HYDROPHOBIC ORGANIC LIQUID COMPOSITIONS FOR THE EXTRACTION OF A MONOVALENT OR DIVALENT ANION SALT FROM SALT WATER OR BRINE

Abstract

------ HYDROPHOBIC ORGANIC LIQUID COMPOSITIONS FOR THE EXTRACTION OF A MONOVALENT OR DIVALENT ANION SALT FROM SALT WATER OR BRINE This composition comprises: (A) at least one cation-extracting compound having a Log K complexation constant for this cation in methanol at 25°C of at least 1; (B) at least one hydrophobic, diprotic organic compound solvating the complementary anion of the cation; and (C) at least one hydrophobic polar organic diluent having a flash point above 60°C.The component(s) (B) is or are chosen from the compounds of formula (I): RA-NH-RB-NH-RC in which RA and RC each independently represent one of a monovalent aromatic or heteroaromatic radical, possibly substituted; a radical –C(=X1)-RA,C, where X1 represents O or S and RA,C represents an aromatic or heteroaromatic radical; an alkyl or alkoxyl radical, linear or branched, or cycloalkyl or cycloalkyl-alkyl, these radicals being possibly substituted; and RB represents one of a divalent aromatic or heteroaromatic radical, possibly substituted; -C(=X2)-, where X2 represents O or S; an ethylene radical -CH2CH2-; and a radical *-C(=X3)-QC(=X3)-* where X3 represents O or S and Q represents a divalent aromatic or heteroaromatic radical, possibly substituted.

Description

Title of the invention: Hydrophobic organic liquid compositions for the extraction of a monovalent or divalent anion salt from salt water or brine

[0001] The present invention relates to a hydrophobic organic liquid composition for the selective or non-selective extraction of a monovalent or divalent anion salt from salt water, and in particular from brine.

[0002] In the context of the ecological and energy transition, minerals, in particular metallic ones, derived from alkali, alkaline-earth, transition metals, the platinum group or rare earths, but also from inorganic salts used in many heavy, chemical, energy or agricultural industries, should see their demand grow strongly and sometimes follow exponential growth as for lithium.

[0003] Thus, let us mention some of these metals such as Manganese, Copper, Nickel, Cobalt, Zinc, silver, lanthanides or actinides and, in particular, the salts of lithium, sodium, potassium, ammonium, fluoride, chloride, bromide, iodide, nitrate, chlorate or certain eutectic mixtures of these salts, used in the storage or transport of heat or, for the operation of nuclear reactors, in particular molten salt reactors.

[0004] The advent of lithium-based electricity storage methods (Li-ion batteries, etc.) is facilitated by the widespread availability of this metal on Earth, either in the form of mineral rock (Spodumene, Lepidolite, Petalite, etc.) or as a salt (LiCl, Li2SO4, etc.) dissolved or undissolved in water. Thus, its extraction (186 kt Li) is still relatively modest today compared to other metals of the energy transition (Iron: 1,500 Mt; Aluminum: 65 Mt; Copper: 20 Mt; Manganese: 19 Mt; Chromium: 12 Mt; Zinc: 12 Mt; Titanium: 8 Mt; Lead: 4.7 Mt; Nickel: 2.5 Mt and Rare Earths: 0.35 Mt).

[0005] These metals and salts are extracted from the natural environment either directly from natural continental brines originating from Andean or Tibetan endorheic basins, from brines of petroleum production waters, or from geothermal and other saline aquifers, or from mineral rocks that are crushed and then enriched in the ore of interest before potentially being solubilized (leached) in water for their subsequent separation and purification (or refining) processing. Thus, these minerals of interest, whether cationic or anionic in their water-solubilized form, must be able to undergo hydrometallurgical treatment that is as efficient as possible, from an ecological and environmental point of view, as well as an economic one.

[0006] Consequently, industry needs technologies capable of producing or recycling these minerals sustainably, with very limited energy and water use, and ideally without chemical inputs or waste. It is also essential that these technologies be rapidly deployable on a large scale, given the significant need.

[0007] The present invention aims to improve the performance of the temperature-modulated liquid-liquid salt extraction process, previously developed by the Applicant Company, used for the treatment of these metals and salts in their form dissolved in water, by implementing new organic formulations incorporating a new series of anion-solvating organic molecules (MSAs), which are more efficient and open the door to the selective or non-selective extraction of salts previously considered to be non-extractable or insufficiently extractable because they are far too hydrophilic.

[0008] This is particularly relevant to enabling efficient extraction of salts whose anion is particularly hydrophilic, such as divalent anion salts, like sulfate (SO42), oxalate (C2O42 in waters with a pH close to or above pKa2 (HC2O47C2O42) = 4.3), chromate (CrO42 in neutral or basic media, pKa2 (HCrO47CrO42) = 6.4), hydrogen phosphate (HPO42 in basic media, pKa2 (H2PO47HPO42) = 7.2), sulfite (SO32 in basic media, pKa2 (HSO37SO32) = 7.2), carbonate (CO32 in basic media, pKa2 (HCO37CO32) = 10.3) or silicate (SiO32 ) in a very basic medium, of pKa2 (HSiO37SiO32 ) = 13.1) for example.

[0009] This gain in extraction performance resulting from more efficient anionic solvates also leads to a gain in performance for the extraction of less hydrophilic salts, with monoatomic or monovalent polyatomic anions, potentially present in aqueous media depending on the pH, such as iodide (I₂), bromide (Br₂), perchlorate (C₁₄O₄), hydrogen sulfate (HSO₄ in very acidic media, pKa₂(HSO₄⁷SO₄²⁻) = 1.9), hydrogen oxalate (HC₂O₄ in acidic media, pKa(HC₂CO₄⁷C₂O₄²⁻) = 4.3), chloride (Cl₂), chlorate (C₁₂O₃), permanganate (MnO₄), bromate (BrO₃), nitrate (NO₃⁻), iodate (IO₃⁻), and hydrogen sulfite salts. (HSO3 in acidic medium, with pKa (SO2aq / HSO3) = 1.8 and pKa2 (HSO37SO32) = 7.2), chlorites (C1O2), hydrogen phosphates (H2PO4 in acidic medium, with pKa (H3PO4 / H2PO4) = 2.1), fluoride (F), nitrite (NO2), formate (HCOO), cyanates (NCO3), thiocyanate (SCN), acetate (CH3COO),of hydrogen carbonates (HCO3 in slightly acidic or basic medium, with pKa2 (CO2aq / HCO3) = 6.4 and pKa2 (HCO3 7CO32) = 10.3), of cyanides (CN) in basic medium, with pKa2 (HCN / CN) = 9.25), , hydrogenosilicates (HSiO3 in basic medium, pKai (H2SiO3 / HSiO3 ) = 9.9), hexafluorophosphates (PF6 ) or trifluoromethylsulfonate (CF3SO3 ) for example.

[0010] The treatment of these numerous and diverse salts of divalent or monovalent anions can of course be carried out for their recovery, recycling or disposal in order to avoid or correct environmental pollution.

[0011] The present invention aims to increase the productivity of hydrophobic organic formulations for extracting hydrophilic salts from an aqueous phase, by improving the properties of the organic phase, to allow better transfer of electrically neutral salts from an aqueous phase to an organic phase.

[0012] To achieve this, the anion-solvating molecule (MSA), described in WO2016116687A1, is modified by the introduction of a second active hydrogen bond. Under certain conditions of molecular structure and NH bond activation, this modification increases the activity of the MSA, thereby promoting the transfer of anions from the aqueous phase to the organic phase through enhanced organic-phase solvation. These molecules are subsequently identified by the acronym MSA2H, for MSA with two hydrogen bond-donating atoms that enable anion solvation.

[0013] Thus, in applications aimed at extracting a cation, whether selective or not, via the extraction of its associated salt, this extraction is improved at each extraction stage. This makes it possible to reduce the number of theoretical extraction stages required to achieve a target extraction or recovery rate, or to increase the extraction yield with a constant number of extraction stages. This effect is all the more favorable when the concentration of the cation to be extracted is relatively low; that is, when the extraction equilibrium of an extraction stage is located in the lower half of the maximum salt concentration level in the organic phase.

[0014] The favorable evolution of the extraction equilibrium isotherms of LiCl between formulations incorporating MSA or MSA2H is exemplified initially through several examples for formulations of the same concentrations of active MEC (cation-extending molecule) and MSA in a diluent chosen to allow good salt extraction.

[0015] Next, the impact of the choice of the MSA / MSA2H anion solvator on extraction performance is presented for different lithium salts, depending on the complementary anion to lithium. This study is presented for the following salts in increasing order of anion hydrophilicity: LiPF6, LiC104, LiL, LiNO3, LiBr, LiCl, LiOAc, Li2SO4, Li2C2O4, Li2SiO3, and Li2CO3.

[0016] Next, it is shown for LiCl and Li2SO4 how the extraction performance of these salts is affected when an ECM with a higher complexation constant Log K(MeOH, 25°C) is used and how the relative MSA / ECM composition of the formulation impacts this extraction performance.

[0017] Also, the extraction isotherms at 20°C are compared for different formulations when it comes to extracting LiCl or Li2SO4.

[0018] Finally, all the MSAs presented are compared for the extraction of LiCl, for a formulation of 0.1 mol / L of MEC and 0.5 mol / L of MSA in the same diluent.

[0019] The present invention relates to a hydrophobic organic liquid composition, also commonly called an extraction solvent, for the extraction, from salt water or brine, of a monovalent or divalent anion salt, comprising a cation and an anion complementary to the cation, said composition comprising: A. at least one cation-extracting organic compound, exhibiting a Log K complexation constant for this cation in methanol at 25 °C of at least 1; B. at least one organic, diprotic, hydrophobic compound that acts as a solvator, complementary to the cation; and C. at least one hydrophobic polar organic diluent having a flash point above 60°C,

[0020] characterized by the fact that component(s) (B) is or are chosen from compounds of formula (I): HH (D II NN Ra Rb rc

[0021] in which: • Ra and Rc each independently represent one of the following: • a monovalent aromatic or heteroaromatic radical, possibly substituted; • a radical ac, °where X1 represents O or S and RAC represents an aromatic or heteroaromatic radical, or an alkyl or alkoxyl radical, linear or branched, or cycloalkyl or cycloalkyl-alkyl, these radicals possibly being substituted; and an alkyl radical, linear or branched, or cycloalkyl or cycloalkyl-alkyl, these radicals possibly being substituted; and Rb represents one of: a divalent aromatic or heteroaromatic radical, possibly substituted; a radical, where X2 represents O or S; X X an ethylene radical -CH2-CH2- ; and a radical where X3 represents O or S and Q represents a divalent aromatic or heteroaromatic radical, possibly substituted.

[0022] In the present invention, the following may be cited as substituents: linear or branched Ci-Cio alkyl, C4-C8 cycloalkyl, halogenated by -F, -Cl, -Br, -CF3, -OCH2CF3, -Si(=O)CH3, C-(=O)CF3, -NO2 in meta and / or para position on an aryl and / or in alpha and / or beta position on an alkyl.

[0023] The compounds of formula (I) are preferentially substituted by at least one halogen and / or at least one electron-withdrawing group in meta and / or para position on at least one aromatic or heteroaromatic radical and, even more preferably on each of the aromatic and / or heteroaromatic radicals constituting (I).

[0024] In the present invention, the following may be cited as electron-withdrawing substituents: -Br, -Cl, -F, -CF3, -OCF3, -SCF3, -CF2CH3, -CH2F, -CHF2, -CH2C1, -CHC12, -CC13, -CH2Br, -CHBr2, -CHFC1, -CHFBr, -CHBrCl, -CC1F2, -CC12F, C(=O)CF3, and -NO2, and other electron-withdrawing groups, in meta and / or para positions on the aromatic or heteroaromatic radical.

[0025] By monovalent anion salt, we mean a salt comprising a cation and at least one mono- or polyatomic anion carrying a negative charge, which alone, or combined with another monovalent anion, makes it possible to neutralize the positive charge(s) of the cation to obtain a salt of neutral charge.

[0026] By divalent anion salt, we mean a salt comprising a cation and at least one mono- or polyatomic anion bearing two negative charges, which alone, or combined with another anion, makes it possible to neutralize the positive charge(s) of the cation to obtain a salt of neutral charge.

[0027] By di-protic compound, we mean a compound capable of donating two H+ ions to its environment.

[0028] Alkyl or alkoxyl radicals are in particular CrCio radicals, cycloalkyl radicals are in particular C3-C8 cycloalkyl radicals, cycloalkyl-alkyls are in particular C3-C8 cycloalkyl radicals linked to a CrC8 alkyl chain.

[0029] Aromatic radicals are based on benzene, of the phenyl radical type, or derived from benzene derivatives such as toluenes, ethylbenzenes or xylenes.

[0030] The heteroaromatic radicals are of pyridinic base, of pyridinyl radical type, or derived from pyridinic derivatives such as picolines (methylpyridines), ethylpyridines, or lutidines (dimethylpyridines).

[0031] The compound or each compound of formula (I) may comprise from 12 to 40 carbon atoms, preferably from 14 to 30 carbon atoms, in particular from 15 to 25 carbon atoms.

[0032] In formula (I), at least one of RA, RB and Rc may represent an aromatic or heteroaromatic radical or containing such a radical, possibly substituted, at least one halogen and / or at least one electron-withdrawing group which may be part of the substituents.

[0033] The radical(s) constituting RA and Rc can be chosen independently from: Rp Ks y O jy— • C(=O)CmH2m+i with m < 10, where m is an integer, • C(=O)CmH2m with m < 10, where m is a non-zero integer, • C(=S)CmH2m+i with m < 10, where m is an integer, • C(=S)CmH2m_i with m < 10, where m is a non-zero integer, • CmH2m+i with m < 10, where m is a non-zero integer, • CmH2mA with m < 10, where m is a non-zero integer, • (CH2)mCpF2q+i with m < 6, where m is a non-zero integer, and where q < 4,

[0034] • (CH2)mCpHqFrClsBrt with m < 6, where m is a non-zero integer, and where p, q, r, s and t are integers of which at least r, s or t is non-zero, and the constituent radical RB can be a radical chosen from: C(=O), C(=S), -ch2ch2-,

[0035] where at least one of the radicals RD, RE and RF is chosen from among the following halogens or electron-withdrawing groups: • 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, • ocf3, • och2cf3, • scf3, • C(=O)CF3, • no2, • 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, • C(=O)CmH2m+i with m < 4, where m is an integer, and • S(=O)CmH2m+i with m < 4, where m is an integer,

[0036] The other radicals RD, RE, RF and the radicals RG may be chosen, identical or different, from among the following non-electro-withdrawing atoms or groups: • H, • ch3, • CH2CH3, c3h7, • CH2CH2CpF2p+i with p < 4, where p is an integer, • CmH2m_i with m < 10, where m is a non-zero integer, and • CmH2m+i with m < 10, where m is a non-zero integer; where only one of the radicals RDàRg can be one of these last two radicals CmH2mA or CmH2m+i, for m >4.

[0037] The alkyl radical entering into the definition of RA or Rc or RAC can represent one of the following: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, 2-methylbutyl, 2-ethylpropyl, n-hexyl, iso-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl.

[0038] The cycloalkyl radical entering into the definition of RA or Rc or RAC can represent one of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopentylmethyl or cyclohexylmethyl.

[0039] The compound of formula (I) may be chosen from:

[0040] triclocarban,

[0041] N,N'-bis(3-chlorophenyl)urea,

[0042] N-(3-bromophenyl)-N'-phenylurea,

[0043] N-(3-chlorophenyl)-N'-cyclohexylurea,

[0044] N-cyclohexyl-N'-[4-(trifluoromethoxy)-phenyl]urea,

[0045] N-(4-bromophenyl)-N'-cyclohexylurea,

[0046] N-(3-chlorophenyl)-N'-(cyclohexylmethyl)urea,

[0047] N,N'-bis(4-bromophenyl)urea,

[0048] 4-bromo-N 1,N2-diphenyl-1,2-benzenediamine,

[0049] 4-chloro-N 1-( 1 -methylethyl)-N2-phenyl-1,2-benzenediamine,

[0050] 4-fluoro-N2-(4-fluorophenyl)-Nl-(l-methylethyl)-l,2-benzenediamine,

[0051] 4,5-dichloro-N 1-(3-methylbutyl)-N2-phenyl-1,2-benzenediamine,

[0052] N,N'-(4,5-dichloro-1,2-phenylene)bis-propanamide,

[0053] N,N'-(4,5-dichloro-1,2-phenylene)bis-hexanamide,

[0054] the N,N'-(4-chloro-l,2-phenylene) bis[benzamide],

[0055] N-[2-(acetylamino)-4-chlorophenyl]benzamide,

[0056] N-[2-(acetylamino)-4-bromo-phenyl]benzamide,

[0057] the N,N'-(4,5-dichloro-1,2-phenylene)-bis[benzamide],

[0058] 5-bromo-N 1,N3-bis(4-butylphenyl)-1,3-benzenedicarboxamide,

[0059] 5-bromo-Nl,N3-bis[3-(trifluoromethyl)phenyl]-l,3-benzenedicarboxamide,

[0060] Nl,N3-bis(3,4-difluorophenyl)-l,3-benzenedicarboxamide,

[0061] 4-chloro-N2,N6-diphenyl-2,6-pyridinedicarboxamide,

[0062] N2-ethyl-N6-phenyl-4-(trifluoromethyl)-2,6-pyridinedicarboxamide,

[0063] N2,N6-diphenyl-4-(trifluoromethyl)-2,6-pyridinedicarboxamide,

[0064] N-(3-chlorophenyl)-N'-octylurea,

[0065] N-(3-chlorophenyl)-N'-(2-ethylhexyl)urea,

[0066] N-(3,4-dichlorophenyl)-N'-octylurea,

[0067] N-(3,4-dichlorophenyl)-N'-(2-ethylhexyl)urea,

[0068] N-(3,5-bis(trifluoromethyl)phenyl)-N'-(2-ethylhexyl)urea,

[0069] the N,N'-(4,5-dibromo-l,2-phenylene)-bis(hexanamide),

[0070] N,N'-(4-chloro-1,2-phenylene)bis-2-ethylhexylamide,

[0071] N,N'-(4,5-dichloro-1,2-phenylene)bis-2-ethylhexylamide and

[0072] N,N'-cthylcncbis|3.4-dichloro-bcnzamidc].

[0073] The expanded formulas of the above compounds are shown below (cis-cis form in particular). TncloCvUbssi, 101-23-2 yy-ïhsi'3-difes»pteiy^ 1.5208^31-6 s-..:y - ';.■•* 2W-97-Î 27-1 3 -Chferoplissyi) -N he 74 ' h-creev -X .x, X 'X- .- .•- X.' .-'•' ' "^ - S'Lv^îœ^l-', H 479413-39-3 i .,{ xr- ,?'X. .-^x S '• <-■•“' ■•p.: N-(4-Bs ora>?pbëiyy&54b?^ .NXS-CMsf^Ùeu^r y-'CVCjfôi' r* X * î ​​3W7O-T " O' & £ X .—i Ch GU / X 9 / -------0 / f 3-XX / 4-8110089-^Qe.^42-6-edù^ubeâmà1 2476151-16-3 ya « - E hi««- N1 - ( 1- méthy îéthÿSj-M2 -phéttyM. 2-bsr. zènediansn e, 40406-45-9 \TM„\ ■'ix--ÿ »r ,* \ ™ - phéaÓ&at >«•<• 9-^.--30-7 .f XX .. x / X. '^S-Didsif' x* <- œédsy&wMXN2^ tieazèàexùaîïiiae, 137'385. 5-8^2^-1 2- X >-î.krv'S i-Picj ' ._ fe; X4-Chk«®-1,2 -çéyléoe) bisPæsz^imde J, 1&614-84-1 ...N - [ 2 - ( Ac éîy 3 .ïsiiiïO ? -4 -ciüüïToplyéi^^^ 2225S46-39-2 / 3.....X: 7.-.-.-.-.-. / N-' ' < 4^ <n LHairssM-bronH.- L- ypjesizaaiïdé, 2417674-84-9 X, ,<‘. X^..'X > ■ \ .-■ X. / X. N,y - (4.5-Director'-L2-part 855263-86-4 . J-'-'ïX ,.,Q" "i, 5-Bromo mX?-te<4-t'kUyiphéisvD-l 3-brtizêsedk •îSbt'X.BBlde. 2801706-96-5 Si ' ■ XV .>;■ ■ ■ S Lit 'AAAX '"J OriSuoromethyt) phényq-L3- 444 W 03-7 Ni - ■330408-29-2-N2,S-N2,ë6-Chlol KH935-92-6 ' ss: W ' ' <•' X'v yy -- 35 LL'-rthYLTLi-pWJ-A- ttnfhKas-risfrvi'-Z 6-vx.ijnlr 5- <<-a '•■■' : ss: : - --. ■ N2,N.5-Dipfaéayï-4-(fci&»K>-^ pjraOœe&cæ&ejtasB&fe, 1.053344-79-0 505'005-80-5 s : éLhyth^ylXsœe,. 221 £llhexy S>4-7yl-48 22164-72-3 N-{3.S-BistTf siltswœéïhyl)-- -éiàyl hexytHirèe, 22263-35-4 ' >1 'fx N3^-{4,5-13&w»sa-l,2.-£4xi)^bis^3yiehae. 32Û78S5-S XX Sas»-5,2 - eîàvll.e^vlsi'.eîe C;?H?;CÎN:O n (AS.Iæa®BB ^V-.'4.Ÿ-&.<hiOTû-L2-phea vkae)bs bî 2 -ethy ihexy l.i r_- •■ • 3e > asCAS : <? «•'-■" Nv ss<: ■•■£ $X^yi^t^3,4-dtdiiç<o-: Benzassidel, 2.8293-33-1

[0074] In one embodiment, the cation extractant(s) may be chosen from compounds of formula (II):

[0075] 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 C3-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, C3-C8 cycloalkyl, C2-C6 alkoxyalkyl and alkoxyalkylaryl; • R4 is chosen from hydrogen, alkyl in linear or branched CrC3; • R5 is chosen from hydrogen, alkyl in linear or branched CrC3; and • R6 is chosen from hydrogen, alkyl in linear or branched Ci-C3.

[0076] In a particular embodiment: • RI and R2 are, 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, iso-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, 2-ethylhexyl, phenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl; or • RI and R2, taken together with the nitrogen atom that bears them, 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,

[0077] 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 Li7Ca2+ selectivity is preferred; and

[0078] RI and R2 being advantageously chosen from iso-propyl, iso-butyl, sec-butyl, tert-butyl, iso-pentyl, 2-methylbutyl, 2-ethylpropyl, cyclopropyl, 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 the Li7Na+ selectivity is preferred.

[0079] In a particular embodiment, the cation extradant(s) may be chosen from the following compounds: / \ \ / X ? / X / X-,-—V 0 Àwl'î O} Q ^--V ~>O Y7 O l À À æ ( ) >;.=: ---,. X'X Ij «J °'"' Z\ ■ . j \.... / "v CTO '■-;x.--J' —X -..Z MEC-3 MEC-1.3 MEC-3.2 0 ClX-X^ Ôv (XO (J t UX^Xx - *| ) ' U f 0J ~J - z ~ ô “O XJ _ C ) MEC-1.3 MEC-1.4 MEC-1. S ÛyO yrs, --” ^"'XXP Z > V. o . ,aJÿV, W SX / \ / ZX / XX v / ^\_ A ( ) >■■■<. ; C) iz X .=- .■ V (1 LXV~|^^ JX x MEC-1,6 MEC-1.7 MEC-Î.S 1^. Z~X 0^-5 “ l M "X ztzr^' C / ?XwA yz X. / \ / < \ / >---z. * X<\Z X.-X.-X. ZA.... / Y.. < 0 Z“or QI . 1 ? z- X<j \^J MEC-l.S MEC-1.10 MEC-1,11 '■;.™v > Y....... ï i Y ' / "■■-- MEC-1.12 MEC-1.13 MEC-Ï.14 „.- . S ■ i MEC-1.15 MEC-lvi6 MEC-1,17 ;.- Y’ Y *‘ S - - ■ y ( S ■ .-■ MEC-1,18 MEC-1,19 MEC-1.20 4 ' ( " ‘ y- / y <hs / M C. .3, L X, x"X —} J :•; / >„« Y Y-•-' y Z ' X MEC-1.21 MEC-1.22 MEC-1,23 CH3 / O O™-’ )■ G“-'"X CkH;? >_ / / V7' ' / ‘ \ # \ N~a5R;; 0 «—z ’-v—*■ M < M ' MEC-1,24 MEC-Ï.25 MEC-1.2S ..---------. y.---'----. ■\ Y"- ; \ Z-"-’, ..y—:'. MEC-1,27 MEC-1.2S MEC-1.Z9 x.....O / .....> O,^J-ry 0 A vy A f.....yr' V MEC-1.30 MEC-131 MEC-1.32 X xy .yXjZ'Y'X / X^ .«X. -A- X---x' MEC-1.39 MEC-1.40 MEC-1.41 MEC-1.42

[0080]

[0081] In one embodiment, the cation extractant(s) may be a substituted calixarene comprising from 32 to 80 carbon atoms, in particular from 50 to 70 carbon atoms. In one embodiment, the cation extractant(s) may be chosen from compounds of formula (III) or formula (IV):

[0082] where • n is an integer ranging from 4 to 8, • p is 1 or 2, • m is 3 or 4, • q and t, whether identical or different, are 0, 1, or 2, • R is a tert-butyl, tert-pentyl, tert-octyl, O-methyl, O-ethyl, O-propyl, O-isopropyl, O-butyl, O-isobutyl, O-pentyl, O-hexyl, O-heptyl, O-octyl, OCH2-phenyl group or a hydrogen atom, • R' and R', identical or different, are chosen from the group consisting of the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secbutyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl groups or R' and R'' together form a pyrrolidine, piperidine or morpholine ring.

[0083] In a particular embodiment of the compounds of formula (III), p=l and R, R', R” and n are defined below: BR* n HP 5 mip ai p -HUM mt : V ( S'*-. HP "S CQ 1 PP oi P Ethyl PI rt (¾ M tert-Butyl dùX.nyis Ethyl 4- tr : Ethyl Ethyl 6 .. . H - Ehe eyle Ethyl 6 C'1; ai et (b Ethyl O-methyl il y. ■. Ethyl C; î't (b H et 1 Ül et l-' fl! Ethyl PQ 1 O et 1-4 (PE thi vâ Ethyl POO ai i P-(br< rt Æ 1) MH (P .-1 PM Ethyl $ O ï Æ-rf H Cl! Ethyl S

[0084] In particular, the cation extractant(s) from among the compounds of formula (III) may be chosen from 4-tert-butyl-calix[4]arene tetrakis(N,N-diethylacetamide) and 4-tert-butyl-calix[6]arene hexakis(N,N-diethylacetamide).

[0085] In one embodiment, the fact that the cation extractant(s) can be chosen from compounds of formula (V) or formula (VI): (V) (VI)

[0086] where: - n is 4, 5 or 6; - p is 1 or 2; - m is 2 or 3; - q and t, whether identical or different, are 0, 1 or 2 - R is a tert-butyl, tert-pentyl, tert-octyl group or a hydrogen atom; - R' is chosen from the group consisting of the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secbutyl, pentyl, hexyl, heptyl and octyl groups for the realization of a ketone-type bonding group, or from the group consisting of the O-methyl, O-ethyl, O-propyl, O-isopropyl, O-butyl, O-isobutyl, O-pentyl, O-hexyl, O-heptyl, O-octyl, OCH2-Phenyl groups for the realization of an ester-type bonding group.

[0087] In a particular embodiment of the compounds of formula (V), p=l and R, R' and n are defined below: RT ^”4 H 0 ï HP" p ID H rd Û H ¢0 H | OH 0 ï dd H d' y and Mi p-* d 4 te r t-but y le «h HP >1' 1 O 4 rt d H ■"i 1 gd' h) QT H-Ù) 0 AC) (U 4 tert -butv le 4) HP bi P kl p I 0 4 tert-octyl Q — è th H >1 P r P (UPH ..C pi 0: 5 rt ÏD H rt J, and (Î! te zt,-butyl 4 ■1) HP q 'ipp ru p O-ebhyle 6 p T ki 05 P ethyl 4) pp 1 P kl (U pa?' d;

[0088] In particular, the cation extractant(s) from among the compounds of formula (V) may be chosen from the tetraethyl ester of 4-tert-butylcalix[4]-arene-0,0',O”,O'”-tetraacetic acid and the pentaethyl ester of 4-tert-butylcalix[5]-arene-O,O' ,0” ,0” '-pentaacetic acid.

[0089] In one embodiment, the cation extractant(s) may be selected from a crown ether, in particular a crown ether having 14 to 80 carbon atoms, especially selected from the group consisting of decahydro-6-tetradecyl-12a,16a-Butano-2H,9H-1,5,8,12-benzotetraoxacyclotetradecin (nC14-Decalino-14-crown-4-ether, CAS No. 151460-03-6), decahydro-6-tetradecyl-12a,16a-Propano-2H,9H-1,5,8,12-benzotetraoxacyclotetradecin (nC14-CyclopetanoCyclohexyl-14- crown-4-ether, Cas n° 151460-02-5), 2,3,5,6,8,9,1 l,12-Octahydro-14-pentadecyl-1,4,7,10,13-benzopentaoxacyclopentadecin (3'-pentadecylbenzo-15-cro wn-5-ether, 88037-72-3), tetradecahydro-7-tetradecyl- 4a,20a: 1 la,15a-Dibutano-17H-dibenzo[b,k] [l,4,7,10,13]-pentaoxacyclohexadecin (tetradecyl-didecalino-16-crown-5-ether, Cas n° 172883-31-7), 2,2,3,3,11,11,12,12-Octamethyl-6-tetradecyl-l,4,7,10,13-pentaoxacyclohexadecane (octamethyl-nC14-16-crown-5-ether, Cas n° 172883-30-6), Eicosahydrodibenzo [b,k] [ 1,4,7,10,13,16]hexaoxacyclooctadecin (Dicyclohexano-18-crown-6-ether, Cas n° 16069-36-6), octadecahydro- 4a,24a:8a,12a:16a,20a-Tributanotribenzo [b,h,n][l,4,7,10,13,16]hexaoxacyclooctadecin (Tridecalino-18-crown-6-ether, Cas n° 104049-01-6), octadecahydro-4a,25a:8a,12a:16a,20a-Tributano-22H-tribenzo[b,h,n] [ 1,4,7,10,13,16]hexaoxacyclononadecin (Tridecalino-21 -crown-6-ether, Cas n° 259874-18-5) ;and a cryptand selected from 5,6,14,15-dicyclohexano-4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane, 5,6,14,15-dibenzo-4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane and 5-decyl-4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane. ;

[0090] The use of some of these extractants makes it possible, within the framework of the invention, to selectively extract lithium, sodium, potassium or ammonium salts or to extract other cation salts that may be suitable for these extractants.

[0091] The present invention can use diluents that are very unusual compared to the state of the art of conventional liquid-liquid ion-exchange extraction, which uses complex mixtures derived from petroleum distillation, based on aromatic and / or parafinic hydrocarbons with long C10 to C20 chains. Furthermore, operational safety has been prioritized by using an upper aqueous phase for this process with hot water solvent regeneration.

[0092] Similarly, operational safety can be prioritized by using a superior aqueous phase for a hot water solvent regeneration process. Thus, the diluent can be chosen to be polar, hydrophobic, and have a density greater than 1.05 kg / L and preferably greater than 1.25 kg / L, a flash point greater than 60°C and preferably greater than 93°C, be chemically and thermally stable (extended pH range from 2 to 12, and up to 120-150°C), and be suitable for safe implementation, both for operators and for the environment (aquatic, flora and fauna).

[0093] The hydrophobic polar organic diluent(s) may be selected from bromochlorobenzenes, bromochlorotoluene, bromochlorooxylenes, bromochloroethylbenzenes, bromochloropropylbenzenes, bromochloroisopropylbenzenes, bromochlorobutylbenzenes, bromoethoxybenzenes, dibromobenzenes, dibromotoluenes, their derivatives and mixtures, and in particular from 2-bromo- l-chloro-3-ethylbenzene, l-bromo-2-chloro-3-isopropylbenzene, 2-bromo-l-chloro-3-isopropylbenzene, 2-bromo-4-chloro-l-isopropylbenzene, 2,3-dichloro-1,4-dimethylbenzene, 2-bromo-l-chloro-4-ethoxybenzene, 2-bromo-4-(2-methylpropyl)-l-(trifluoromethyl)benzene, l-bromo-3-ethylbenzene, 1-bromo-3,5-dimethylbenzene, 3,4-dichlorotoluene, l-ethyl-2-nitrobenzene and 1-bromo-2-chlorobenzene.

[0094] Hydrophobic polar organic diluents according to the invention are listed below by way of non-limiting examples: » * case Sxii>s t-11 Where did you go? '2- brcsi'Æ-±— r- o - 3- & thy.1 - — 21,. — rSXyC Cf Br X / 2 4 . is C-.HtS hC 4 213. .3 c.: ? these. 2 ?'zs\ xx 3 X. 3 31 3 22 2—313-4 \ XXX 1 “ S Ci"O'- 2 _ 2?;.;: " C ~ . — f / / Br Ci ij: * 3 £ sos-ropylberiz L.5:'-^ÏOW1 yC 2 " 2 " r5 5 i çAvC.2 s i. In Br \ 2 h I ; 2 33, 33 4: .ÿ S\ Ü-2- X- _. ■ ' : - î - s 4 - 2. \ \ x \ C — SX OIT', O— 4— -'L-fï > C'X 'L “ i — te. GJ Ùj C; '1! ■”-1 -jI C 2.1 23! Ci CÎ i ;- C' 4 hv 3 Cf hs is ready to return. C 1--- o ■ n Vf, »-r- i ■y / & l'd û ' ,J> W [•' • h H '2 -5 N 2. >r 0 1 3 tï' i œ.' ri k œ Kl 1 1 fr.- Û #•, - UZ. 1---- >.n " 1.--.-( ap? '.0 c 2 - 4 - 3 2 23 - 1- tt r £f 2^ -CH2CH :2H 3 ; 2 Z'XC. x , e -e 2- <1 Sïï-3 / L vy -2-,-. ne s: 7 £ C — 4 .

[0095] The following diluents may also be considered: l-bromo-3-ethylbenzene (CAS No. 2725-82-8; Tgel = -20.5°C; 1.349 kg / L; Bucket = 20 mg / L; Tflash = 71 ± 9.3°C), l-bromo-3,5-dimethylbenzene (CAS No. 556-96-7; Tgel = -20.5°C; 1.362 kg / L; Bucket = 19 mg / L; Tflash = 87°C), 3,4-dichlorotoluene (CAS No. 95-75-0; Tgel = -15.2°C; 1.256 kg / L; Bucket = 26 mg / L; Tflash = 85.6°C), l-ethyl-2-nitrobenzene (CAS No. 612-22-6; Tfreeze = -12.3°C; 1.123 kg / L; Bucket = 200 mg / L; Tclair = 86.9+ / -11.5°C), or l-bromo-2-chlorobenzene (Case no. 694-80-4; Tclair = -12.3°C; 1.644 kg / L; Bucket = 23 mg / L; Tclair = 91°C)

[0096] The cation of the salt to be extracted can be chosen from the cations of alkali metals, alkaline earth metals, transition metals, lanthanides or actinides such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, manganese, cobalt, copper, zinc, silver, cadmium, indium, gold, lanthanum, cerium, neodymium, europium, gadolinium, thorium and water-soluble metal salts.

[0097] The anion can be chosen from oxalate, sulfate, silicate, carbonate, fluoride, chloride, nitrate, bromide, chlorate, perchlorate, iodide, bromate, cyanide, chlorite, iodate, hydrogen carbonate, hydrogen sulfate, hydrogen sulfite, hydrogen silicate, cyanate and hexafluorophosphate.

[0098] At least one component (A) (MEC cation extracting molecule) may be present in the composition at a concentration of 0.10 to 1 mol / L, preferably 0.3 to 1 mol / L, more preferably 0.45 to 1 mol / L.

[0099] The ratio of the molar concentration of at least one component (B) (MSA anion solvating molecule) to the molar concentration of at least one component (A) can be from 1 to 15, preferably from 1.5 to 5 and more preferably from 2 to 4.

[0100] The present invention also relates to a use of the hydrophobic organic liquid composition as defined above in a process for extracting monovalent or divalent anion salt, said process comprising a step of mixing, at a first temperature, the hydrophobic organic liquid composition and the brine to be treated, a step of separating the hydrophobic organic liquid composition loaded with monovalent or divalent anion salt and the treated brine, and a step of regenerating the hydrophobic organic liquid composition by treating the hydrophobic organic liquid composition loaded with monovalent or divalent anion 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.

[0101] Regeneration of the solvent with water at room temperature can also be carried out but the water consumption can then be multiplied by four.

[0102] For example, about forty compounds meeting the above definition of MSA2H anion-solvating molecules with two hydrogen bond-donating hydrogens, incorporating at least two halogens and / or electron-withdrawing groups, are presented in the table below:

[0103] The development of anion-solvating molecules (ASMs) according to the present invention, based on aromatics with urea, thiourea, dual amide, dual thioamide, dual amine, or a mixture of these functional groups, for example, makes it possible to double the number of hydrogen atoms capable of forming strong hydrogen bonds between the organic anion-solvating molecule and the anion to be solvated. This solvation capacity is further increased when the NH₄⁺ bond is activated by the nearby presence of an aryl group preferentially substituted in the meta and / or para positions by a halogen and / or an electron-withdrawing group. Thus, by increasing the anion's solvation capacity in the organic phase, the free energy transfer of the salt from the aqueous phase to the organic phase can be reduced, thereby promoting the transfer of the salt to the organic phase.

[0104] The gain in extraction performance of the targeted salt can be quantified via the use of this new family of anionic solvatants by constructing an extraction (or absorption) isotherm at room temperature, to be compared with the use of anion solvating molecules (called anionic solvating molecules - MSA) of the previous families described in WO2016116687A1.

[0105] This absorption isotherm represents the partition equilibrium of a salt between the organic and aqueous phases. If, for example, the extraction equilibrium of lithium chloride, LiCl, between the organic and aqueous phases is to be studied, this can simply be modeled by a Langmuir isotherm, which is modeled by:

[0106] or by r -,+ -, _ [£ / 1^ lorg-

[0107] The second equation on the right, although less precise in fitting the experimental data, allows the absorption isotherm to be characterized by a single non-zero parameter b, .[Ext]org being known by design of the organic formulation.

[0108] Through this equation, it appears that the partitioning of lithium towards the organic phase is higher the higher the product KHeniyb, or the higher the b2.[Ext]org constant, with, by equivalence KHem^b-tEx / ]^, and where: • Kueniy is Henry's constant, or the slope of the isotherm at the origin; • b is the curvature of the isotherm (if b=0, the Langmuir is a straight line of slope K-Henry), and • [Ext}ors is the concentration of cationic extractant EC (CEc) in the organic phase, corresponding to the maximum concentration of lithium in the organic phase for a 1:1 (Host:Guest) type complexation.

[0109] Since this lithium is extracted in the form of LiCl, for example, these equations (1) are absolutely equivalent to equations (2) below when it comes to evaluating the expected extraction performance of a liquid organic salt extraction formulation.

[0110] , or by [LtCl] = blEx^LiC^ (2) (WiCiy (WiQW [YES] Thus, tracking the parameters KHenry, b, and the products KHeniy-b, or [Ext]org allows to quantify and compare the performance of the different organic formulations tested through the quantification of their isotherms or the relative measurement of the salt absorbed (then desorbed) from the same initial conditions (relative compositions of the salt water and the formulation).

[0112] The two-hydrogen-bonded anion solvating molecules (MSA2H) according to the present invention make it possible to increase the products KHeniyb, or [Ext}org of a factor of the order of 10 and potentially more compared to the previous state of the art.

[0113] The following examples illustrate the present invention without, however, limiting its scope.

[0114] In these Examples, the following abbreviations have been used: • MSA-1 to -8: known anion-solvating molecule • MSA2H-1 to -8: anion-solvating molecule with two hydrogen bonds according to the present invention • MEC: cation-extracting molecule • Mm: molar mass • TA: ambient temperature • TF: melting point, or freezing point • Po / w: oil / water partition coefficient • Wedge: calculated • S: solubility in water • 2CBB: 2-bromochlorobenzene (C6H4BrCl, CAS 694-80-4; 191.45 g / mol; liquid with a density of 1.656 g / cm3 at 20°C) • OAc: acetate ion • DCM: Dichloromethane • TEA: triethylamine • A / O: aqueous to organic volume ratio

[0115] Example la: Description of the MSA and MSA2H used Indicator SAME>>u <Lîhne, »'■< AS. Mm, TF. Leg r»^. s Naœ&t formules tn aies H dêveîappées MSA-I tiC sHî -XHC\=<) fbÇtHï, 42SS6255.44 sdsfote TF = 164*1' Los ?<,„ = <5^fc 8 = 56 IC” mole L = 14 3 mg-lb''*' N-Octyiocmaimâe, V .••'•"y.. .•-'-‘V. .•■•"••., .■-•"'•y .•''■'■-X •? •• ■• '•j?'' '?' -s' M.SA-2 Ph-NHL^3) -A-H, éQ^S 10-? , 21^ 32 mate 1 r = C I <\o P. = 43^ S = 2 ? B mole L = 4ô J. ’ 34-Phéayl O octosamsde, Cj-^jNO ,.x M8A-3 3MeOPlpNHC(=O}-nC7Hî; 34^^5-96-8 ; 249.35 g / mole Lapide Log P^ = 4.59 S = 1 2 104 mcWL = 29,9 mgÆ2î%" NX3-Mét <x hoæ^6nyl)'oc&»mù^ -x .ex-. MSA-4 3€ lPh-NH€'(=O î-aC-H s « 34S594-S2-5. 253.77 g / mote Lxiaide, Log Pc^ = 516 < •Xs'Xs'^ S = 3,2.10 ’ tuole’L = 8,12 rag / LX y 43 -Chtersphs sr\4)<K.î3sœtefe, C ■ ^sjClNG x 1b ■•■-._ -■•- Ù ~ MSA-5 34ClPWH34Cmi 1207319-21-S . 507 g / male Liquide, L©g P^ = 6.4 S = 4.3.10'' md«Æ = 0.13 mg / L25'" 3.4-didlh Beazêüss wra-N-{3.4-Æcteorepitesiyl)-wac C^&CUN MSA-« 3 "XlPh-NTTCMT.^OHs 20398-46-3 2SS.21 ÿmste TF = 59.5 "C. Lvg P^ = OS = :<.a 10'4 mok'L = 1.44 mg^L^ NU D&hL>i<^4teiiylj«£fcwK^ ni - xx li 1 ! - ' i MSA-7 34CÎPh ?7HCZ=O1 nC^« 730-2'-e 23S 21 surate TF = 4i T, Log 7^= 5.9^ S = 5.4.10^ mcWL = 1.56 îag / L2''*" Nt 3 4-Ds£lü^4&é»ÿl)Q^^ £ ^H;«CÎ;Xy' > . x "K ; Jl J l........ MSA-S 35 TFMPls-XHCt =0^-^½¾ ; 197431£-14-5. 353 32 g uiole TF = 4?*C Log Po^= ë 43 S = 2.9 1Q'5 n»k*L = 1.03 mg.^^ N -[3.5 Bis(td3sw>Btethyl)phe^^^ . ïadkaïif SA Nomeuciaisre, a < Ax Ma, TF» Tcg P&». S numbers, many brutes and teeth MSA2H-1 3CiPh-ÿJHC(=Q)NH-ûQ^ 501003-80-1 , 282.81 g / mok TF = 71-V Log P»* = 5.54ÏS&: S = 2.4 If* mète-L = 0.68 mg / L"5^ 5?-(3-£hforoplk&yl)-^^ CssH^CSN-L* vW— M 1 MSA2H-2 3C»T*HC(=D)N&^ 22164-77-8 ; 282..SI g.Wte TF = 51¾ Log P^ = 5.38 e* S = 2.7.10'* = 0,76 .N-Ç3-Chlo£»plsêayl)-7r-f2-éll3ylhex^ CjÆjCW? H >!} < \ U-:-- . <1 MSA2H-3 34CSPh-NHC(=O}NH^^^ 5089-84-9 ; 317,25 TF = 102®C LcgP^-638^ S = 3.3. KC mok / L = 0,11 mg^L25^ Fl U .4 ^¢^¢¢^110171)-145-0645(^1066-, r^H^CTNTl ..--¼. .--''X ..-^¼ .>■■• IJ 1 • ....... MSA2H-4 34Cl?h XH»"t=OÏNH-2EmiKK 22164-7<3 31 ? 25 g.W4e TF = ^,5®C, Log ^.= 6,43* ■S--3-J.10'7ii»ie^ 6,12 N-( 3,4-D^ysrapfeiyl)-^^ ¢-..<■ • •.:: •■ ''>v^. Ç1^Î22C^)O -¼ MSA2H-5 UC F;Ph-N HC v=O j2?H-2Effisx 22263-35-4.38436 g Wk Los P, w -6 06 S = 2,6 10' mole L - C 10 mg / L2^' N -(S ,5-BisCTrüIiwee*8niêthyl)phéïsy 1)-N* 42 - hexyljîixée. already ,.---,, 3 ^.C. .,.2, ...... C -HoF^.Ô 1 1 ' MSA2H-6 2EiHex-C(=O)W-MNHCn^ 2EtHsx CAS-5487S7-20-8; 360.54 g / mc4e TF = 63.5'C. Log P^= 5.77 e* S = 3.3:10'* mok / L =1.19 mg.C2:x N,NM.2-Phêsylèaebis(2-étk5!$h«s^^ ■\ V / / "'"'VJ Crfî-js^Ch' / V...... \ M< 2ErHex-a=O)^-3ClPli- NHC(=G)- 2EtHex CAS meoan»' 394.98 gniole TF = 9G°C, Lcg P^ = 7.07 e* S = 2.2.10'* tnoWL = * / L'35^ s. l-glié«yl«se)bis-2-tS'A ^ewlï, i , * - \ / \ j. y-—“ 2? 5 YES . J 'À >y In . SA N&SSeiU'ïidSïe, O^CAS^ Mia, TF, Log S Names. fcï mities braies and dé¥^»ppées MSA2H-8 NHCf=O)- lEHiex CAS taximi 429 43 2 mole TF=i2 <v Log A S= 1,2.104 -jæledL = 0,S5 mg / L”'

[0116] The aliphatic chain amines considered for the construction of these MSA2H are preferentially chosen from among the amines providing sufficient hydrophobic character to the target molecule while having a very low solidification / melting temperature (TF). This is generally possible by choosing branched aliphatic chains, such as, in particular, 2-ethylhexylamine (C8H9N, CAS: 104-75-6, FT = -76°C), 2,4,4-trimethyl-2-pentanamine (C8H9N, FT = -66.9°C, 107-45-9), 6-methyl-2-heptanamine (C8H[9N, 543-82-8), isooctylamine (C8H[9N, 1321-35-3, 44855-53-0), 2,5-dimethyl-1-hexylamine (C8H9N, 74038-59-8), isoheptylamine (C7H17N, 4746-31-0), and 2,4-dimethyl-1-pentanamine. (C7H17N, 146845-08-2), 2-amino-2,3-dimethylbutane (C6Hi5N, 4358-75-2, TF = -70.5°C), isohexylamine (C6Hi5 N, 5344-20-7, TF = -94.4°C), or 2-methyl-l-pentanamine (C6Hi5N, 13364-16-4, TF = -40.7°C).

[0117] All of these amines have low melting points compared to octylamine (C8H[9N, 111-86-4, TF = 0°C), heptylamine (C7H17N, 111-68-2, TF = -23°C), or hexylamine (C6Hi5N, 111-26-2, TF = -21.3°C), which correspond to linear-chain molecules, and are therefore unbranched as previously described. These low TF values ​​also allow for a reduction in the TF of the synthesized ureas, thioureas, amides, thioamides, or amines, while simultaneously improving their corresponding solubility range for the hydrophobic aromatic polar diluents considered.

[0118] Fig. 18 presents a 3D image showing the positioning of the chloride anion when it is solvated by MSA2H-8. Example 1b: Description of the MECs used

[0119] Xom d"essai Nenseadatare, Mm, TF, Log Po?w» & ForisHfe brute et développée MEC-ï Lïthiæm losophoie 4.4',4' '-proçyüdyaeirisfS -ok â butyrantids) Î3333S-S5-9 ; 793,19 EF=PWC = Log. Î&.64, S = 1.7 W* mofe / L = 1.36 mgÆsx\ or o.HAvP n^Ô X^""z Q-sSsjN;^ MEC-2 DibeïïEO-lS- Dibsazo[b kj-i A7,10,13,10-he'KaosuKV-12-37-kvta ; 76<*4 g TF = 16v;CL <sg = 2 20 tExf; S = 2,03 ItC mute L = 7 * ms T :"‘Y .«v.. .ô- à. CV ;Ç ■ E > < .-y'-' MEC-3 Najdï&s-îS-dOWSl-Ô 2.3,5.6 8,9,11,1214,15- Deca&y&x>83ph&Q[23 -b] [ 1.4,7,10.13. laj&exaoxacycfo&ctadecine 17454-52-3 ; 362.42 glnole, EF = H TC, Los P^. = 2.12, S = 2.21. ir' moleZL = 80 aga?5"®. MEC-4 Calsx[4]ar«ie te&seBlerB teEaacedc Acid Tetrsethyl Estes, Sodiœa joaopb&ï^ 97600-39-6 ; 993.27 gôaaie, TF= 154.5, 154,000 Lo Wn mokX = 0.02 ng / L^ cl ï.■ T. .■' MEC-d teteaasudes-diEihyl. 4-tert-»uty!-€ëM4]srene te»r $kis(^,N-diethytacetam 1 of}# 114155-1&-7; 1101.55 gusctfe. :u=2'2 E Las =“ S < 3.5.1Ô': srsefe / L = 0.39 mgÆ / 5 -. MEC-7 Cstlæ(6]areæ bexaamides- 4 -im-b&tyl- C alix] S];a:ene texafcss(N 14 -dièthydaœtaiïMde), !ir\eo-> i"'^de L©gP^.= 24, w >f ■'si ''C 'rj .

[0120] By way of example, multiple Log(K) complexation constants in methanol at 25°C, for these ECM families in the context of 1:1 type interactions, are presented below: Log KtM*T Lf nV K" Ri? c? M"" Ba3* À*" TF NH? L'-joriicf-0 L: VBIiMEC-L y 7 0.9 KXX 4.9 IS-tJcnsn-:? (3314l>-27-5« i,2.4 ' ' ■? - 4; 2.76 2.54 ■J 2.63 — ' 3.62 3.31 ,3,G3':' iô-C îo^ts-? (554" 1-28-8« 4.10 2.92 2.46 2.09 / 1S-C (17433-H-:?! t 36 6.09 SJ 5 4.ô4 ï'2 6.84; 1 • 4 59 7 77 4„2Ç DC 13-3 4.27 5.97 4.88 4.25 3.54 / 4.41 5.83 4 30 3.55 2 95 3.2'7 443 4.04 3.91 NPI B-Crewa-d s MEC -S? 3 19 4.03 4.62 4.07 / esta 'MEC-4) 57 2.4 3 J 2 7 < t < 1 ■2' &:■ 4.0' 1.6 C ahx[5]arene esîet SMEC -5) 1.0 4.4 5.3 57 5.5 2 1 < 1 * 4.0 Caüx[4]areae amidated-djEthyi (MEC-6) •4..0 7.9 5.8 3.8 2.45: 9 >9 7 7 T -TC Ci?" 6.5 Qîlix[6]æreiie ssusde-djEthyf (MEC-7) 2.6 2.8 3 3 2.6' 2'.8 8.2$ 8JS 8.3*

[0121] “IUPAC reference, *Estimate, xToo small to be measurable, / not evaluated, See publications of F. Arnaud-Neu Example 2: Synthesis of MSA2H-1

[0122] The compound MSA2H-1 was synthesized as follows:

[0123] In a 250 mL flask under argon, 11.9 mL of 3-chlorophenyl isocyanate (15.0 g, 97.7 mmol, 1.2 eq. CAS: 2909-38-8) and 30 mL of dichloromethane were added. 13.5 mL of octylamine (10.5 g, 81.4 mmol, 1.0 eq.) were added dropwise, ensuring the reaction mixture did not exceed 25°C. Stirring was maintained at room temperature for 18 h. The mixture was concentrated under vacuum, then filtered and washed with 10 mL of cold dichloromethane. The filtrate was then concentrated, filtered, and washed with 10 mL of cold dichloromethane. The solids were combined and dried under vacuum for 24 h.

[0124] The compound of the title was obtained in the form of a white solid with a yield of 75% (17.2 g).

[0125] TF:71°C.

[0126] 'H NMR (CDC13): 0.86 (t, 3H), 1.23 (si, 10H), 1.84 (t, 2H), 3.18 (m, 2H), 5.47 (s, 1H), 6.96 (s, 1H), 7.06 (s, 1H) 7.14 (m, 2H), 7.34 (s, 2H). Example 3: Synthesis of MSA2H-2

[0127] The compound MSA2H-2 was synthesized as follows:

[0128] In a 50 mL flask under argon, 7.0 mL of 3-chlorophenyl isocyanate (8.82 g, 56.3 mmol, 1.0 eq. CAS: 2909-38-8) and 11 mL of dichloromethane were added. 9.22 mL of 2-ethylhexylamine (7.27 g, 56.3 mmol, 1.0 eq.) were added dropwise, ensuring the reaction mixture did not exceed 25°C. Stirring was maintained at room temperature for 18 h. The mixture was concentrated under vacuum. 10 mL of acetonitrile was added, and the mixture was then filtered and washed with 10 mL of cold acetonitrile. The filtrate was then concentrated, filtered, and washed with 10 mL of cold dichloromethane. The solids were combined and dried under vacuum for 24 h. The product was then purified by silica gel chromatography (petroleum ether / ethyl acetate 85 / 15).

[0129] The compound of the title was obtained in the form of an off-white solid with a yield of 54% (8.53 g). TF: 51°C.

[0130] 'H NMR (CDC13): 0.75 - 0.90 (m, 6H), 1.13 - 1.33 (m, 8H), 1.37 (d, J = 5.7 Hz, 1H), 3.14 (dd, J = 6.0, 3.3 Hz, 2H), 5.71 (s, 1H), 6.87-7.04 (m, 1H), 7.06-7.20 (m, 2H), 7.35 (s, 1H), 7.71 (s, 1H). Example 4: Synthesis of MSA2H-3

[0131] The compound MSA2H-3 was synthesized as follows:

[0132] In a 100 mL flask under argon, 10.0 g of 3,4-dichlorophenyl isocyanate (53.2 mmol, 1.1 eq. CAS: 102-36-3) and 35 mL of dichloromethane were added. 8.0 mL of octylamine (6.2 g, 48.4 mmol, 1.0 eq.) were added dropwise, ensuring the reaction mixture did not exceed 25°C. Stirring was maintained at room temperature for 18 h. The mixture was concentrated under vacuum, then filtered and washed with 10 mL of cold dichloromethane. The filtrate was then concentrated, filtered, and washed with 10 mL of cold dichloromethane. The solids were combined and dried under vacuum for 24 h.

[0133] The compound of the title was obtained in the form of a white solid with a yield of 85% (13.0 g).

[0134] TF: 102°C.

[0135] 'H NMR (CDC13): 0.84 (t, 3H), 1.21-1.26 (m, 10H), 1.39-1.47 (m, 2H), 3.17 (m, 2H), 5.21 (s, 1H), 7.07-7.11 (m, 2H), 7.24 (d, 1H), 7.41 (d, 1H) Example 5a: Synthesis of MSA2H-4

[0136] The compound MSA2H-4 was synthesized in the following manner:

[0137] In an argon-filled IL flask, 75.2 g of 3,4-dichlorophenyl isocyanate (400 mmol, 1.0 eq. CAS: 102-36-3) and 400 mL of dichloromethane were added. 65.3 mL of 2-ethylhexylamine (51.6 g, 400 mmol, 1.0 eq.) were added dropwise, ensuring the reaction mixture did not exceed 25°C. Stirring was maintained at room temperature for 18 h. The mixture was concentrated under vacuum. 200 mL of pentane was added, and the mixture was then filtered and washed with 100 mL of cold pentane. The filtrate was then concentrated, filtered, and washed with 100 mL of cold pentane. The solids were combined and dried under vacuum for 24 h.

[0138] The compound of the title was obtained in the form of an off-white solid with a yield of 96% (121.5 g).

[0139] TF: 66-67°C

[0140] H NMR (CDC13): 0.85 - 0.93 (m, 6H), 1.25 - 1.31 (m, 8H), 1.35 (m,lH), 3.21 (dd, J = 6.0, 3.3 Hz, 2H), 5.45 (s, 1H), 7.15 (m, 1H), 7.31 (m, 1H), 7.45 (s, 1H), 7.51 (m, 1H). Example 5b: Synthesis of MSA2H-5

[0141] A process similar to Example 5a, replacing 3,4-dichlorophenyl isocyanate (Cas No. 102-36-3) with 3,5-bis(trifluoromethyl)phenyl isocyanate (Cas No. 16588-74-2). Example 6a: Synthesis of MSA2H-8

[0142] The compound MSA2H-8 was synthesized as follows: Triethylamine Dichloromethane [ 0°C to TA

[0143] In a 250 mL flask, 1.50 g of 4,5-dichloro-ortho-phenylenediamine (8.47 mmol, 1.0 eq. CAS: 5348-42-5) and 70 mL of dichloromethane were added. The mixture was stirred and cooled to 0°C, and then 4.73 mL of triethylamine (3.43 g, 33.9 mmol, 4 eq.) were added. 2.96 mL (2.83 g, 17.4 mmol, 2.05 eq.) of 2-ethylhexanoyl chloride (CAS: 760-67-8) diluted in 30 mL of dichloromethane were added dropwise at 0°C. The mixture was left to stir at room temperature for 18 h. A wash with 30 mL of water followed by a wash with 30 mL of a saturated sodium chloride solution were prepared. The organic phase was dried over magnesium sulfate, filtered, and then concentrated under vacuum. The resulting solid was washed with filtered pentane and then dried under vacuum for 24 hours.

[0144] The compound of the title was obtained in the form of a white solid with a yield of 84% (2.82 g), TF: 125°C.

[0145] 'H NMR (CDC13): 0.89 (t, 6H, 3J = 7.4 Hz), 0.95 (t, 6H, 3J = 7.3 Hz), 1.25-1.37 (m, 8H), 1.47-1.75 (m, 8H), 2.08-2.23 (m, 2H), 7.63 (s, 2H), 8.39 (s, 2H). Example 6b: Synthesis of MSA2H-6

[0146] A process similar to Example 6a, replacing 4,5-dichloro-o-phenylenediamine (Cas No.: 5348-42-5) with o-Phenylenediamine (Cas No.: 95-54-5). Example 6c: Synthesis of MSA2H-7

[0147] A process similar to Example 6a, replacing 4,5-dichloro-o-phenylenediamine (Cas No.: 5348-42-5) with 4-chloro-o-phenylenediamine (CAS No.: 95-83-0).

[0148] Example 7: Measurement of the absorption isotherms at 20°C of LiCl via various extraction formulations with MSA and MSA2H from Example 1b and with MEC-1

[0149] Different formulations according to the invention were composed and tested for the extraction of LiCl from four salt water compositions in order to determine the extraction isotherms at room temperature.

[0150] The diluent selected for these tests is 2CBB. The chosen MEC is MEC- 1, namely Lithium lonophore VIII, characterized by a moderate lithium complexation constant which allows for better discrimination of the relative performance of the different anion solvating molecules.

[0151] The MEC-1 is characterized in the Tables of Example 1b.

[0152] The 2CBB was purchased from TCI Chemicals, for a purity of >99% and was used as is.

[0153] MEC-1 was synthesized in three successive steps as described in patent application FR2301758. Step 1: Synthesis of the secondary amine

[0154] R' r1 R2 + R--NH2 )--R2 / ! / □ R3-NH

[0155] With R1 and R2 representing a cyclohexyl and R3 representing an ethyl.

[0156] In a clean, dry flask, introduce the ketone (10 mmol, 1 eq), the solvent (17 volumes), the amine (45 mmol, 4.5 eq) and then the reagent(s). Depending on the reagent, heating may be necessary. The conversion is monitored by TLC with the disappearance of the starting ketone. Evaporation of the solvent (and sometimes the residual amine) under reduced pressure. Filtration, if necessary, through Fontainebleau sand, then addition of methanol (12 volumes). Add NaBH4 by portion (30 mmol, 3 eq.). Beware of gas evolution and an ice bath may be necessary. Agitation 1-15 h at cold or room temperature as appropriate.

[0157] Addition of NaOH IM to stop the reaction. 3 Extractions with DCM. Evaporation of volatiles under reduced pressure.

[0158] Purification of the residue obtained on silica gel if necessary. (DCM to DCM / ethyl acetate). Yield: 20-77% Step 2: Synthesis of chloroacetamide

[0159] Cl R 1 \ TEA ( R 1 NH-R2 / DCM / f~ \ Or2

[0160] In a round-bottom flask, introduce the previously formed amine (10 mmol, 1 eq), dichloromethane (3 volumes, 15 eq), and triethylamine (30 mmol, 3 eq). Add chloroacetyl chloride (20-25 mmol, 2-2.5 eq) at room temperature under an argon atmosphere. Shake at room temperature for 5-24 h. Add 2 volumes of water and perform two counter-extractions of the aqueous phase with 2 volumes of DCM. Concentrate the organic phase using a rotary evaporator.

[0161] Purification of the product on a silica gel column (DCM eluent 100%). Yield: 30-70% Step 3: Synthesis of the compound of interest

[0162] / h3 N—R2 Ri

[0163] In a three-necked flask, introduce NaH (3.5-4 eq) in 10 volumes of anhydrous THF. Heat the mixture under reflux in argon. Add the triol solubilized in 10 volumes of THF while still hot, followed by the synthesized chloroacetamide solubilized in 15-20 volumes of THF. Stir the mixture under reflux for 1-24 hours. Neutralize the mixture by adding 10 volumes of water. Perform two back-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.

[0164] Purify the crude product obtained by silica gel chromatography (eluent: heptane / ethyl acetate). Yields are generally between 50-70% for obtaining MEC-1.

[0165] The various formulations tested were adjusted in concentrations of MEC-1 and MSA to obtain a formulation with 0.1 mol / L of MEC-1 and 0.5 mol / L of MSA or MSA2H in the 2-CBB.

[0166] In particular, to 9.3 mL (15.4 g) of 2CBB, 1.533 g of MSA-1 and 0.958 g of MEC-1 were added, to obtain after mixing 12 mL of organic formulation at 0.1 mol / L of MEC-1 and 0.5 mol / L of MSA-1.

[0167] The volumes and masses of solvent and the masses of MSA and MEC-1 of the different formulations are summarized in the following Table: ïaâkafif S .4 Vol2€BB {mL} m 2ï BB (g) iu lisX<g) 1 g) §...39 i > .39® 1 M '5 3 MsA-2 àsss 1 - MSA- 3 9.72. -12 O CO MSA -4 9.79 Lu.y-.'O' MS AS 07: 1 $,3¾ 1 SM MsAû 9..72 .J 1.545 * MSA-' 9.72 4 A <^'5. 1.545 QO MS AS 9.39:t. jr r 2.139 Indicative s>A Me 2CBB (ni) if 15.874 1.9035 UMR MSA2H-4 9.48 45.03 1.9335 •> ^3 MSA2H-5 9.24 15.297 2.3135 0 s

[0168] Then the 12 mL of each of these formulations that were taken were placed in orbital shaking at 500 rpm overnight after adding 4 mL of distilled water twice to allow water saturation of the whole.

[0169] The following morning, four aqueous saline solutions of LiCl / MgCl2 were prepared, having concentrations of 25, 50, 100, and 250 mmol LiCl / L respectively and spiked with 1.5 mol MgCl2 / L from MilliQ water, while the formulations that had been stirred overnight were allowed to settle. Clear separation of the two colorless phases was obtained within a few minutes. Three mL of the various organic extraction solutions were then taken and transferred to a flask containing 3 mL of one of the four prepared LiCl / MgCl2 saline solutions (A / O=l). The flask was then sealed and placed under orbital shaking (generally at 800 rpm) for 2 hours at room temperature. It was verified that droplets of the order of 1-2 mm were indeed present in quantity at the chosen stirring speed (400 to 900 rpm).

[0170] Once the 2 hours of stirring were completed, the stirring was stopped and the mixture was allowed to settle for at least 10 minutes until the two phases had completely separated. The upper aqueous phase was then collected and diluted for salinity analysis by a Metrohm Ion Chromatograph incorporating a suitable cation analysis column and a cation analysis column. adapted anions. Similarly, the initial aqueous solutions of LiCl / MgCl2 were also analyzed by this ion chromatography to determine their relative concentrations of lithium, magnesium and chloride.

[0171] To duplicate the measurement and validate the desorbability of LiCl from the formulation under investigation by contact with hot water, 2 mL of the lower organic phase was taken and mixed with 10 mL of MilliQ water in a sealed flask. The mixture was then stirred at 800 rpm for 40 minutes at 95°C (A / O=5). Afterward, the stirring was stopped, and the mixture was allowed to settle for 10 minutes, still at 95°C. Rapid settling was generally observed. The upper aqueous phase was then collected and diluted for salinity analysis by ion chromatography to determine the equilibrium concentration of LiCl in the organic phase.

[0172] The isotherms obtained are shown on [Fig.1] with the concentration em lithium in the organic phase deduced from desorption at 95 °C on the ordinate (the saturation of the absorbent being at 694 mg Li / L, the isotherms make an asymptote up to this value at very high concentrations of lithium in the aqueous phase -not shown here).

[0173] It appears that these isotherms obtained at room temperature are very well modeled by a Langmuir isotherm (the curves are close to the four experimental points of each formulation). Moreover, the extraction performance is generally increasing from MSA-1 to MSA-8, with a clearly visible jump as soon as one moves to the two-hydrogen solvates, MSA2H, all five of which occupy the high performance level.

[0174] The Langmuir parameters obtained for these isotherms in mg / L have been quantified and are given in the following tables: Indicator SA K iW.b 0 043 0.422 GAIS 1..23 0.621 MSÀ-3 ■'$ 1.44 0.817 MSA-4 1 5S 70' 3.714 MSA-5 1.82 3 OS . Ck MSA2H-3$2? 14.73 135 795' 31x4211-4 10.05' 16.14 162.854 ^Ix42&5 3.53 13.17 112.431

[0175] We observe a factor of 8 between the best MSA-8 and MSA2H-4 for the value of 1000.KH.b (162.854 / 20.330=8), which validates the interest of having these new families of anion solvating molecules, which are described according to the present invention, for liquid-liquid salt extraction processes.

[0176] Overall, between MSA-4 amide and MSA2H-1 urea, both with the same mono-chlorinated aromatic ring, an absorption capacity gain of 52.94% is observed, while between MSA-7 amide and MSA2H-3 urea, both with the same di-chlorinated aromatic ring, an absorption capacity gain of 23.35% is observed. See Figures 2 and 3.

[0177] Example 8: Influence of the relative MSA / MEC concentration on the extraction performance of LiCl via formulations incorporating MEC-1

[0178] This example demonstrates that the performance gap in extraction between MSA and MSA2H is maintained globally until extraction saturation is reached, regardless of the relative concentration between MSA and MEC-1. Thus, a salt water containing 200 mmol / L of LiCl, doped with 1.5 mol / L of MgCl2, was considered, which was then brought into contact with different formulations composed of 0.1 mol / L of MEC-1 and having 100, 500 or 1000 mmol / L of MSA or MSA2H in the diluent 2CBB.

[0179] The procedure for preparing the various formulations and quantifying the extracted LiCl is identical to that of Example 7.

[0180] The results obtained using the two methods for estimating the lithium concentration in the organic phase (desorption at 95 °C and difference in lithium concentration of the water before and after extraction) are summarized in the following Table and Figures 4 and 5: îtK&aîsf SA Eq. MSA / MEC-Ï C wg'Lî (ütgïl) ALI aq (mg / L) MSA-2 200 2 107.9 125.6 ftSSA-2 500 5 273.5 297.3 1008 10 414.7 428.8 WSA-4 500 5 431.8 MSA-7: 200 2,247.7 28§.8 MSA-7 500 5 48S, S 535.7 WSA-7 1800 1S 588.3 840.8 Indicator SA C MSA (mmaEX) Eq. MSA / MEÇ-Ï C arg Et (mg.-l) AU aq (m$ <L) MSA2H-1 500 5 575,0 634,5 200 2 470.7 484,0 MSA2«-4 500 5 575,5 681,7 MSA2H-4 .1£W 10 600,4 711,4

[0181] Magnesium is not indicated because it is not extracted.

[0182] It appears that for the highest-performing MSAs (MSA2H), the usual desorption procedure (5 volumes of water per volume of organic phase, at 95°C) no longer allows for the complete desorption of the absorbed LiCl, and that MSA2H-4 has reached saturation with absorbed LiCl (694 mg Li / L). We clearly observe superior performance of the two MSA2Hs compared to the other three MSAs.

[0183] Example 9: Impact of Fanion hydrophilicity on extraction performance

[0184] The extraction performance of a lithium salt is evaluated here as a function of the anion associated for both MSA-7 and MSA2H-4, and for the following salts ranked in increasing order of anion hydrophilicity: LiPF6, LiC104, Lil, LiNO3, LiBr, LiCl, LiOAc, Li2 SO4, Li2C2O4, Li2SiO3 and Li2CO3.

[0185] This hydrophilicity is generally characterized by the free enthalpy of hydration of the anion, AG°hyd, expressed in kJ / mol, which is more negative the more hydrophilic the anion is, and / or the higher the electron density of the anion.

[0186] The comparative performance between two formulations at 0.1 mol / L of MEC-1 and at 0.5 mol / L of MSA-7 and MSA2H-4, all in 2CBB, is presented below.

[0187] A salt water containing 100 mmole / L of lithium ion was considered, which was then brought into contact with the two formulations presented above.

[0188] The procedure for preparing the various formulations and quantifying the different lithium salts extracted is identical to that of Example 7.

[0189] The results obtained for MSA-7 and MSA2H-4 are summarized in the following Table and Figures 6 and 7: Sel AG Anion^1' [Liàwg ung L> A|Lt] aq MSA-7 ÜagÆ) [Ls]©rg 1! 4[Lî] MSA2H-4 iïBg Lj tiPFg -l&7a * 901 505 * LiBF, * 36ëx $ T: iictog -239£ 442 520 444 428 lif -280 357 398 433' 405 _. at -3½ 187 223 323 322 liBr -313 163 198 370 277 lia -344 74 111 173 173 CHsCOOli -374 5 21 63 77 -§75 s 10 85 §5 0 15 74 93- -B24 ÎOO 111 LijSiÜj 4393* 505-

[0190] *Value not measured, xLow value not considered, “Estimated value.

[0191] 'Data from various publications by: Yizhac Marcus,

[0192] bOther literature, Tonie Hydration Enthalpies Derek W. Smith Journal of Chemical Education 1977, 54(9), 540-542

[0193] It appears that anions with an enthalpy of hydration below -400 kJ / mol, whether monovalent or divalent, are now extracted with MSA2H-4 with comparable strength (organic phase concentration of the same order of magnitude), while anions with a free enthalpy of hydration between -400 and -280 kJ / mol see their extraction performance increase with the use of MSA2H-4 compared to MSA-7.

[0194] The following experiments show that the use of an extradant with a higher complexation constant Log K(MeOH, 25 °C) makes it possible to further develop the extractability of salts and thus enable the industrial extraction of sulfate salts and more generally of salts with divalent anions.

[0195] Example 10: Impact of the choice of the ECM on extraction performance

[0196] Various ion-extracting compositions according to the invention have been formulated and tested. The seven cation-extracting molecules (CEMs) used in these compositions are those shown in Example 1b.

[0197] The implementation of MSA2H type molecules in combination with these ECMs makes it possible to improve the extraction performance of salts associated with these cations and with mono-charged hydrophilic anions (-) and makes it possible, by combination with ECMs with Log K(MeOH, 25°C) >1.4 to extract salts with divalent anion (2-).

[0198] Fig. 8, through the two isotherms shown, shows that by using the extradant MEC-6 (log K(Li+, MeOH, 25°C) = 4.0), associated with MSA2H-4 (0.1 mol / L MEC / 0.5 mol / L MSA2H), the lithium concentration of the organic phase is significantly higher than that observed during the extraction at 20°C of the sulfate salt Li2SO4 with an equivalent formulation using the extradant MEC-1 (log K(Li+, MeOH, 25°C) = 2.2).

[0199] Example 11: Influence of the relative MSA / MEC concentration on the extraction performance of LiCl via formulations incorporating MEC-6

[0200] Here, MEC-6 was chosen which has the highest complexation constant for lithium for the series of extractants presented (LogK(Li+, MeOH, 25°C) = 4.0).

[0201] This example demonstrates that the extraction performance gap between MSA and MSA2H is generally maintained until extraction saturation is reached, regardless of the relative concentration between MSA and MEC-6. Thus, a salt water containing 200 mmol / L of LiCl, doped with 1.5 mol / L of MgCl2, was considered, which was then brought into contact with different formulations composed of 0.1 mol / L of MEC-6 and having 100, 500 or 1000 mmol / L of MSA in the 2CBB diluent.

[0202] The procedure for preparing the various formulations and quantifying the extracted LiCl is identical to that of Example 7.

[0203] The results obtained are summarized in the following Table and Figures 9 and 10: ladkatif SA C MSA Eq. MSA / MEC-^ Coac. fEtlerg A [Lî] üq (mf / L) MSÀ-2 2£® 2 244.2 304.4 MSA2 500 5 449.5 593.3 MSA-2 1600 10 347.5 6--41 MSÀ-4 sos 5 S35.3 551.3 MSA-7 20S 2 3? 6.4 452.6 MSA-7 500 5 555.6 700.S MSA-7 1000 lü 557.3 703.2 ïad&s tif SA C MSA (mmoVL) Eq. MSA / MEC-â This sk. [Li]osg (mg-l) AfLIJ aq (sfigÆj MSA2H-1 SOS 5 345.5 596.9 MSA2H-4 200 2 477.3 502.9 MSA2H-4 500 500.,3- 599.3 MSA2H4 1000 10 473.4, 710.2

[0204] Magnesium is not indicated as it is not extracted.

[0205] It appears here that for all MSAs, the usual desorption procedure (5 volumes of water per volume of organic phase, at 95°C) no longer allows the entire absorbed LiCl to be desorbed and that MSA-7, MSA2H-1 and MSA2H-4 all reached saturation in absorbed LiCl (694 mg Li / L) from 5 eq. MSA / MEC, showing a net gain in extraction performance.

[0206] Example 12: Influence of the relative MSA / MEC concentration on the extraction performance of Li2SO4 via formulations incorporating MEC-1

[0207] We return here to the experimental conditions of Example 7 but replacing LiCl with Li2SO4 for which we saw via Example 8 that the extraction performance of this very hydrophilic salt was very limited with MSA-7.

[0208] This example demonstrates that the introduction of MSA2H allows the extraction of Li2SO4 to take off and that this increases with the concentration of MSA2H. Thus, a salt water containing 100 mmol / L of Li2SO4 (200 mmol / L of Li+), doped with 1.5 mol / L of MgSO4, was considered, which was then brought into contact with different formulations composed of 0.1 mol / L of MEC-1 and having 100, 500 or 1000 mmol / L of MSA in the diluent 2CBB.

[0209] The procedure for preparing the various formulations and quantifying the extracted Li2SO4 is identical to that of Example 7.

[0210] The results obtained are summarized in the following Table and Figures 11 and 12: ïadstative SA G MSA (mmsEL) Eq. MSA / MEC Casiç, fLî]org' A[Li] aq (mg / L) MSA-2 508 5 22 3. 923 MSA -4- 503 5 13.3 813 MSA-7 280 2 223 33.4 MSA -7 580 5 15.7 80.3 MSA-7 1038 10 3.1 / 5.5 Indicator SA € MSA fæœaiZL) £q. MS A / MEC €Wç. (mg / T) MSA2H-1 200 -■y 14.8 75 8 MSA2H-Î 508 5 120.7 230.1 MSA2H-1 IDC® $ 258.3 •315.7 MSAZH-4 203 2 18.5 72.5 MSA2H-4 500 5 14^ / 7 228.1 MSA2H-4 ieæ 10 281.1 345.0

[0211] Magnesium is not indicated as it is not extracted.

[0212] If the Li2SO4 extraction performance takes off with this new family of MSA2H, it remains below 50% with this MEC-1 which has a complexation constant for lithium, Log K, limited to the value of 2.2.

[0213] Example 13: Influence of the relative MSA / MEC concentration on the extraction performance of Li2SO4i via formulations incorporating MEC-6

[0214] This example, through the combination of MSA2H with maximum Fanion solvation and MEC-6 with Log K complexation constant of 4.0, demonstrates a very interesting performance for enabling an industrial application of Li2SO4 extraction

[0215] Here, MEC-6 was chosen which has the highest complexation constant for lithium for the series of extractants presented (LogK(Li+, MeOH, 25°C) = 4.0).

[0216] This example demonstrates that the extraction performance gap between MSA and MSA2H is maintained globally until extraction saturation is reached, regardless of the relative concentration between MSA and MEC-6. Thus, a salt water containing Li2SO4 (200 mmol / L of Li+), doped with 1.5 mol / L of MgSO4, was considered, which was then brought into contact with different formulations composed of 0.1 mol / L of MEC-6 and having 100, 500 or 1000 mmol / L of MSA or MSA2H in the 2CBB diluent.

[0217] The procedure for preparing the various formulations and quantifying the extracted Li2SO4 is identical to that of Example 7.

[0218] The results obtained are summarized in the following Table and Figures 13 and 14: ïndfcaiif SA Cm (snmalT.) E< MSA'MEC Cesc. fU]srg (mgîïj AfLifaq (isg / L) soo O 108.1 MSA -4 500 5 15.3 101.7 MSA-7 200 2 4.8 85.5 MSA-7 500 5 25.7 08.1 MSA-7 1000 13 89.1 200.0 Ist {festive SA C MSA Eq, MSAiMEC Ço»ç, [Li]arg MSA2H-1 200 2 133.2. 232.7 MSA2H-1 500 5 344.9 432.3 MSÀ2H-1 1000 10 4 S 5.4 828.0 MSA2H 4 300 2 153.1 353.2 MSA2H 4 500 5 377.3- 503.3 MSA2tM 1000 10,444.2 550.8

[0219] Magnesium is not indicated as it is not extracted.

[0220] It appears that the two anionic solvatants MSA2H-1 and MSA2H-4 have a similar Li2SO4 extraction performance, without reaching the saturation of the extradant MEC-6.

[0221] Example 14: Measurement of the absorption isotherms of Li 2 SO i via various extraction formulations with different formulations of MEC-1 and MSA2H-4.

[0222] We saw in Example 8 that the extraction of Li2SO4 was only slightly or not at all achieved when the anion solvating molecule MSA-7 was implemented at a rate of 0.5 mol / L for 0.1 mol / L of MEC-1, in the presence of 0.1 mol / L of Li2SO4 in aqueous solution.

[0223] This example considers the implementation of the anion solvating molecule MSA2H-4 through various formulations where the concentration of MEC-1 has evolved from 0.1 mol / L to 0.25 mol / L for different concentrations of MSA2H-4 ranging from 0.5 mol / L to 1 mol / L, the diluent remaining 2CBB.

[0224] The experimental conditions are identical to those of Example 7, the difference being limited to the saline composition of the waters brought into contact, of Li2SO4 in pure form and the number of points carried out, from 4 to 6, to construct the isotherms at 20°C.

[0225] The volumes and masses of diluent and the masses of MSA2H-4 and MEC-1 of the different formulations prepared to obtain approximately 18 mL of formulation for each composition are summarized in the following Table: MEC-1 M-A1H-4 Vol. 9.7SM 12.38 20.501 4 293 2.155 8, ISM / 1,&M 18.481 5 718 2.155 10.51 17.399 5.71 î 2.873 &35M / 1.8M S.85 16.317 5.711 3,592

[0226] The equilibrium isotherms of extraction of Li2SO4 at 20°C obtained are presented in [Fig. 15].

[0227] It appears that with this new family of two-hydrogen anionic solvator molecules, the extraction of Li2SO4 becomes industrially possible, even with an extradant, MEC-1, having a relatively modest extraction constant, Log K(MeOH, 25°C), with a value of 2.2+ / -0.2.

[0228] The isotherms obtained at room temperature are well modeled by a Langmuir isotherm (the curves are close to the 4 to 6 experimental points of each formulation). Furthermore, the extraction performance is generally improved for higher concentrations of MEC-1 and by increasing the MSA2H-4 / MEC-1 ratio.

[0229] The Langmuir parameters obtained for these isotherms in mg / L have been quantified and are given in the following table: Csïs.pasiSi.sns MEC-i M-A2H-4 K Li^SQ* K Henry LiCl 1896.6 OîSQ4 nn+M? LiCl 1888.KH.b Lia «MM 8.SM 9.279 0.49 û 432 0.84 0.121 9.317 9.15M <>.5M 0.11 0.14 9.9! 5 » ISM O.~SM 0.27 0.31 0 032 iHSM l.+M 9 33 0.38 0.115 tUM / MM 0.28 0.755 0.20 0.50' 0.052 9.375- §.25M / I.ÔM 0.24 0.17 0.039

[0230] While the extraction of pure LiCl naturally remains higher than the extraction of Li2SO4, it is observed in [Fig. 16] that the presence of the anion solvator MSA2H-4 ensures a suitable and significant extraction of Li2SO4 for its implementation at the industrial level.

[0231] Example 15: Comparative extraction of bisamide anion solvating molecules, MSA2H-6 to MSA2H-8 by comparison to the other MSAs presented.

[0232] Three new formulations according to the invention have been composed and tested for the extraction of LiCl from one of the 4 salt water compositions used in Example 7.

[0233] The diluent selected for these tests is 2-chlorobromobenzene (2CBB, C6H4BrCl, CAS 694-80-4). The cation-extending molecule is MEC-1 and the The MSAs considered are MSA2H-6, MSA2H-7 and MSA2H-8 for obtaining a formulation at 0.1 mol / L of MEC-1 and 0.5 mol / L of MSA2H in this 2-chlorobromobenzene.

[0234] The volumes and masses of diluent and the masses of MSA2H and MEC-1 of the different formulations prepared (12 mL) are summarized in the following table: lïtdkatif SA VU 2CBB (inL) bs 3CBE (g) ni M&À ig) m MEC-1 MSA2H-4 9. G0 14,897 2,170 0,958 MSA2H-7 8,32 14,778 2,377 0,958 MSA2H-S S, 85 14,658 2,535 ■0,956

[0235] The procedure presented in Example 7 is repeated for the preparation of three extraction points from salt water composed of 0.1 mole LiCl / L and doped with 1.5 mole MgCl2 / L, produced from MilliQ water (Salt water from Example 7 measured at 669.5 mg Li / L).

[0236] These bisamide-based MSA2Hs perform very well among the experimental points from Example 7, with an increase in extraction performance associated with an increase in the number of chlorides positioned meta or para on the aromatic. The combined experimental results of Examples 7 and 15 are summarized in the following Table and [Fig. 17]. MSA indices 1 2 3 4 5 6 7 8 673.7 479.1 476.0 4ÛG.2 355.6 3 03.S 3iü,è 311.0 .70.6 151.8 101.1 260.4 304.9 345.6 350.5 358.6 MSA2H indices 1 £ 3 4 5 5 7 8 Ïmg / 'O 233.8 237.7 173.2 163.9 227.2 262.1 196.4 €(Ls|org 434.1 447.3 46g.9 467.9 442.4 .7 468.4 473.1

[0237] It appears here that the extraction performance for these MSA families is all the stronger when the MSA has electron-deficient hydrogen NH groups and when they are all the more activated by the presence of several halogens and / or electron-withdrawing groups in RD, RE and / or RF positions.

Claims

1. Demands - Hydrophobic organic liquid composition for the extraction, from salt water or brine, of a monovalent or divalent anion salt, comprising a cation and an anion complementary to the cation, said composition comprising: A. at least one cation-extracting organic compound, exhibiting a Log K complexation constant for this cation in methanol at 25 °C of at least 1; B. at least one organic, diprotic, and hydrophobic compound that solvates the complementary anion of the cation; and C. at least one hydrophobic polar organic diluent having a flash point above 60°C, characterized by the fact that component(s) (B) is or are chosen from compounds of formula (I): HH (D II NN Ra Rb r c in which: • Ra and Rc each independently represent one of: • a monovalent aromatic or heteroaromatic radical possibly substituted; • a radical AC> ™ X1 represents O or X S and Ra represent an aromatic or heteroaromatic radical, or an alkyl or alkoxyl radical, linear or branched, or cycloalkyl or cycloalkyl-alkyl, these radicals possibly being substituted; and • an alkyl radical, linear or branched, or cycloalkyl or cycloalkyl-alkyl, these radicals possibly being substituted; and Rb represents one of: • a divalent aromatic or heteroaromatic radical, possibly substituted; • a radical represents 0 or S; • an ethylene radical -CH2-CH2-; and • a radical 3 3 where X3 represents 0 XX *v* or S and Q represents a divalent aromatic or heteroaromatic radical, possibly substituted.

2. - Composition according to claim 1, characterized in that the compound or each compound of formula (I) comprises from 12 to 40 carbon atoms, preferably from 14 to 30 carbon atoms, in particular from 15 to 25 carbon atoms.

3. - Composition according to any one of claims 1 and 2, characterized in that, in formula (I), at least one of RA, RB and Rc represents an aromatic or heteroaromatic radical or contains such a radical, possibly substituted, at least one halogen and / or at least one electron-withdrawing group which may be part of the substituents.

4. - Composition according to any one of claims 1 to 3, characterized in that the radicals constituting RA and Rc are chosen independently from: ' Y / / / \ Y to > - \ \ H • ^.8 ' X'YY'Y $ ,;à" RY'""Y s / £ • C(=O)CmH2m+i with m < 10, where m is an integer, • C(=O)CmH2m with m < 10, where m is a non-zero integer, • C(=S)CmH2m+i with m < 10, where m is an integer, • C(=S)CmH2m_i with m < 10, where m is a non-zero integer, • CmH2m+i with m < 10, where m is a non-zero integer, • CmH2m_i with m < 10, where m is a non-zero integer, • (CH2)mCpF2q+i with m < 6, where m is a non-zero integer, and where q<4, • (CH2)mCpHqFrClsBrt with m < 6, where m is a non-zero integer, and where p, q, r, s and t are integers of which at least r, s or t is non-zero, and the constituent radical RB is a radical chosen from: C(=O), C(=S), -ch2ch2-, O. R® where at least one of the radicals RD, RE and RF is chosen from among the following halogens or electron-withdrawing groups: • 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, • ocf3, • OCH2CF3, • scf3, • C(=O)CF3, • no2, • 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, • C(=O)CmH2m+i with m < 4, where m is an integer, and • S(=O)CmH2m+i with m < 4, where m is an integer, the other radicals RD, RE, RF and the radicals RG are chosen, identical or different, from among the following non-electro-withdrawing atoms or groups: • H, • ch3, • CH2CH3, c3h7, • CH2CH2CpF2p+i with p < 4, where p is an integer, • CmH2mA with m < 10, where m is a non-zero integer, and • CmH2m+i with m < 10, where m is a non-zero integer; where only one of the radicals RD to RF can be one of these last two radicals CmH2m or CmH2m+i, for m > 4.

5. - Composition according to any one of claims 1 to 4, characterized in that the alkyl radical included in the definition of RA or Rc or Rac represents one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, 2-methylbutyl, 2-ethylpropyl, n-hexyl, iso-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and the cycloalkyl radical included in the definition of RA or Rc or RAC represents one of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopentylmethyl or cyclohexylmethyl.

6. - Composition according to any one of claims 4 and 5, characterized in that the compound of formula (I) is selected from: triclocarban,

7. N,N'-bis(3-chlorophenyl)urea, N-(3-bromophenyl)-N'-phenyl urea, N-(3-chlorophenyl)-N'-cyclohexylurea, N-cyclohexyl-N'-[4-(trifluoromethoxy)phenyl]urea, N-(4-bromophenyl)-N'-cyclohexylurea, N-(3-chloropheny-1)-N'-(cyclohexy-1-Imethy-1)urea, N,N'-bis(4-bromophenyl)urea, 4-bromo-N 1,N2-diphenyl-1,2-benzenediamine, 4-chloro-N 1-( 1 -methylethyl)-N2-phenyl-1,2-benzenediamine, 4-fluoro-N2-(4-fluorophenyl)-Nl-(l-methylethyl)-l,2-benzenediamine, 4,5-dichloro-Nl-(3-methylbutyl)-N2-phenyl-1,2-benzenediamine, N,N'-(4,5-dichloro-1,2-phenylene)bis-propanamide, N,N'-(4,5-dichloro-1,2-phenylene)bis-hexanamide, the N,N'-(4-chloro-l,2-phenylene) bis[benzamide], N-[2-(acetylamino)-4-chlorophenyl]benzamide, N-[2-(acetylamino)-4-bromophenyl]benzamide, the N,N'-(4,5-dichloro-1,2-phenylene)bis[benzamide], 5-bromo-Nl,N3-bis(4-butylphenyl)-l,3-benzenedicarboxamide, 5-bromo-Nl,N3-bis[3-(trifluoromethyl)phenyl]-l,3-benzenedicarboxamide, N1,N3-bis(3,4-difluorophenyl)-1,3-benzenedicarboxamide, 4-chloro-N2,N6-diphenyl-2,6-pyridinedicarboxamide, N2-ethyl-N6-phenyl-4-(trifluoromethyl)-2,6-pyridinedicarboxamide, N2,N6-diphenyl-4-(trifluoromethyl)-2,6-pyridinedicarboxamide N-(3-chlorophenyl)-N'-octylurea, N-(3-chlorophenyl)-N'-(2-ethylhexyl)urea, N-(3,4-dichlorophenyl)-N'-octylurea, N-(3,4-dichlorophenyl)-N'-(2-ethylhexyl)urea, N-(3,5-bis(trifluoromethyl)phenyl)-N'-(2-ethylhexyl)urea, N,N'-(4,5-dibromo-l,2-phenylene)bis(hexanamide), N,N'-(4-chloro-1,2-phenylene)bis-2-ethylhexylamide, N,N'-(4,5-dichloro-1,2-phenylene)bis-2-ethylhexylamide and N,N'-ethylenebis[3,4-dichlorobenzamide]. - Composition according to any one of claims 1 to 6, characterized in that the cation extractant(s) are chosen from compounds of formula (II): 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 C3-C8 cycloalkyl; or RI and R2, taken together with the nitrogen atom that bears them, form a ring of five, six, seven or eight links; R3 is chosen from hydrogen, linear or branched CrC8 alkyl, C3-C8 cycloalkyl, C2-C6 alkoxyalkyl and alkoxyalkylaryl; R4 is chosen from hydrogen, alkyl in linear or branched CrC3; R5 is chosen from hydrogen, alkyl in linear or branched Ci-C3; and R6 is chosen from hydrogen, alkyl in linear or branched Ci-C3.

8. - Composition according to any one of claims 1 to 6, characterized in that the cation extradant(s) are selected from compounds of formula (III) or formula (IV): Or n is an integer ranging from 4 to 8,

9. • p is 1 or 2, • m is 3 or 4, • q and t, whether identical or different, are 0, 1, or 2, • R is a tert-butyl, tert-pentyl, tert-octyl, O-methyl, O-ethyl, O-propyl, O-isopropyl, O-butyl, O-isobutyl, O-pentyl, O-hexyl, O-heptyl, O-octyl, OCH2-Phenyl group or a hydrogen atom, • R' and R”, identical or different, are chosen from the group consisting of the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secbutyl, pentyl, hexyl, heptyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl groups or R' and R” together form a pyrrolidine, piperidine or morpholine ring. - Composition according to any one of claims 1 to 6, characterized in that the cation extractant(s) are chosen from compounds of formula (V) or formula (VI): Or : n is 4, 5 or 6; p is 1 or 2; m is 2 or 3; q and t, whether identical or different, are 0, 1, or 2. R is a tert-butyl, tert-pentyl, tert-octyl group or a hydrogen atom; R' is chosen from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secbutyl, pentyl, hexyl, heptyl and octyl groups for the realization of a ketone-type bonding group, or from the group consisting of O-methyl, O-ethyl, O-propyl, O-isopropyl, O-butyl, O-isobutyl groups,

10. O-pentyl, O-hexyl, O-heptyl, O-octyl, OCH2-Phenyl for the formation of an ester-type bonding group. - Composition according to any one of claims 1 to 6, characterized in that the cation extractant(s) are selected from a crown ether, in particular a crown ether having 14 to 80 carbon atoms, in particular selected from the group consisting of: decahydro-6-tetradecyl-12a,16a-Butano-2H,9H-1,5,8,12- benzotetraoxacyclotetradecin (nC14-Decalino-14-crown-4-ether, Cas no. 151460-03-6), decahydro-6-tetradecyl-12a, 16a-Propano-2H,9H-1,5,8,12-benzotetraoxacyclotetradecin (nC14-CyclopetanoCyclohexyl-14-crown-4-ether, Cas n° 151460-02-5), 2,3,5,6,8,9,ll,12-Octahydro-14-pentadecyl-l,4,7,10,13-benzopentaoxacyclopentadecin (3'-pentadecylbenzo- 15-crown-5-ether, 88037-72-3), tetradecahydro-7-tetradecyl- 4a,20a: 1 la, 15a-Dibutano- 17H-dibenzo[b,k] [ 1,4,7,10,13]-pentaoxacyclohexadecin (tetradecyl-didecalino-16-crown-5-ether, Cas n° 172883-31-7), 2,2,3,3,ll,ll,12,12-Octamethyl-6-tetradecyl-l,4,7,10,13- pentaoxacyclohexadecane (octamethyl-nC14-16-crown-5-ether, Cas n° 172883-30-6), Eicosahydrodibenzo[b,k] [1,4,7,10,13,16]hexaoxacyclooctadecin (Dicyclohexano-18-crown-6-ether, Cas n° 16069-36-6), octadecahydro- 4a,24a:8a,12a:16a,20a-Tributanotribenzo [b,h,n] [l,4,7,10,13,16]hexaoxacyclooctadecin (Tridecalino-18-crown-6-ether, Cas n° 104049-01-6), octadecahydro-4a,25a:8a,12a:16a,20a-Tributano-22H-tribenzo[b,h,n] [1,4,7,10,13,16]hexaoxacyclononadecin (Tridecalino-21 -crown-6-ether, Cas n° 259874-18-5); et un cryptand choisi parmi le 5,6,14,15-dicyclohexano-4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8.8.8]hexacosane, le 5,6,14,15-dibenzo-4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8.

8. 8]hexacosane et le 5-décyl-4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.

8. 8]hexacosane.

11. - Composition according to any one of claims 1 to 10, characterized in that the hydrophobic polar organic diluent(s) is or are selected from bromochlorobenzenes, bromochlorotoluene, bromochlorooxylenes, bromochloroethylbenzenes, bromochloropropylbenzenes, bromochloroisopropylbenzenes, bromochlorobutylbenzenes, bromoethoxybenzenes, dibromobenzenes, dibromotoluenes, their derivatives and mixtures, and in particular from 2-bromo-1-chloro-3-ethylbenzene, 1-bromo-2-chloro-3-isopropylbenzene, 2-bromo-1-chloro-3-isopropylbenzene, 2-bromo-4-chloro-1-isopropylbenzene, 2,3-dichloro-1,4-dimethylbenzene, the 2-bromo-l-chloro-4-ethoxybenzene, 2-bromo-4-(2-methylpropyl)-l-(trifluoromethyl)benzene, l-bromo-3-ethylbenzene, 1-bromo-3,5-dimethylbenzene, 3,4-dichlorotoluene, l-ethyl-2-nitrobenzene and l-bromo-2-chlorobenzene.

12. - Composition according to any one of claims 1 to 11, characterized in that the cation is selected from cations of alkali metals, alkaline earth metals, transition metals, lanthanides or actinides such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium, manganese, cobalt, copper, zinc, silver, cadmium, indium, gold, lanthanum, cerium, neodymium, europium, gadolinium, thorium and water-soluble salt metals.

13. - Composition according to any one of claims 1 to 12, characterized in that the anion is selected from oxalate, sulfate, silicate, carbonate, fluoride, chloride, nitrate, bromide, chlorate, perchlorate, iodide, bromate, cyanide, chlorite, iodate, hydrogen carbonate, hydrogen sulfate, hydrogen sulfite, hydrogen silicate, cyanate and hexafluorophosphate.

14. - Composition according to any one of claims 1 to 13, characterized in that at least one component (A) is present in the composition at a concentration of 0.10 to 1 mol / L, preferably 0.3 to 1 mol / L, more preferably 0.45 to 1 mol / L.

15. - Composition according to claim 14, characterized in that the ratio of the molar concentration of at least one component (B) to the molar concentration of at least one component (A) is 1 to 15, preferably 1.5 to 5 and more preferably 2 to 4.

16. - Use of the hydrophobic organic liquid composition according to any one of claims 1 to 15 in a process for extracting monovalent or divalent anion salt, said process comprising a step of mixing, at a first temperature, the hydrophobic organic liquid composition and the brine to be treated, a step of separating the hydrophobic organic liquid composition loaded with monovalent or divalent anion salt and the treated brine, and a step of regenerating the hydrophobic organic liquid composition by treating the hydrophobic organic liquid composition loaded with monovalent or divalent anion 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.

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