), CAS: 106868-24-0

[0124] The results are summarized in Table 6. ta U SF 1 *■ ta M H. *4 S JS tV. NK and tnl $ SR' 'L i M. ~ | ¢8¾ | § to' | | Does S XGO have 1 83¾ S^3 | | 83¾ | 88¾ -x % Cl g, -n-- O | | 88¾ | 3t8 % i B 3 1 ■Vt u> r<ï you £5) .. to | 537 | w 1 Ç>| "*! to m| ■SR wh BS uy uS nh ui -■i uh W s

[0126] It appears that the four ionophores based on 14-crown-4 ethers achieve only a very modest LiCl extraction with less than 2.25% usage (or loading) of the extractant with less than 1.8 mmol / L of LiCl extracted for a formulation with 80 mmol / L of extractant (EC).

[0127] On the other hand, the ionophore Li VIII confirms its effectiveness with a rate of 45.4% The extradant is used (or loaded) with 36.30 mmol / L of LiCl absorbed by this formulation. Furthermore, the separation factors (SF) are very good, with values ​​of "infinite" for Li / Mg and Li / Ca, 469 for Li / K, and 153 for Li / Na.

[0128] In summary, it appears that in a single contact at ratio (O / A)ext = 1, 28.5% of the lithium and less than 5% of the other ions are extracted with Li VIII on a liquid-liquid extraction stage, as illustrated in Table 7 via analyses of the composition of the treated brine.

[0129] [Tables?] (O / A)ext = 1 Li+ Na+ K+ Mg2+ Ca2+ Cl Brine to be treated (mmol / L) 142.8 4071.2 246.2 287.4 23.3 5081.6 Brine to be treated (mmol / L) 102.1 4032.1 238.0 274.3 23.2 4967.1 EMn+(%) 28.5% 1.0% 3.3% 4.6% 0.5% 2.3% SF(Li / Mn+) / 153,469 Inf. Inf. /

[0130] If an ionic balance is carried out from the composition of the formulation extracted at 80°C in five volumes of demineralized water, the result is even more favorable with regard to the impurities Na+, K+, Mg2+ and Ca2+ which are then practically not extracted, while retaining 25.4% of extracted lithium, as can be seen in Table 8.

[0131] [Tables8] (O / A)ext = 1 Li+ Na+ K+ Mg2+ Ca2+ Cl Brine to be treated (mmol / L) 142.8 4071.2 246.2 287.4 23.3 5081.6 Brine to be treated (mmol / L) 106.5 4061.8 246.0 287.4 23.3 5081.6 EMn+(%) 25.4% 0.2% 0.1% 0.0% 0.0% 0.0% SF(Li / Mn+) / 148,465 Inf. Inf. /

[0132] Note the strong competition between Li+ and Ca2+ for the extractant, since Experiment 1 had 34.55 mmol / L of CaCl2 absorbed alone, whereas this trial showed no absorption of CaCl2 in the presence of lithium. Another potential reason may be due to an AS eq here of 3 instead of 10 for the previous experiment.

[0133] Experimental plans 1 and 2 having been carried out with respectively 10 and 3 equivalents of anionic solvator AS, the impact of this parameter on the extraction capacity in LiCl, NaCl and CaCl2 of an 80 mmol / L formulation of ionophore Li VIII was examined in order to increase the utilization rate of the extractant.

[0134] Experimental design no. 3: Extractions and stoichiometric coefficient of solvation of &

[0135] This involves carrying out extraction tests of aqueous solutions of LiCl, NaCl, and CaCl2 respectively, in pure form and in duplicate, in the presence of an excess of MgCl2, for 4 liquid organic formulations composed of [cgV ~ 80 mmol / L of LJ or g ionophore Li VIII for respectively 1, 3, 5 and 10 equivalents of anionic solvator (AS), i.e. 80, 240, 400 and 800 mmol / L of N-(3,5-bis(trifluoromethyl)-phenyl)octanamide, all dissolved in 1,2-dichlorobenzene (2DCB).

[0136] The different aqueous phases and brines to be tested in extraction were created in the laboratory from demineralized water and pure salts (> 99.9%). Their compositions are shown in Table 9.

[0137] [Tables9] Ions Li+ Na+ Ca2+ Mg2+ Cl Salinity Test 3.1 0.165 mol / L (1150 mg / L) / / 1.62 mol / L (39.36 g / L) 3.405 mol / L (120.7 g / L) 161.2 g / L Test 3.2 / 0.201 mol / L (4639 mg / L) / 1.59 mol / L (36.59 g / L) 3.377 mol / L (119.7 g / L) 163 g / L Test 3.3 / / 0.205 mol / L (8251 mg / L) 1.62 mol / L (39.36 g / L) 3.605 mol / L (129.4 g / L) 177 g / L

[0138] The extraction and de-extraction protocol previously presented is maintained for each of these tests.

[0139] The results are summarized in Tables 10 to 13 and Figures 2 and 3.

[0140] [TableauxlO] lons / Usage CE Eq.SA = 1 Eq.SA = 3 Eq.SA = 5 Eq.SA = 10 Keq Test 3.1 - ELi(%) / %Use(Li) 7.4% / 15.4% 26% / 53.8% 36.7% / 75.9% 42.5% / 88.1% 59.060 Test 3.2 - ENa (%) / %Use(Na) 1.0% / 2.4% 3.2% / 8.1% 6.4% / 16.0% 10.9% / 27.4% 0.859 Test 3.3 - ECa (%) / %Use(Ca) 0.2% / 0.5% 2.3% / 5.9% 6.3% / 16.3% 9.9% / 25.5% 0.366

[0141] [Tableauxll] 5. | L^ ■ri £ < $ P H en «i te <*î Tk U»ge 1 a. rtï Lfl îg < Ts Est 1 cN | %£'5£ LT! IN 1S WW ÎRfeæ | S s W$ :--4 Lfl Çh uS O g rï sa a È <3 O I— a Mm C o- 1 s‘8 1 | 5¾ | 1-j Ci g n" IVÎ PX SS'’3S vH Sfr r" , ri ’** $ f\T ■•-•i hs ffi «4- | $ 6' r- Dsïî'ïfè F yî IZÏl «> r^ rj >'î CM ?4 Q §1 O 243 | 1 | < -i (fj wl O ■H

[0142] [Tableaux 12] & s* CM tf-! tù {ÿi £> LH *4 $ «i <<■ 9' iM & 9 ^4 rts & 9’ Tx Usage N $ S 13 Tx Ext £ O 6j rû l£ & JS ça S •$ rn «1 9. < CM tN ? Q u - O P £3 Ç> d' <5 <'■ 1 BS S S<’ <2 C' & €5' 9. £& SI 1 % ® l»>4 CN -:-4 OH oÿ rv <0 LTi en -.-4 CM »? % i % ai t™4 1^ iri, u? C4 «J ^-- CM i*-! O 4g <î • « s ® 'ï «1 >'î •.'■4 «) ^-X ïy i>4 > «' Ô -sJ i «ç a KwJ S CM S 8 CS? < UJ ri rft i4-> Q ■>M

[0143] [Tableauxl3] s MQQOQ q OS i <0 d" S ki irf d CM q- + & $ HO tn KO rd KM d é'JF s «HS CTÏ 6- sH K Cd A:. sws -Kl ■» ¢-1 i S e* S 1X4 O") US

[0144] It appears that the anionic solvator AS effectively performs its role as a facilitator of salt transfer to the organic phase, as the amount of LiCl, NaCl, or CaCl2 extracted increases with eq.SA. Thus, the extraction yield ([Fig. 2]) and the extractant utilization rate ([Fig. 3]) increase with eq.SA, but there is a significant difference in performance. is observed at equilibrium between test 3.1 and tests 3.2 and 3.3, showing significant selectivity for lithium.

[0145] It appears that the very high selectivity of the Li VIII ionophore makes it possible to recover overall the same level of lithium extraction performance whether or not sodium is present, compared to experiments 1 and 2.

[0146] From the data in these tables and figures, it is clear that the equilibrium constants Keq are very different (Tests 3.1 / 3.2: 68 / 1 and Tests 3.1 / 3.3: 161 / 1). Thus, the proposed formulation is well suited to the selective extraction of LiCl in the presence of NaCl and / or CaCl2 due to the significant difference in equilibrium constants Keq and the non-extraction of magnesium and potassium ions.

[0147] Experimental design no. 4: Influence of the O / APXt ratio on salt extraction.

[0148] This involves carrying out extraction tests on a multi-salt brine with increasing O / Aext ranging from 0.1 to 10, for a liquid organic formulation with 3 equivalents of anionic solvator (AS), i.e. of V-(3,4-dichlorophenyl)-octanamide (Ci4H 19Cl2NO, CAS 730-25-6) for, [ ££ |z = 0.3 mol / L of Li VIII ionophore, all dissolved in 2-chlorobromobenzene (2CBB) (C6H4BrCl, CAS 694-80-4).

[0149] The brine to be tested by extraction, representative of a real lithium-rich brine, with the presence of the sulfate ion, was created in the laboratory from demineralized water and pure salts (> 99.9%). Its salinity is 425 g / L and its composition is shown in Table 14.

[0150] [Tables 14] Ions Li+ Na+ K+ Ca2+ Mg2+ Cl SO42 Test 4 0.415 mol / L (2883 mg / L) 4.059 mol / L (93.30 g / L) 1.166 mol / L (45.60 g / L) 0.021mol / L (845 mg / L) 0.820 mol / L (19.92 g / L) 7.06 mol / L (250.2 g / L) 0.132 mol / L (12.7 g / L)

[0151] The O / Aext tested are 0.1; 0.25; 0.5; 1; 2; 4 and 10. These tests make it possible to evaluate the influence of this ratio on the extraction yields of the different ions.

[0152] The extraction and de-extraction protocol previously presented is maintained for each of these tests with the exception of the O / Aext given above.

[0153] The results are summarized in Tables 15 to 17 and [Fig.4].

[0154] [Tables 15] (O / A)ext 0.1 0.25 0.5 1 2 4 10 Eu(%) 10.1% 20.1% 34.6% 58.7% 78.0% 94.0% 98.1% ENa(%) 0.0% 0.1% 0.2% 0.5% 1.8% 6.9% 20.7% Ek(%) 0.0% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% ECa(%) 0.5% 1.2% 2.6% 6.5% 14.8% 39.6% 72.6% EMg(%) 0.0% 0.00% 0.01% 0.01% 0.03% 0.09% 0.08% Es(m(%) 0.00% 0.00% 0.00% 0.00% 0.00% 0.00% 0.00%

[0155] Note the total absence of extraction for K+, Mg2+ and SO42 ions.

[0156] [Tables 16] (O / A)ext [zT]z »- ^aq (mol / L) [(Va* / LJ aq (mol / L) [^]7 L Saq (mol / L) [Ctf2+fl laq (mol / L) (mol / L) r if W (mol / L) (mol / L) 0 0.415 4.059 1.166 0.021 0.820 0.132 7.058 0.1 0.374 4.058 1.166 0.021 0.820 0.132 7.014 0.25 0.332 4.056 1.166 0.021 0.820 0.132 6.970 0.5 0.272 4.051 1.166 0.021 0.820 0.132 6.905 1 0.172 4.038 1.166 0.020 0.820 0.132 6.789 2 0.091 3.986 1.166 0.018 0.819 0.132 6.653 4 0.025 3.779 1.166 0.013 0.819 0.133 6.368 10 0.008 3.218 1.166 0.006 0.819 0.133 5.776

[0157] [Tableauxl7] (O / A)ext SF(Li / Na) SF(Li / K) SF(Li / Ca) SF(Li / Mg) SF(Li / SO4) 0,1 375 Infini 22 5254 Infini 0,25 309 Infini 22 16561 Infini 0,5 270 Infini 19 4203 Infini 1 266 Infini 20 17425 Infinite 2 192 Infinite 20 10609 Infinite 4 212 Infinite 24 16973 Infinite 10 201 Infinite 20 69144 Infinite

[0158] These experiments show the relevance of the tested formulation for carrying out a selective extraction of LiCl in the presence of other alkali and alkaline-earth salts.

[0159] From these data, a distribution curve of LiCl between organic and aqueous phases at constant temperature and pressure is also obtained in [Fig.5], which we call the absorption isotherm of LiCl at 20°C for the excess chloride concentration studied.

[0160] Experimental plan no. 5: Calorimetric measurements in methanol at 25°C

[0161] In order to validate the complexation capacity of the Li VIII ionophore, for these Li+, Ca2+ and Na+ cations, an isothermal calorimetric titration (ITC) study of their complexation was carried out.

[0162] The experiments were performed on an ITC200 (GE Healthcare) and a TAM 2277 (TA Instruments) at room temperature. The analytical solvent was methanol (Chromasolv®, Sigma-Aldrich), and the ionic strength was fixed at 0.1 M with Et4NCl. Stock solutions of Li (0.1232 mol / L), Ca (0.1300 mol / L), and Na (0.1074 mol / L) were prepared from chloride salts, and their concentrations were determined by ICP analysis.

[0163] On 1TTC200, each titration consisted of 26 additions of 1.5pL of metal stock solution into the 0.2022 mL analysis cell containing the ionophore ligand Li VIII under stirring.

[0164] On the TAM 2277, each titration consisted of 17 additions of 15 pL of metal stock solution into the ImL analysis cell containing 0.8 mL of solution incorporating the ionophore ligand Li VIII under stirring.

[0165] For each study, several titrations were carried out to determine the best analysis conditions, then replicates (at least 3) were performed.

[0166] The ionophore extractant Li VIII forms complexes with a 1:1 stoichiometry (Mn+:CE, Mn+ = Li+, Na+ or Ca2+). The complexation equilibrium and the associated complexation constant in methanol (KMe0H) are defined as follows:

[0167] Mn+ + CE <==> MCE, KMe0H = [MCE] / [M] [CE]

[0168] (M = Li, Na or Ca and CE = Li VIII)

[0169] The average of the results obtained is given in Table 18.

[0170] [Tables 18] Ions Log KMeOH AGa (kj / mol) AH (kj / mol) -TASb (kj / mol) IAH / (TAS)I Li+ 2.2 + / - 0.2 -12.6 -14.7 2.1 7 Ca2+ 4.9 + / - 0.2 -28.0 -26.0 -2.0 13 Na+ 0.9 + / - 0.3 -5.1 Not measurable / /

[0171] Calculated from the relation AG = -RT ln(K) (T= 298K, R=8.314 J / mol / K)

[0172] b Calculated from the relation AG = AH - TAS (T= 298K).

[0173] The heat of reaction could not be determined for NaCl with the equipment used due to insufficient complexation.

[0174] These thermodynamic parameters (AH, AS) indicate an exothermic complexation reaction for lithium and calcium with a negative and predominant enthalpy component AH in the calculation of the free enthalpy AG, with for example here, at temperature T=298K, a ratio IAH / (TAS)I of 7 for the complexation of lithium.

[0175] It follows that the Li VIII ionophore's ability to complex these cations is highly temperature-dependent. Therefore, hot water deextraction was considered.

[0176] Experimental design no. 6: Destraction at 80°C of a salt-loaded formulation

[0177] For a liquid organic formulation composed of [ £'£']' = 0.3 mol / L of LV-I or g ionophore Li VIII and 3 equivalents of anionic solvator (AS), i.e. 0.9 mol / L V-(3,4-dichlorophenyl)-octanamide (C14H19Cl2NO, CAS 730-25-6), all dissolved in 2-chlorobromobenzene (2CBB) (C6H4BrCl, CAS 694-80-4), an extraction is carried out at 23°C on a multi-salt brine, then the deextraction of the previously absorbed salts is evaluated by contacting demineralized water at 80°C for increasing A / Odesext values ​​ranging from 0.02 to 5.

[0178] The brine used in extraction, representative of a real lithium-rich brine, was created in the laboratory from demineralized water and pure salts (> 99.9%).

[0179] After analysis, it has a salinity of 360 g / L and its composition is indicated in Table 19.

[0180] [Tables 19] Ions Li+ Na+ K+ Ca2+ Mg2+ Cl SO42 Test 6 0.373 mol / L (2585 mg / L) 3.413 mol / L (78.46 g / L) 0.997 mol / L (38.99 g / L) 0.012mol / L (475 mg / L) 0.689 mol / L (16.75 g / L) 5.93 mol / L (210.2 g / L) 0.128 mol / L (12.3 g / L)

[0181] The A / OdeSext tested at 80°C are 0.02; 0.033; 0.05; 0.067; 0.1; 0.2; 0.5 and 5. These tests make it possible to evaluate the influence of this ratio, and therefore of the quantity of demineralized water used, on the deextraction yields of the different ions.

[0182] The extraction and de-extraction protocol previously presented is maintained for each of these tests with the exception of the A / Odesext given above and the O / Aext given below.

[0183] Firstly, a single-contact extraction with a ratio (O / A)ext = 1.43 is carried out with 95 mL of organic phase and 66.5 mL of brine.

[0184] The liquid-liquid extraction performance is illustrated in Table 20 via analyses of the composition of the treated brine.

[0185] [Tables20] (O / A)ext = 1.43 Li+ Na+ K+ Ca2+ Mg2+ Cl SO42 Brine to be treated (mmol / L) 372.5 3413 997.1 11.8 689.1 5928 128.2 Treated brine (mmol / L) 114.4 3351 995.2 10.9 687.6 5601 128.2 EMn+(%) 69.3% 1.8% 0.2% 8.0% 0.2% 5.5% 0.0% SF(Li / Mn+ ) / 174 2453 13.1 2450 174 /

[0186] If an ionic balance is carried out from the composition of the formulation de-extracted at 80°C in 5 volumes of demineralized water, the result is more favorable with regard to the extraction of lithium which goes from 69.3% to 74.5% while the impurities remain very poorly extractable, except for calcium, in very low initial concentration, as we see in Table 21.

[0187] [Tables21] (O / A)ext = 1.43 Li+ Na+ K+ Ca2+ Mg2+ Cl SO42 Brine to be treated (mmol / L) 372.5 3413 997.1 11.8 689.1 5928 128.2 Treated brine (mmol / L) 95.0 3366 996.2 9.8 688.4 5597 128.1 EMn+(%) 74.5% 1.4% 0.1% 17.0% 0.1% 5.6% 0.1% SF(Li / Mn+ ) / 210 2958 14.3 2955 210 /

[0188] These balances indicate an ability of the formulation to provide an effective first separation of lithium from other ions.

[0189] The results of the deextraction with demineralized water at 80°C are summarized in the Tables 22 and 23 and Figures 6 and 7.

[0190] ITable. 22] (A / O) désextraction LJ or g (mol / L) (mol / L) LJ org (mol / L) LJ OFg (mol / L) (mol / L) LJ org (mol / L) r ? if SO42' LJ org (mol / L) 0 194 32.8 0.69 1.41 0.476 231 0.10 0.020 157 4.0 0.00 0.57 0.033 162 0.04 0.033 1 3.20 .20 .20 0.000 135 0.03 0.050 110 1.8 0.00 0.24 0.000 112 0.03 0.067 96 1.7 0.08 0.12 0.017 98 0.02 0.100 8.015 0.096 0.026 83 0.02 0.200 45 1.3 0.06 0.06 0.032 47 0.01 0.500 21 1.2 0.06 0.05 0.021 22 0.01

[0191] [Tables23] (A / O)ext 0.02 0.033 0.05 0.067 0.1 0.2 0.5 5 E'u(%) 19.3% 31.9% 43.3% 50.5% 58.2% 76.6% 89.2% 100.0% E'(8.7%) 92.7% 94.4% 94.7% 95.5% 95.9% 96.4% 100.0% E'k(%) 100.0% 100.0% 100.0% 88.4%* 91.5%* 91.4%* 90.6%* 100.0% E'C(a) 89.4% 89.0% 82.7% 91.2% 93.7% 95.6% 96.2% 100.0% E'w(%) 93.1% 100.0% 100.0% 96.4%* 94.5%* 93.2%* 95.6%* 100.0% E'sO( 67.8% 57.5%) 72.1% 76.3% 80.2% 84.9% 90.7% 100.0%

[0192] *Within the limit of analytical accuracy.

[0193] From these results, a distribution curve of LiCl between organic and aqueous phases at constant temperature and pressure is also obtained in [Fig.8], which we call the LiCl de-extraction isotherm with demineralized water at 80°C.

[0194] By combining Figures 5 and 8, two lithium partition curves at 20°C and 80°C are obtained in [Fig.9] for the implementation of the LiCl separation and purification process.

[0195] The gap between these isotherms expresses the possible breathing of the formulation for the implementation of the temperature-modulated liquid-liquid extraction process of LiCl.

[0196] These LiCl partition isotherms allow the construction of the associated McCabe-Thiele equation for determining the necessary number of unit stages to be put in works both in the extraction phase and in the de-extraction phase for two given operational lines, as illustrated in [Fig. 10].

[0197] Experimental design no. 7: Extractability of nitrate salts, other di-ionic salts. LiNO3, NaNQ^ and Ca(NO3)2.

[0198] This involves carrying out extraction tests of aqueous solutions of LiNO3, NaNO3 and Ca(NO3)2 respectively in pure form, at varying concentrations, with or without an excess of Mg(NO3)2, for liquid organic formulations composed of [ ]1 ~ 250 mmol / L of Li VIII ionophore for 3 equivalents of LJ or g anionic solvator (AS), i.e. 750 mmol / L of V-(3,4-dichlorophenyl)-octanamide (Ci4 Hi9C12NO, CAS 730-25-6), all dissolved in 2-chlorobromobenzene (2CBB) (C6 H4BrCl, CAS 694-80-4).

[0199] The various aqueous phases and brines to be tested in extraction were created in the laboratory from demineralized water and pure salts (> 99.9%). Their compositions are shown in Table 24.

[0200] [Tables24] Ions Li+ Na+ Ca2+ Mg2+ no3 Salinité Essai 7.01 0.006 mol / L / / / 0.006 mol / L 0.434 g / L Essai 7.02 0.090 mol / L / / / 0.090 mol / L 6.230 g / L Essai 7.03 0.494 mol / L / / / 0.494 mol / L 34.04 g / L Essai 7.04 0.977 mol / L / / / 0.977 mol / L 67.36 g / L Essai 7.05 1.990 mol / L / / / 1.990 mol / L 137.2 g / L Essai 7.06 0.087 mol / L / / 1.5 mol / L 3.087 mol / L 228.4 g / L Essai 7.07 0.478 mol / L / / 1.5 mol / L 3.478 mol / L 255.4 g / L Essai 7.08 0.969 mol / L / / 1.5 mol / L 3.969 mol / L 289.2 g / L Essai 7.09 1.937 mol / L / / 1.5 mol / L 4.937 mol / L 356.0 g / L Essai 7.11 / 0.015 mol / L / / 0.015 mol / L 1.277 g / L Essai 7.12 / 0.093 mol / L / / 0.093 mol / L 7,952 g / L Essai 7.13 / 0.484 mol / L / / 0.484 mol / L 41.18 g / L Essai 7.14 / 0.971 mol / L / / 0.971 mol / L 82.57 g / L Essai 7.15 / 2.020 mol / L / / 2.020 mol / L 171.7 g / L Essai 7.16 / 0.102 mol / L / 1.5 mol / L 3.102 mol / L 231.1 g / L Essai 7.17 / 0.521 mol / L / 1.5 mol / L 3.521 mol / L 266.7 g / L Test 7.18 / 1.027 mol / L / 1.5 mol / L 4.027 mol / L 309.7 g / L Test 7.19 / 2.024 mol / L / 1.5 mol / L 5.024 mol / L 394.5 g / L Test 7.21 / / 0.109 mol / L 1.5 mol / L 3.218 mol / L 240.4 g / L Test 7.22 / / 0.511 mol / L 1.5 mol / L 4.022 mol / L 306.2 g / L Test 7.23 / / 1.010 mol / L 1.5 mol / L 5.020 mol / L 388.1 g / L Test 7.24 / / 1.992 mol / L 1.5 mol / L 6.984 mol / L 549.3 g / L

[0201] The previously presented extraction and de-extraction protocol is maintained for each of these tests.

[0202] For contact at 20°C with (O / A)ext = 1, for each of these initial water compositions, five distribution isotherms at 20°C were obtained representing the relative concentrations of the different salts between the organic extract and the aqueous phases at equilibrium, as shown in [Fig. 11].

[0203] It appears that saturation of the 0.25 mol / L formulation is rapidly reached for the doped LiNO3 and Ca(NO3)2 salts, while NaNO3 is weakly absorbed. This demonstrates that, as with chloride salts, diionic nitrate salts are also extractable.

[0204] Experimental design no. 8: Evolution of the density and viscosity of formulations with Li VIII

[0205] The aim is to evaluate the impact of the relative concentrations of cationic extradant and anionic solvator on the density and viscosity at 20°C of the formulation. To this end, different formulations with Li VIII, N-(3,4-dichlorophenyl)-octanamide, all dissolved in 2-chlorobromobenzene (2CBB), were prepared for different relative concentrations of EC and AS.

[0206] The results obtained are summarized in Figures 12 and 13.

[0207] It appears that the density decreases linearly with the EC concentration at iso-equivalence AS. It is also noted that for the treatment of brines with a density of 1.22 kg / L, it is not possible to exceed a certain EC concentration if, for example, the formulation must remain at a density greater than 1.27 kg / L.

[0208] It appears that the viscosity of the formulation with increasing concentrations of This Li VIII extractant can become limiting for its industrial implementation in these liquid-liquid extraction systems, in particular those where gravity decanters are used, where decantation is all the more difficult as the continuous phase is viscous.

[0209] Other compounds were therefore examined to identify extractants that maintained good selectivity and extraction for lithium while generating less viscosity. In particular, liquid extractants are of interest to study because they are potentially more soluble and generate less formulation viscosity.

[0210] Compounds of formula:

[0211] The synthesis of the compounds of interest is carried out in three successive steps. Step 1: Synthesis of the secondary amine

[0212] R1 R1 □ r3-nh

[0213] In a clean, dry flask, introduce the ketone (10 mmol, 1 eq), the solvent (17 Vol), the amine (45 mmol, 4.5 eq), and then the reagent(s). Depending on the reagent, heat if necessary. The conversion is monitored by TLC, with the disappearance of the starting ketone. Evaporate the solvent (and sometimes the residual amine) under reduced pressure. Filter, if necessary, through Fontainebleau sand, then add methanol (12 Vol). Add NaBH4 (30 mmol, 3 eq) in portions, if necessary, and stir for 1–15 h at room temperature.

[0214] Purification on silica gel if required. (DCM to DCM / ethyl acetate). Yield: 20-77% Step 2: Synthesis of chloroacetamide

[0215] C| ci < + _TEA^ { "nh-r2 DCM □ r2

[0216] In a flask, introduce the previously formed amine (10 mmol, 1 eq), dichloromethane (3 Vol, 15 eq), and triethylamine (30 mmol, 3 eq). Add cold and Under an argon atmosphere, add chloroacetyl chloride (20-25 mmol, 2-2.5 eq). Shake at room temperature for 5-24 h. Add 2 volumes of water and perform 2 counter-extractions of the aqueous phase with 2 volumes of DCM. Concentrate the organic phase using a rotary evaporator.

[0217] Purification of the product on a silica gel column (DCM eluent 100%). Yield: 30-70% Step 3: Synthesis of the compound of interest zn-r2 Ri

[0219] In a three-necked bottle, NaH (3.5-4 eq) is introduced into 10 volumes of anhydrous THF. Heat the medium under reflux in argon. Add the triol dissolved in 10 volumes of THF while still hot, followed by the synthesized chloroacetamide dissolved in 15-20 volumes of THF. Stir the medium under reflux for 1-24 hours. Neutralize the medium by adding 10 volumes of water. Perform two counter-extractions of the aqueous phase with 5 volumes of DCM. Then perform one or two washes of the organic phase with 5 volumes of water. Concentrate the organic phase using a rotary evaporator.

[0220] Purify the crude product obtained by silica gel chromatography (eluent: heptane / ethyl acetate). Yields are generally between 50-70%.

[0221] Table 25 shows the formulas of the synthesized compounds, with Li VIII being renamed CE00. < i---b? Q»---' ) Q"—X >----' \.....y- / x xx ° O 7 / .....> \ / \ \ / Z -....." X / X / <' '•• yyy >•-■■ '\r yy Z ..-X. 77 V y' x •%•■■■ -xZ '■'x"-' Z''''xxZ^ ■ \ yyq CïY 7-0 ô CE00 (133338-85-9) CEOl CE02 x ---, o X / x—0. O'ri x— ' X-— Q >""> oW s < > rvj 7 X p— -■■' \ b—-< >—-> y,,,, / o S—txï / x / \ \ x / x / } ( ; \i-< \ \ X____A X $J X...7 y, .XCE'—- •;3 Q4, 'xk ? b—' >-—■■' \X / 7 X .---- y— 0 7--N / A 3 Z... / X. i / X / / XX *_____ / Z x 'x / GG— -■ y O—-< '----- _ 'W dw / = \ > y.... ; / / y / X 7 x, \ Vy p—A .>—y 6' '^O \ j CE06 CE07 (148303-04-2) CE08 \ / ''k ^.-0. çy ■isC ■' / -—> " \ x / x / x / / X x \ • >--f4 ) 0—-xz / / -- $ ô ) 0' x—ch-5 □ ::::X y—"xx ......' bHs X / X. ...yX yx K-^9> tJ '0 < (133338-84-8) CE11 . -, --^ ' ' ' l : 1 .."'X y" CE12 CE13 CE14 .....”xf ■ " • xs,.--vx _,.'x . , c y..... £ X •■' \ •' \ .••s, x ..•• -X,-: CE15 CE16 CE17 >••• -X 7 CE18 CE19 CE20 / \ \ CH-, . M-.C CHi ' X 7 ' / x \ " \ y ' p- / > O - A > ' P d ? Ô' y—GH:: pH3. .( Hr£ H—Z CH-, "--< k--ÇHs ÇHÿ r—•■ A. / À'-- ,X / —- CH . s: N—, CH.;. HC— / / ( '----N CHs y \ , CH? .....\ oo —s / ^\ H3C M - - - .< CH, \----N CHS VO y CHî H^C---Ç H?C CH? CE-12 83 CE22 (746656-32-6) \______ ap— / ) 'bx csh,3 HssCs'X ' 6' GsH<;i <% O-""< ^""CsHts \ y™ / y y-?• / ) df. X 1X. ç, O—-X ? b—XK .' . > * '■XXX; '^'js CE24 CE25 CE26 < :•.••••:■; v--; y y... x X-'-'-d . CE27 CE28 CE29 PH3 { \ %---, \ / '' \ V '—ht 0-----•■ 7 0—v / ------y ----- / Q / d' ) o '—' O \ N— / X \ \ / o O i ° °—\ ! r" \ ^ch* / 1 f''' 0 —\j CE30 (405264-17-7) CE31 CE32 ÇH3; ■—H Ô- ; 0— s CH, \ \ ' )rJ 0 ;>--NG 0 X1 'CHÎ q— x 39 ' / 0' X~X k..c-4 > d" Xhs O» 0:~<' CE33 (405264-15-5) CE34 (405264-16-6) CE35 c / \ / \ x G 'W .....\ S----X >2, Ô—'' y G—'>■ y"" K?? W-----

[0223] Tables 26 and 27 present the characteristics of the synthesized compounds. «s ee X X X X X X X x X x X X X X X X X X X X X X X X X X uh es X X X X X X X X X X æ X X X æ X X X a; X X X X X X X œ X T X T i ai X X X X X X X X X æ X æ X X X X X X X X X té ij.1 & P té 1 é fS 0 «sS i UJ s X Cl 'Çi té bj £ ai à X i LU i iJJ i UJ s g & i i ÜJ g & i 4 G +? i-i-l £ o U, 1 +3 ij-I té g Cl i g té p) $ Lli i LU LU! I LU i LU eu & té g té g S ¢4 £5 iS té S JS f O U LJ s JS •8 & Ü P d JS t U X G I 1 G i G 'm 1 § 'S <^s f iü à $ â Ë' a, i ls g ex j ï 4 à jn ï JS è #1 ï ù <5 § ÈÏÙ S t P •P g G g-& à s ÜJ !& C< y té I >& 1 V Çê en r. $ X à i & j ili £ Cî P Sef ai "b "ù ai X Cj $ ai s c s X 0 <s T 0 0 X ü Cî a n* y i 1 0 aî X 0 y *3 iü G Ô ai "q y *3 ï£' g & <3 S G M 0 ai y Q $ i" y té .G § SX G té <x» ç< 01 Cl & Q s ■ç 1 & té S! S X s i té é) ni ü & Sh us i^ P En 3 Q $ U1 |X: Ml q$ ¢0 i / ï ket îTi H O r-LÜ sM !« 'S X ai X '3 X 01 X & '3 X 01 X '3 X «J g a '3 X «J ai S X LU S X P Ml Ch 01 rS X & '3 $ a< S X dj '3 X a* S X Çh té sh té té LG £0 «N té <*4 ex> tO P in £ *4 e>x eh en r-^ fYi Ml U> ch rJ CM °\ u4' rn rté LÙ CS C3 f< en iN H rn >•■4 sa* rN O té nü >•■•4 ■té ni i-Yi té >vï M3 té Xt u3 u& u ■ ■ * you ^-en ■te <4 t0 you r» that you are) you know K) you £ 'J Çy h èâ Ü £ 1 G g té Ci 1 g 1 si 1 UN 4 ed <i â fe Çi jl ¢0 efc in en M & £ Ci 1 1 g: i U g j K i U g 1 5g i U g sa i S u g sa i c i U g 1 & ÎÔ g «H F-4 h5 té in Ü5 Æ< s g Js & « u S iïi 65 X Q § R5 S X l\ 3 «1 Ù5 X <x Q tX S rn pi X S U 8 Ên X a Q s rn X rq b-'i U i X •n Q S 22 1 i Qÿ s? & i O s 22 $! x: 3 g s in O s 22 4-M È Oi fVï U S 8 k X $ 3 s ù5 k X 3 ên i 65 *t s in e3 rn B 3 s s X èrt 3 S b5 $ rn 8 L0 l\ U g 3 8 X SR U g NI U Ë Ci 8 22 X SR U g NI ij*ï g R 8v 0>i B CX gS s © ZWU ai & UAS ÜJ N ¢S 'S' Xï x gy xS ç ç ¢1 If A Ks* v*4 or S tea X 0 0J $ % ,u. b fc & tÇ S w X ftl ■« Q ( <S\ +;< ÜJ § ÜÙ Ç| +. < ÜJ ÎH â X ô' LU g I y <3 W &î '& g â X tea 5* ü i£ 1 as »: < LU ¥ X tea ¥ CI G 5 & X tea SS ij +\-£ X ■3-' tea tea X tea § i$ 1" S W À g g eu 1 But ■^-î is AT I? 1 '¥ here J, k£ LU N Ü LU s X À. <h-i lli 9 té LU § LU -4 LU éj e UJ Ùh à LU O LU O u"i O LU té à LU U Q LU O téJ a LU U g LU té Q H LU té s-1 LU té e-j H LU té LU téi \t~ H LU Lh ^1 LU té té y-M UJ té LU té té LU sy> In Q te iN ÜJ ri IN O eN C5J IN CG M IN UT ùh CN IN .

[0225] [Table. 27] (Me = Methyl) your XX ■ii i XXXXXXXXXXX you XXXXXXXXXXXX «sj3 XXN O&t 0) ga; Æ Æ Æ : <t; a; X X X X os £ *4 LU +3 LU *? LU J* 4» LU 4» LU n UJ ÿ LU «t» LU «t» LU •t» LU +X LU A& 4M LU X 4M LU 4M LU FM es s .g w s M~ H < £ < Q ’w Skx tu +U 25 o5 ix IV Ê | CM æ 0 'S O <y X (S Ï3 u SU ÉS &. ë£ g œ Gk llü £ K ù < kü «B dà 1 't JC 4» UJ g s Èi Kx O 6\a & £ iS m u.l <N ï' X $ U c>X $ UUS: S £ $ É t $ & ■& tu X à 1 & J& 4M IN MJ X & X :^K 0J X ^1 *s & *s ^1 'BX *s X JI 'SX ÿj 'SX a? X to> 'SX 0J X FM uï vM ■H CM<h s LIS CM fi) M? en O Uï F^ r- ■H U'i Uï Lfi m Ch m æ M> uî l\-, Uï CS) Fri ■U Çh sa sn Ch kÙ •X1 < LU Lfi m Fx A. Lfi Lh & M £ CS £ B £ K i M 5$ S iw K trig sa ¢5 § U sa SS § u< Lh LTi 4 8 ​​L / i ? 4' i L / iii B *T Fv cA ©5 k£à £ 0 u £ c> SS 0 U gs Çx 0 U g & t<y X N r> 1 ■H OC O MS w 52 Si ¢3 X *M Ltj ü 52 K èm X æ B SD N- «JX r.s B tg ris ua XO g rh Lh X Prt rh O s ■v< X ïrt rh O g rh N- X Lp rù O 8 rh iv^ hS OS O'' Xi È Q 52 k X «! 52 & with St 0? s 52 s SJ rl ''JJ VjW "B s LM Q fN & è LU X UJ A iv kk-î C£ 'ssf & *Ÿ JM LU t |V| AA CJ '^T & *7' SM LU A r "u • È A *r il» ku & sâ. $ ?2 *is ■M THE i © i^' THE 'w 1 sx< CL w THE THE 1 j£ % ÜU su X À lU i «F "ÇJ W â! & § * 1 ,c X F-. & t* <N U XL FM S S lu h Xy»-.' ai' rkv n $ s B U LU x< tu '1" LU $ i «tx 4c> Lil >> LU CM LU QN UJ (J KJ eM LU QQ> cm LU QQ ¢0 LU Q LU U FM CO LU U CO in LU U in LU Q in LU U LÜ sn LU Q r% en UJ Q en cô ILJ U fj'l ÜJ y

[0226] Experimental design no. 9: Synthesis of extractants and densities of formulations

[0227] As the different extractants CE00 to CE39 were synthesized, the impact of the extractant on the density of formulations with 3 equivalents of anionic solvates and molar concentrations of CE of 0.2 and 0.3 mol / L respectively was observed in 3 to 5 mL of formulation. The results obtained are illustrated for a number of them in [Fig. 14].

[0228] A relatively logical trend was obtained. The higher the molar mass of the extractant, the more negative its impact on the density of the formulation.

[0229] Thus, lowering the molar mass of the extractant is of interest with the limitation of its solubility in water.

[0230] Experimental design no. 10: Viscosity of a formulation with a low molar mass extractant

[0231] Since the viscosity measurement requires 15 to 20 mL of formulation, it was chosen to synthesize a low molar mass extractant that is relatively easy to synthesize in order to obtain more than 50 grams of Et-NPiperidin (CAS No. 405264-17-7) (1H NMR: 4.02 (s, 6H), 3.53 - 3.40 (m, 6H), 3.34 (s, 12H), 1.54 (dd, J = 20.0, 14.4 Hz, 18H), 1.38 (d, J = 7.6 Hz, 2H), 0.81 (t, J = 7.6 Hz, 3H)) for the preparation of formulations incorporating 1.5 to 5 grams of this extractant.

[0232] Beyond its low molar mass, this product has proven to be an oil, which suggests that the tested formulations are representative of the minimum viscosities that can be obtained with this family of tripod extractants.

[0233] The results obtained are summarized in [Fig. 15].

[0234] It appears that the viscosity is lowered on average by 53% which makes it possible to approach CE concentrations of 400 mmol / L by giving a limit of 20 centipoise at 20°C, i.e. a gain in extraction capacity of the order of 33% compared to formulations with the ionophore Li VIII / CE00.

[0235] Experimental design no. 11: Extraction performance of compounds of interest

[0236] This involves implementing exactly the experimental plan no. 1 already presented but for new cationic extractants CE01 to CE39.

[0237] Part of the extraction results obtained are given in Table 28.

[0239] These results show that: 1. For all compounds, with the exception of Et-N(Morpholine), CE39, a high rate of extractant use relative to lithium is maintained with variability in Keq(Li) but Keq(Na) and Keq(Ca) always low, 2. A liquid extractant is readily accessible through the functionalization of the amide (RI, R2), 3. The use of cyclic and / or branched chains in RI, R2 promotes Li / Na selectivity and therefore the extraction of Li+ / Na+. 4. The use of linear alkyl chains with more than 4 carbons promotes Li / Ca selectivity and therefore the extraction of Li+ / Ca2+. 5. The use in R3 of an elongated or branched alkyl chain or of an electron-donating group promotes the utilization rate of the extractant. 6. Replacing a hydrogen in R4, R5 and / or R6 with at least one short-chain alkyl improves lithium extraction capacity while lowering the melting temperature of the extractant.

[0240] Following these promising results, work continued on the study of extraction phases at 20°C and deextraction at 80°C on multi-salt brines for formulations incorporating the targeted extractants, some of which are presented below.

[0241] Experimental design no. 12: Implementation of a formulation incorporating CE21 for demonstrate the possible use of these various tripodants in the selective extraction of LiCl

[0242] For a liquid organic formulation composed of [qe]1 = 80 mmol / L of LJ or g using ionophore CE21 and 4 equivalents of anionic solvatant (AS), i.e. 320 mmol / L of A-(3,4-dichlorophenyl)-octanamide (C14H19Cl2NO, (CAS 730-25-6), all dissolved in 2-chlorobromobenzene (2CBB) C6H4BrCl, CAS 694-80-4), an extraction is carried out at 23°C on a multi-salt brine, then the de-extraction of the previously absorbed salts is evaluated by contacting it with demineralized water at 80°C for A / Odesext ratios of 0.2 and 1. These tests allow the influence of this ratio on the de-extraction yields of the different ions to be evaluated.

[0243] The brine used in extraction, representative of a real lithium-rich brine, was created in the laboratory from demineralized water and pure salts (> 99.9%).

[0244] After analysis, it has a salinity of 286.5 g / L and its ionic composition is indicated in Table 29. Tests / Ions Li+ Na+ K+ Ca2+ Mg2+ Cl 10 0.156 mol / L (1082 mg / L) 3.878 mol / L (89.17 g / L) 0.247 mol / L (9.675 g / L) 0.033mol / L (1.33 g / L) 0.327 mol / L (7.95 g / L) 5.00 mol / L (177.3 g / L)

[0246]

[0247]

[0248]

[0249]

[0250]

[0251] The extraction and de-extraction protocol previously presented is maintained for each of these tests with the exception of the A / Odesext given above. Firstly, a single-contact extraction with a ratio (O / A)ext = 1 is implemented with 10 mL of organic phase and 10 mL of brine. The liquid-liquid extraction performance is illustrated in Table 30. [Tables30] (O / A)ext= 1 Li+ Na+ K+ Ca2+ Mg2+ Cl Brine to be treated (mmol / L) 155.9 3879 247.4 33.1 327.0 5002 Treated brine (mmol / L) 135.4 3880 247.4 28.4 321.6 4964 EMn+(%) 13.2% 0.0% 0.0% 14.3% 1.7% 0.8% SF(Li+ / Mn+) / 22.4 197 0.94 2585 / The results of the deextraction with demineralized water at 80°C are summarized in the Tables 31 and 32. [Tables 31] (A / O) de-extraction LJ or g (mol / L) [^+]ZL Jorg (mol / L) (mol / L) rr, 2+T^ Ca LJ arg (mol / L) tu 7+1 ■ / Mg L 'jorg (mol / L) [C / YLJ org (mol / L) 0 21.04 26.92 0.20 4.689 0.019 57.6 0.2 1.25 2.14 0.10 0.65 0.02 4.82 1 0.36 3.82 0.13 0.148 0.008 4.62 (A / O) de-extraction E'Li(%) E'Na(%) E'k(%) E'Ca(%) E'Mg(%) E'ci(%) 0.2 94% 92% 46% 86% 12% 92% 1 98% 86% 35% 97% 60% 92%

[0253] By comparison, by replacing CE21 with CE00, the Li VIII ionophore, the extraction performance obtained is illustrated in Table 33.

[0254] [Tables33] (O / A)ext= 1 Li+ Na+ K+ Ca2+ Mg2+ Cl Brine to be treated (mmol / L) 155.9 3879 247.4 33.1 327.0 5002 Treated brine (mmol / L) 104.3 3867 246.2 32.0 319.6 4920 EMn+(%) 33.1% 0.3% 0.5% 3.5% 2.3% 1.6% SF(Li+ / Mn+) / 136 717 47 9119 /

[0255] Lithium extraction performance is improved, increasing from 13.2% to 33.1%, but more importantly, calcium extraction is reduced from 14.3% to 3.5%. It should also be noted that the separation factors (SF) are significantly improved for all cations.

[0256] The same work on other tripods has given, for example, for CEI 1, a liquid extractant, a lithium extraction yield of 30.1% and of calcium of 4.5%, while others are even better. Example :

[0257] For a liquid organic formulation composed of çj? p = 0.34 mol / L of ionophore CE11 and 3 equivalents of anionic solvatant (AS), i.e. 1.02 mol / L of V-(3,4-dichlorophenyl)-octanamide (C14H19Q2NO, CAS 730-25-6), all dissolved in 2-chlorobromobenzene (2CBB)(C6H4BrCl, CAS 694-80-4), the aim is to implement a liquid-liquid extraction process of LiCl by temperature modulation between a multi-salt brine to be treated at 20°C and demineralized water at 80°C by the use of 4 stages of mixer-settlers in extraction at 20°C and a stirred column with 3 theoretical stages to carry out the deextraction at 80°C.

[0258] The LiCl extraction phase is carried out with an (O / A)ext of 1.1 at 20°C and the phase LiCl desextraction is carried out with an (O / A) desext of 10 to 80°C.

[0259] The brine used in extraction is a reconstituted brine based on a published reference composition from the Maricunga salt flat in Chile. It was created in the laboratory from demineralized water and pure salts (> 99.9%).

[0260] After analysis, it has a salinity of 306.4 g / L and its composition is indicated in Table 34.

[0261] [Tables34] Tests / Ions Li+ Na+ K+ Mg2+ Ca2+ Cl 10 0.163 mol / L (1132 mg / L) 3.718 mol / L (85.48 g / L) 0.211 mol / L (8.260 g / L) 0.302mol / L (7.345 g / L) 0.338 mol / L (13.53 g / L) 5.36 mol / L (189.9 g / L)

[0262] The associated McCabe-Thiele diagram is given in [Fig. 16].

[0263] The process diagram considered to illustrate this implementation is shown in [Fig. 17],

[0264] The four extraction stages are carried out by the four series mixers [1a] to [4a] associated with the four series decanters [Idc] to [4d], of which [Idc] is a centrifugal decanter. The heat exchangers [1e] and [2e] serve both to heat and cool the organic phase and the deextraction water, respectively. Finally, the counter-current hot deextraction column is represented at [1e].

[0265] The material balance obtained for a production equivalent to 12,285 tonnes of LiCl per year is given in Table 35 for 21.5 tonnes of water / h supplied with [Al].

[0266] The lithium extraction and production yield here is 93%. Feed Ions [SI] Refined [S5] Deextracted [P2] SF(Li+ / Mn+) Compositions in g / L Li+ 1.132 0.080 10.229 / Na+ 85.479 84.770 11.175 972 K+ 8.260 8.302 0.84 665 Mg2+ 7.345 7.382 0.0110 85 677 Ca2+ 13.531 12.473 10.916 146 SO42 0.722 0.726 0.007 137 450 Cl- 1899.2388 .738 / h2o 894,840 899,514 959,445 TDS-Total Salinity 306,393 295,463 121,180 Feed Ions [SI] Refined [S5] Desextrated [P2] SF(Li+ / Mn+) in Composition 0.013 / L / L Li 1.474 / Na+ 3.718 3.687 0.486 972 K+ 0.211 0.212 0.0003 85 665 Mg2+ 0.302 0.304 0.0004 85 677 Ca2+ 0.338 0.31 0.274 SO 0.008 0.008 0 137 450 Cl- 5.357 5.126 2.506 / h2o 49.671 49.931 53.257 Volumetric mass (kg / L) 1.201 1.195 1.081m Flow rate (28.28) 217.1 22.4 Main flow rates in ton / h LiCl 1.51 0.11 1.40 NaCl 47.4 46.8 0.64 CaCl2 8.18 7.50 0.68 h2o 195 195 21.5

[0268] This basic material balance can be significantly improved with regard to the purity of the desorbed LiCl by implementing intermediate washing steps of the organic phase after the LiCl extraction phase from the brine. Thus, a single washing step of the organic phase after extraction with (A / O)iav = 0.05 makes it possible to lower the sodium Na+ concentration of the Desextrext from 0.486 mol / L to 0.076 mol / L (SF = 3330) and the calcium Ca2+ concentration from 0.272 mol / L to 0.026 mol / L (SF = 865) without major degradation of the lithium production yield, which decreases from 93% to 90.5% for an (O / A)ext of 1.1. References

[0269] [1] Gabra & Tonna - Hydrometallurgy, 1978, 3, pp. 23-33

[0270] [2] Bukowsky & Uhlemann - Separation science and Technology, 1993, 28(6), pp. 1357-1360

[0271] [3] Hano et al. - Solvent Extraction and Ion Exchange, 1992, 10(2), pp. 195-206

[0272] [4] D. Gao & al. - Journal of Chemical Engineering of Japan, 2016, Vol. 49, No. 2, pp. 104-110

[0273] [5] Zhou & al - J. Chem. Eng. Data 2011, 56, pp. 3518-3522

[0274] [6] Zhou & al - Ind. Eng.Chem. Res., 2012, 51, pp. 12926-12932

[0275] [7] Hui-fang & al - Hydrometallurgy, 2016, 160, pp. 1-5

[0276] [8] Zhou & al. - ACS Sustainable Chem. Eng., 2019, 7, 9, pp. 8885-8892

[0277] [9] Kamenica & al. - Sensors, 2017, 17, pp 2430 < / x>

Claims

Demands

1. - Hydrophobic organic liquid composition for selective extraction of a diionic lithium salt comprising a lithium cation and an anion complementary to the lithium cation chosen in particular from Cl, I, Br, CN, NO3, HCO3 from a brine rich in lithium to be treated, said composition comprising: (A) at least one lithium cation extracting compound, selected from compounds of formula: in which: • RI and R2, whether identical or different, are, regardless of their position on a nitrogen atom, independently chosen from linear or branched C1-C12 alkyl, aryl, or C4-Cs cycloalkyl; or • RI and R2, taken together with the nitrogen atom that bears them, form a ring with five, six, seven or eight links; • R3 is chosen from hydrogen, linear or branched CrC8 alkyl, C4-C8 cycloalkyl, C2-C6 alkoxyalkyl and alkoxy-alkylaryl; • R4 is chosen from hydrogen, linear or branched C1-C3 alkyl; • R5 is chosen from hydrogen, linear or branched C1-C3 alkyl; • R6 is chosen from hydrogen, linear or branched C1-C3 alkyl; (B) at least one organic, protic, and hydrophobic compound that solvates the complementary anion of the lithium cation; and (C) at least one hydrophobic polar diluent having a flash point at atmospheric pressure above 60°C, preferably above 75°C, more preferably above 90°C.

2. - Hydrophobic organic liquid composition according to claim 1, characterized in that the lithium cation extracting compound has a molar mass of at least 450 g / mol, preferably of at least 550 g / mol.

3. - A hydrophobic organic liquid composition according to claim 1 and 2, characterized in that the lithium cation-extracting compound has a Log K complexation constant for this cation in methanol at 25°C of at least 1, preferably greater than

4. X. - Hydrophobic organic liquid composition according to any one of claims 1 to 3, characterized in that the lithium cation extracting compound exhibits a negative enthalpy change upon complexation of the lithium cation, AH, associated with an absolute value of the ratio of the enthalpy change upon complexation of the lithium cation AH to the entropy change upon complexation of the lithium cation, AS, at temperature T=298K, IAH / (TAS)I greater than 2, preferably greater than 5.

5. - Hydrophobic organic liquid composition according to any one of claims 1 to 4, characterized in that the lithium cation extracting compound has a melting temperature below 200°C, preferably below 50°C and more preferably below 25°C.

6. - Hydrophobic organic liquid composition according to any one of claims 1 to 5, characterized in that: • RI and R2 are, regardless of their position on a nitrogen atom, independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, 2-methylbutyl, 2-ethylpropyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, 2-ethylhexyl, phenyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl; or • RI and R2, taken together with the nitrogen atom on which they are borne, form a pyrrolidine, piperidine, azepane or azocane ring; R3 is chosen from hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, 2-methylbutyl, 2-ethylpropyl, n-hexyl, cyclohexyl, methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl and -CH2-O-CH2-Phenyl; and R4, R5 and R6 are hydrogen or methyl,

7. RI and R2 are advantageously chosen from butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, or phenyl in cases where the brine to be treated has a calcium concentration greater than 10 g / L and / or where Li+ / Ca2+ selectivity is preferred; and RI and R2 being advantageously chosen from iso-propyl, iso-butyl, sec-butyl, tert-butyl, iso-pentyl, 2-methylbutyl, 2-ethylpropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or RI and R2, taken together with the nitrogen atom which bears them, form a pyrrolidine, piperidine, azepane or azocane ring in the case where the brine to be treated has a calcium concentration of less than 10 g / L and / or where Li+ / Na+ selectivity is preferred. - Hydrophobic organic liquid composition according to any one of claims 1 to 6, characterized in that the lithium cation-extracting compound is selected from: Y—fv 0—- > ¢--, >—■ X / \ / / XO ,ÿ--N _ ■' / X / X / \ / ' "■y"' ' W < Q o O'X X0 X "in à CEOO CE01 CE02 X .-—x 0 < / X / .....\ ?.....■ / \x X / < yp—-• ) O- x y-—' X— / ' 0 V__ and-4 . / '-V ( ; X ..... / ' X______ / ' CHj oq—z S ¢-. y—-'' / -"v, / -7 < / "V / ““xx / x. -•••.. .X , s-' y' Y' ..À. CE03 CE04 CE05 H \ J / ' XC' 0-^ ) D— )--7 .••—XV—Z df / ^-7 / "-yM ) / ■ \ Z™. <( \ / \ n -„ / / X ( > r<{—< > 7—1 o V- z- \ / / Z""\ CE06 CE07 CE08 Z"”\ CHX 'X y... / ..... r ., ZTM'- 7-7.....V}--\X \ ? ■• •■ ..•• S--- x. ••' \ : \___ / CE12 CE13 CE14 X'\<'X' x';< Y . J. J CE16 CE17 CE17 CJ j' ” Z' > " '^ \ - 1 ,2 / j' HeC CHj hX )—■ the £- / the ; C-“< 0^3 ( n— / as ( < \ X---, .... / \... À. rpAl X CE21 CE22 CE23 5'- '3 A X______k ,A~y / ^*9 ) 0 <y^S CR. M. <7.;-7Ï >in AA;. / XX !À.A,S <( ) A CE24 CE25 CE26 '"■A ^.A" ......: CE27 CE28 CE29 >--Ô--> 0--y--- / —■•'■ $ X—-N ) :d' ) ô? / ---¾ ^H;> C;-: / . CE33 CE34 CE35 > ■ X ÿ—on A.

8.

9. - Hydrophobic organic liquid composition according to any one of claims 1 to 7, characterized in that the organic, protic and hydrophobic compound, solvating the complementary anion of the lithium cation, has a pKa in water at 25°C of at least 9, preferably of at least 10.5 and preferably less than the pKa of water at 25°C, or at least less than 15 at 25°C and whose solubility in water at 25°C is less than 0.01 mol / 1. - Hydrophobic organic liquid composition according to claim 8, characterized in that the organic, protic and hydrophobic, solvent compound Fanion complementary to the lithium cation is a compound of formula (B): (B) in which: at least one of the radicals RB, Rc and RD, identical or different, is a halogen atom or an electron-withdrawing group chosen from the following group: F, Cl, Br; C mF2m+i with m < 4, where m is a non-zero integer; CF2CF2CpH2p+i with p < 4, where p is an integer; CF2CpH2p+i with p < 4, where p is an integer; CH2CpF2p+i with p < 4, where p is an integer; OCH2CF3; C(=O)CF3; CmHnFpClqBrs with m < 4, where n, p, q, s are integers of which at least p, q or s is non-zero; C(=O)OCmH2m+i with m < 4, where m is an integer; and C(=O)CmH2m+i with m < 4, where m is an integer; The remaining radicals RA, RB, Rc, Rd and RE are chosen, identical or different, among the following non-electro-attracting radicals: H; CH3; CH2CH3; CH2CH2CpF2p+i with p < 4, where p is an integer; CmH2mA with m < 10, where m is an integer greater than 1; and CmH2m+i with m < 10, where m is a non-zero integer; where only one of the radicals RA to RE can be one of these last two radicals CmH2m_i and CmH2m+i; and X is chosen from the following radicals: OH; ; / .C—R' \ R" where R' and R”, identical or different, are chosen from the following radicals: H; CnH2nA with n < 4, where n is an integer greater than 1; CnH2n+i with n < 4, where n is a non-zero integer; CH2CH2CpF2p+i with p < 4, where p is an integer; CH2CpF2p+i with p < 4, where p is an integer; CF2CpH2p+i with p < 4, where p is an integer; CF2CF2CpH2p+i with p < 4, where p is an integer; CmF2m+i with m < 4, where m is a non-zero integer; CmHnFpClqBrs with m < 4, where n, p, q, s are integers of which at least p, q or s is non-zero; and where R” ' is chosen from the following radicals: CmH2m+i with m < 20, where m is an integer; CmH2mA with m < 20, where m is an integer greater than 1; CmHnFpClqBrs with m < 10, where n, p, q, s are integers of which at least p, q, or s is non-zero; CH2CH2CpF2p+i with p < 4, where p is an integer; CH2CpF2p+i with p < 4, where p is an integer; CF2CpH2p+i with p < 4, where p is an integer; CF2CF2CpH2p+i with p < 4, where p is an integer; CmF 2m+i with m < 4, where m is a non-zero integer; and an aryl radical of formula (b): where Ra, Rb, Rc, Rd and Re, identical or different, are such as previously defined in formula (B).

10. - Hydrophobic organic liquid composition according to claim 9, characterized by the fact that in the compound of formula (B) X re- present: Q H

11. - Hydrophobic organic liquid composition according to claim 10, characterized in that compound (B) is represented by the formula: (C): ,o or (D): Fx. \ Q HR in which R'” is chosen from the following radicals: CmH2m+i with m < 20, preferably < 15 where m is an integer; CmH2m.i with m < 20, where m is an integer greater than 1; CmHnFpClqBrs with m < 10, where n, p, q, s are integers of which at least p, q or s is non-zero; and an aryl radical of formula (b):

12.

13.

14.

15. Rc where Ra, Rb, Rc, Rd and Re, identical or different, are such as defined in formula (B) in claim 8. - Hydrophobic organic liquid composition according to claim 11, characterized in that the radical R'” is n-C7H5, n-CgH^, n-CnH23 or nC[3H27 - Hydrophobic organic liquid composition according to any one of claims 1 to 12, characterized in that at least one lithium cation extracting compound is present in the composition at a concentration of 0.15 to 1 mol / L, preferably 0.3 to 1 mol / L, more preferably 0.45 to 1 mol / L. - Hydrophobic organic liquid composition according to claim 13, characterized in that the ratio of the molar concentration of at least one organic, protic and hydrophobic compound, solvating the complementary anion of the lithium cation to the molar concentration of at least one compound extracting the lithium cation is 1 to 10, preferably 1.5 to 5 and more preferably 2 to 4. - Hydrophobic organic liquid composition according to one of the following:

16.

17.

18. indications 1 to 14, characterized by the fact that the hydrophobic polar organic diluent has a viscosity at 20°C of less than 5 mPa.s, preferably less than 2 mPa.s. - Hydrophobic organic liquid composition according to any one of claims 1 to 15, characterized in that it has a density at 20°C greater than 1.20 kg / L, preferably greater than 1.25 kg / L, more preferably greater than 1.30 kg / L, for a viscosity at 20°C less than 50 mPa.s, preferably less than 25 mPa.s, for a brine to be treated having a density at 20°C at least 0.05 kg / L less. - Hydrophobic organic liquid composition according to any one of claims 1 to 15, characterized in that it has a density at 20°C greater than 1.25 kg / L, preferably greater than 1.30 kg / L, more preferably greater than 1.35 kg / L, for a viscosity at 20°C less than 30 mPa.s, preferably less than 15 mPa.s, for a brine to be treated having a density at 20°C at least 0.15 kg / L less. - Compound chosen from the compounds with the following formula: • •'X ' Cx..--'' 'x<''' 9 Q [ î T y '-O / ] z---O 0 "An ô / 0-7 y Q— J \ / / \ / X / / ' ■ ? o x____ CE04 CE05 CE06 , Lj x"~\ or •?" .... .•—■ • '-■: • C.< \ ■'■■■' ••• ••• x...K, CE08 CE09 CE11 yx ■■ y___ ,,- X. \-.Z 7' "y CE' ' 3 CE ... CE1 v …. >„.0 ...J ; ( ■ '" X-. CE15 CE16 CE17 Z.....^,^ s ï i. > \ JA y'"'""'"■""" CE18 CE19 CE20 1^-. CH-, X—- HsC C«- >— X— / 0 y—\ \ \ / \ ? z .' HjC c / yN \t. OO j V-, $ S— p-app;. { X'X XX ;• CE26 CE27 CE28 Yy ; THE 3 ÿ- THE N. THE JL. / -'-x \___ / 0 / \Z »1 \ ï ( o CE29 CE31 CE32 Xrî;. G £>…..} G—Y <x     ?                  x p™•    o v”ci      p—-n ç.   p""’ x            ou ce35 ce37 ce38

19. - Use of the hydrophobic organic liquid composition according to any one of claims 1 to 17 in a lithium salt extraction process, said process comprising a mixing step, at a first temperature, between the hydrophobic organic liquid composition and the brine to be treated, a separation step of the hydrophobic organic liquid composition loaded with lithium salt and the treated brine, and a regeneration step of the hydrophobic organic liquid composition by treating the hydrophobic organic liquid composition loaded with lithium salt with a treatment water, said regeneration step being carried out at a second temperature, higher than the first temperature, the difference between the first temperature and the second temperature being from 30 to 150°C, preferably from 50 to 100°C, more preferably from 60 to 80°C.< / x>

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