Hydrophobic organic liquid compositions for extracting a monovalent- or divalent-anion salt from saltwater or brine

Abstract

The invention relates to a composition comprising: (A) at least one cation extraction compound having a stability constant Log K for this cation in methanol at 25°C of at least 1; (B) at least one organic, diprotic and hydrophobic compound solvating the complementary anion of the cation; and (C) at least one hydrophobic polar organic diluent having a flash point higher than 60°C, the at least one component (B) being selected from among compounds of formula (I): wherein RA and RC are each independently one of an optionally substituted monovalent aromatic or heteroaromatic radical; a radical of formula (a), where X1 is O or S and RA,C is an aromatic or heteroaromatic radical; a linear or branched alkyl or alkoxyl or cycloalkyl or cycloalkyl-alkyl radical, the radicals optionally being substituted; and RB is one from among an optionally substituted divalent aromatic or heteroaromatic radical; formula (b), where X2 is O or S; an ethylene radical -CH2CH2-; and a radical of formula (c) where X3 is O or S and Q is a bivalent, optionally substituted aromatic or heteroaromatic radical.

Description

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, particularly 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 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 oil production waters, or from geothermal and other saline aquifers, or from mineral rocks that are crushed and then enriched with the ore of interest before potentially being solubilized (leached) in water for subsequent separation and purification (or refining) processing. Thus, these minerals of interest, whether cationic or anionic in their water-soluble form, must be able to undergo hydrometallurgical processing that is as efficient as possible, from both an ecological and environmental perspective, as well as an economic one.

[0006] Therefore, 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 important to enable efficient extraction of salts whose anion is particularly hydrophilic, such as divalent anion salts, like sulfate salts (SO4 2- ), of oxalate (C2O4 2- in waters with a pH close to or greater than the pKa2(HC2O4 - / C2O4 2- ) = 4.3), of chromate (CrO4 2- in neutral or basic medium, of pKa2(HCrO4 - / CrO4 2- ) = 6.4), of hydrogen phosphate (HPO4 2- in basic medium, of pKa2(H2PO4 - / HPO4 2- ) = 7.2), of sulfite (SO3 2- in basic medium, of pKa2(HSO3 - / SO3 2- ) = 7.2), of carbonate (CO3 2- in basic medium, of pKa2(HCO3 - / CO3 2- ) = 10.3) or silicate (SiO3 2- ) in a very basic medium, of pKa2(HSiO3 - / SiO3 2- ) = 13.1) for example.

[0009] This gain in extraction performance, resulting from more efficient anionic solvates, also leads to a performance gain 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 salts (I₂O₅). - ), of bromides (Br - ), of perchlorates (ClO4 - ), of hydrogen sulfates (HSO4 - in a very acidic environment, of pKa2(HSO4 - / SO4 2- ) = 1.9), of hydrogen oxalate (HC2O4 - , in acidic medium, of pKa (HC2CO4 - / C2O4 2- )=4.3), of chlorides (Cl - ), of chlorates (ClO3 - ), of permanganates (MnO4 - ), of bromates (BrO3 - ), of nitrates (NO3 - ), of iodates (IO3 - ), of hydrogen sulfites (HSO3 - in acidic medium, of pKa1(SO 2aq / HSO3 - ) = 1.8 and pKa2(HSO3 - / SO3 2- ) = 7.2), of chlorites (ClO2- ), hydrogen phosphates (H2PO4 - in acidic medium, of pKa1(H3PO4 / H2PO4) - ) = 2.1), of fluoride (F - ), nitrite (NO2 - ), of formate (HCOO - ), of cyanates (NCO₃ - ), of thiocyanate (SCN - ), acetate (CH3COO - ), hydrogen carbonates (HCO3 - in a slightly acidic or basic environment, of pKa1(CO 2aq / HCO3 - ) = 6.4 and pKa2(HCO3 - / CO3 2- ) = 10.3), of cyanides (CN - ) in basic medium, of pKa1(HCN / CN - ) = 9.25), of hydrogenosilicates (HSiO3 - in basic medium, of pKa1(H2SiO3 / HSiO3 - ) = 9.9), hexafluorophosphates (PF6 - ) or trifluoromethylsulfonate (CF3SO3 - ) For example.

[0010] The treatment of these numerous and diverse divalent or monovalent anion salts 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 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 donors 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 allows for a reduction in the theoretical number of extraction stages required to achieve a target extraction or recovery rate, or for an increase in extraction yield with a constant number of extraction stages. This effect is even more pronounced 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 equilibrium isotherms of LiCl extraction between formulations incorporating MSA or MSA2H is exemplified initially through several examples for formulations of the same concentrations of active MEC (cation extracting molecule) and MSA in a diluent chosen to allow good salt extraction.

[0015] Next, the impact of the choice of MSA / MSA2H anion solvator on extraction performance is presented for various lithium salts, depending on the complementary anion to the lithium. This study is presented for the following salts in increasing order of anion hydrophilicity: LiPF6, LiClO4, LiI, LiNO3, LiBr, LiCl, LiOAc, Li2SO4, Li2C2O4, Li2SiO3, and Li2CO3.

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

[0017] Also, 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 mole / L of MEC and 0.5 mole / 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: at least one cation-extracting organic compound having a Log K complexation constant for this cation in methanol at 25°C of at least 1; at least one diprotic and hydrophobic organic compound solvating the anion complementary to the cation; and 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): (I)

[0021] in which: R A and R Ceach independently represent one of the following: a monovalent aromatic or heteroaromatic radical, possibly substituted; a radical , where X 1 represents O or S and R A,C 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 R B represents one of: a divalent aromatic or heteroaromatic radical, possibly substituted; a radical , where X 2 represents O or S; an ethylene radical -CH2-CH2-; and a radical where X 3 represents O or S and Q represents a divalent aromatic or heteroaromatic radical, possibly substituted.

[0022] In the present invention, the following substituents can be cited: C1-C alkyl 10linear or branched, 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 preferentially 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, -CH2Cl, -CHCl2, -CCl3, -CH2Br, -CHBr2, -CHFCl, -CHFBr, -CHBrCl, -CClF2, -CCl2F, C(=O)CF3, and -NO2, and other electron-withdrawing groups, in meta and / or para positions on the aromatic or heteroaromatic radical.

[0025] A monovalent anion salt is understood to be 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 with a neutral charge.

[0026] A divalent anion salt is defined as a salt comprising a cation and at least one mono- or polyatomic anion carrying two negative charges, which alone, or combined with another anion, allows the positive charge(s) of the cation to be neutralized to obtain a neutrally charged salt.

[0027] A diprotic compound is defined as a compound capable of donating two H+ ions. + to its environment.

[0028] Alkyl or alkoxyl radicals are notably C1-C radicals 10, cycloalkyl radicals are notably C3-C8 cycloalkyl radicals, cycloalkyl-alkyls are notably C3-C8 cycloalkyl radicals linked to a C1-C8 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] Heteroaromatic radicals are based on pyridines, of the pyridinyl radical type, or derived from pyridine derivatives such as picolines (methylpyridines), ethylpyridines, or lutidines (dimethylpyridines).

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

[0032] In formula (I), at least one among R A , R B and R Cmay 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 R A and R C can be chosen independently from: C(=O)C m H 2m+1 with m ≤ 10, where m is an integer, C(=O)C m H 2m-1 with m ≤ 10, where m is a non-zero integer, C(=S)C m H 2m+1 with m ≤ 10, where m is an integer, C(=S)C m H 2m-1 with m ≤ 10, where m is a non-zero integer,C m H 2m+1 with m ≤ 10, where m is a non-zero integer,C m H 2m-1 with m ≤ 10, where m is a non-zero integer, (CH2) m C q F 2q+1 with m ≤ 6, where m is a non-zero integer, and where q ≤ 4, (CH2) m C p H q F r Cl s Br twith 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,

[0034] and the constituent radical R B can be a radical chosen from: C(=O), C(=S), -CH2CH2-, , ,

[0035] where at least one of the radicals R D , R E and R F is chosen from among the following halogens or electron-withdrawing groups: F, Cl, Br, C m F 2m+1 with m ≤ 4, where m is a non-zero integer, CF2CF2C p H 2p+1 with p ≤ 4, where p is an integer, CF2C p H 2p+1 with p ≤ 4, where p is an integer, CH2C p F 2p+1 with p ≤ 4, where p is an integer, OCF3, OCH2CF3, SCF3, C(=O)CF3, NO2, C m H n F p Cl q Br s with m ≤ 4, where n, p, q, s are integers of which at least p, q or s is non-zero, C(=O)OC m H 2m+1 with m ≤ 4, where m is an integer, C(=O)C m H 2m+1with m ≤ 4, where m is an integer, and S(=O)C m H 2m+1 with m ≤ 4, where m is an integer,

[0036] the other radical(s) R D , R E , R F and the radicals R G can be chosen, identical or different, from among the following non-electromagnetic atoms or groups: H, CH3, CH2CH3, C3H7, CH2CH2C p F 2p+1 with p ≤ 4, where p is an integer,C m H 2m-1 with m ≤ 10, where m is a non-zero integer, andC m H 2m+1 with m ≤ 10, where m is a non-zero integer; where only one of the radicals R D to R G maybe one of these last two radicals C m H 2m-1 or C m H 2m+1 , for m ≥ 4.

[0037] The alkyl radical that is part of the definition of R A or R C or R A,Ccan 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 that is part of the definition of R A or R C or R A,C may represent one of the following: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopentylmethyl or cyclohexylmethyl.

[0039] The compound with formula (I) can 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-N1,N2-diphenyl-1,2-benzenediamine,

[0049] 4-chloro-N1-(1-methylethyl)-N2-phenyl-1,2-benzenediamine,

[0050] 4-fluoro-N2-(4-fluorophenyl)-N1-(1-methylethyl)-1,2-benzenediamine,

[0051] 4,5-dichloro-N1-(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-1,2-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-N1,N3-bis(4-butylphenyl)-1,3-benzenedicarboxamide,

[0059] 5-bromo-N1,N3-bis[3-(trifluoromethyl)phenyl]-1,3-benzenedicarboxamide,

[0060] N1,N3-bis(3,4-difluorophenyl)-1,3-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] N,N′-(4,5-dibromo-1,2-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′-ethylenebis[3,4-dichlorobenzamide].

[0073] The expanded formulas of the above compounds are shown below (cis-cis form in particular).

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

[0075] in which: R1 and R2, identical or different, are, regardless of their position on a nitrogen atom, independently chosen from among C1-C alkyl groups 12linear or branched, aryl, C3-C8 cycloalkyl; or R1 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 C1-C8 alkyl, C3-C8 cycloalkyl, C2-C6 alkoxyalkyl and alkoxyalkylaryl; R4 is chosen from hydrogen, linear or branched C1-C3 alkyl; R5 is chosen from hydrogen, linear or branched C1-C3 alkyl; and R6 is chosen from hydrogen, linear or branched C1-C3 alkyl.

[0076] In a particular embodiment: R1 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 R1 and R2, taken together with the nitrogen atom to which they are attached, 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, isopentyl, 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] R1 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 the selectivity Li + / That 2+ is privileged; and

[0078] R1 and R2 being advantageously chosen from isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 2-ethylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or R1 and R2, taken together with the nitrogen atom on which they are borne, 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 selectivity Li + / N / A + is preferred.

[0079] In a particular embodiment, the cation extractant(s) may be chosen from the following compounds:

[0080] 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.

[0081] In one embodiment, the cation extractant(s) may be chosen from compounds of formula (III) or formula (IV):

[0082] where n is an integer from 4 to 8, p is 1 or 2, m is 3 or 4, q and t, 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 ring, Piperidine or morpholine.

[0083] In a particular embodiment of compounds of formula (III), p=1 and R, R', R'' and n are defined below:

[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):

[0086] where: n is 4, 5 or 6; p is 1 or 2; m is 2 or 3; q and t, 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=1 and R, R' and n are defined below:

[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-O,O',O'',O'''-tetraacetic acid and the pentaethyl ester of 4-tert-butylcalix[5]-arene-O,O',O'',O'''-pentaacetic acid.

[0089] In one embodiment, the cation extractant(s) may be chosen from a crown ether, in particular a crown ether having 14 to 80 carbon atoms, especially chosen 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 No. 151460-02-5), 2,3,5,6,8,9,11,12-Octahydro-14-pentadecyl-1,4,7,10,13-benzopentaoxacyclopentadecin (3′-pentadecylbenzo-15-crown-5-ether, 88037-72-3), tetradecahydro-7-tetradecyl- 4a,20a:11a,15a-Dibutano-17H-dibenzo[b,k][1,4,7,10,13]-pentaoxacyclohexadecin (tetradecyl-didecalino-16-crown-5-ether, Cas n° 172883-31-7), 2,2,3,3,11,11,12,12-Octamethyl-6-tetradecyl-1,4,7,10,13-pentaoxacyclohexadecane (octamethyl-nC14-16-crown-5-ether, Cas no. 172883-30-6), Eicosahydrodibenzo[b,k][1,4,7,10,13,16]hexaoxacyclooctadecin (Dicyclohexano-18-crown-6-ether, Cas No. 16069-36-6), octadecahydro- 4a,24a:8a,12a:16a,20a-Tributanotribenzo [b,h,n][1,4,7,10,13,16]hexaoxacyclooctadecin (Tridecalino-18-crown-6-ether, Cas No. 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 No. 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 (also known as Dicyclohexylcryptand[2.2.2] CAS No. 84731-60-2), 5,6,14,15-dibenzo-4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane (also known as Dibenzocryptand 222, CAS No. 40471-97-4) and 5-decyl-4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane (CAS No. 69878-46-2).,

[0090] The use of some of these extractants allows, within the framework of the invention, the selective extraction of lithium, sodium, potassium or ammonium salts or the extraction of other cation salts that may be suitable for these extractants.

[0091] The present invention employs diluents that are quite unusual compared to the state of the art in conventional liquid-liquid ion-exchange extraction, which uses complex mixtures derived from petroleum distillation based on long-chain C10-C20 aromatic and / or parafin hydrocarbons. Instead, it considers hydrophobic, polar organic diluents, particularly polar aromatic diluents, due to their superior ability to solubilize salts when combined with solvating molecules for anions and / or cation extractants. Furthermore, operational safety has been prioritized for this hot-water solvent regeneration process by using an upper aqueous phase with a diluent denser than the brine being treated or produced.

[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, chemically and thermally stable (extended pH range from 2 to 12, and up to 120-150°C), and suitable for safe implementation, both for operators and the environment (aquatic, flora and fauna).

[0093] The hydrophobic polar organic diluent(s) may be selected from bromochlorobenzenes, bromochlorotoluenes, bromochlorooxylenes, bromochloroethylbenzenes, bromochloropropylbenzenes, bromochloroisopropylbenzenes, bromochlorobutylbenzenes, bromoalkyloxybenzenes, bromophenyl ketones, bromophenyl esters, 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, 2-bromo-1-chloro-4-ethoxybenzene, the 2-bromo-4-(2-methylpropyl)-1-(trifluoromethyl)benzene, 1-bromo-3-ethylbenzene, 1-bromo-3,5-dimethylbenzene, 3,4-dichlorotoluene, 1-ethyl-2-nitrobenzene, 1-Bromo-4-propoxybenzene, 2'-Bromoacetophenone and 1-bromo-2-chlorobenzene.

[0094] Hydrophobic polar organic diluents according to the invention are listed below by way of non-limiting examples:

[0095] The following diluents may also be considered: 1-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), 1-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), 1-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 1-bromo-2-chlorobenzene (Cas n°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 salt metals.

[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) may 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] Solvent regeneration with water at room temperature can also be carried out, but 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 atoms, 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 mixed functional groups, for example, allows for doubling 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 enhanced when the NH₄⁺ bond is activated by the nearby presence of an aryl group preferentially substituted at 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 salt transfer 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) from 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 being studied, this can simply be modeled by a Langmuir isotherm, which is modeled by:

[0106] or by (1)

[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. being known by design of the organic formulation.

[0108] This equation shows that the partitioning of lithium towards the organic phase is greater the higher the product K Henry .b, or that is raised with, by equivalence K Henry =b , and where :K Henry 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 curve is a straight line with slope K). Henry ) ; And is the concentration in cationic extractant EC (C EC ) in the organic phase, corresponding to the maximum concentration of lithium in the organic phase for a 1:1 type complexation (Host:Guest).

[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 = (2)

[0111] Thus, monitoring the K parameters Henry , b, and the K products Henry .b, or 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 allow for the increase of K products Henry .b, or by a factor of approximately 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: room temperature; TF: melting or freezing point; P o / w : oil / water partition coefficient Calc: calculated S: solubility in water 2CBB: 2-bromochlorobenzene (C6H4BrCl, CAS 694-80-4; 191.45 g / mol; liquid density 1.656 g / cm³) 3 (at 20°C) OAc: acetate ion DCM: dichloromethane TEA: triethylamine A / O: aqueous to organic volume ratio

[0115] Example 1a: Description of the MSA and MSA2H used

[0116] The aliphatic amines considered for the construction of these MSA2H are preferentially chosen from among those that provide sufficient hydrophobicity to the target molecule while having a very low solidification / melting point (MPP). This is generally possible by choosing branched aliphatic chains, such as 2-ethylhexylamine (C8H2H2O). 19 N, CAS: 104-75-6, TF = -76°C,) 2,4,4-trimethyl-2-pentanamine (C8H 19 N, TF = -66.9°C, 107-45-9,), 6-methyl-2-heptanamine (C8H 19 N, 543-82-8), isooctylamine (C8H 19 N, 1321-35-3, 44855-53-0), 2,5-dimethyl-1-hexylamine (C8H 19 N, 74038-59-8), isoheptylamine (C7H 17 N, 4746-31-0), 2,4-dimethyl-1-pentanamine (C7H 17 N, 146845-08-2), 2-amino-2,3-dimethylbutane (C6H 15 N, 4358-75-2, TF = -70.5°C), isohexylamine (C6H 15N, 5344-20-7, TF= -94.4°C), or 2-methyl-1-pentanamine (C6H 15 N, 13364-16-4, TF = -40.7°C).

[0117] All of these amines have low melting points compared to octylamine (C8H 19 N, 111-86-4, TF = 0°C), heptylamine (C7H 17 N, 111-68-2, TF = -23°C) or hexylamine (C6H 15 N, 111-26-2, TF = -21.3°C) corresponding to molecules with linear chains, and therefore unbranched as before. These low TF values ​​also allow for lowering the TF of synthesized ureas, thioureas, amides, thioamides, or amines, while improving their corresponding solubility range for the hydrophobic aromatic polar diluents considered.

[0118] 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]

[0120] As an 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:

[0121] a IUPAC reference, *Estimate, x Too small to be measured, / not evaluated, See publications of F. Arnaud-Neu et al. 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] NMR 1 H (CDCl3): 0.86 (t, 3H), 1.23 (sl, 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 temperature 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 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 as an off-white solid with a yield of 54% (8.53 g). TF: 51°C.

[0130] NMR 1 H (CDCl3): 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] NMR 1 H (CDCl3): 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 as follows:

[0137] In a 1 L argon-filled round-bottom 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 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] NMR 1H (CDCl3): 0.85 – 0.93 (m, 6H), 1.25 – 1.31 (m, 8H), 1.35 (m, 1H), 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:

[0143] In a 250 mL round-bottom 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 hours. The mixture was washed with 30 mL of water followed by 30 mL of a saturated sodium chloride solution. 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] NMR 1 H (CDCl3): 0.89 (t, 6H, 3J = 7.4 Hz), 0.95 (t, 6H, 3 J = 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 chosen for these tests is 2CBB. The chosen ECM is ECM-1, namely Lithium Ionophore VIII, characterized by a moderate lithium complexation constant, which allows for better discrimination of the relative performance of the different anion-solvating molecules.

[0151] 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]

[0155] With R 1 and R 2 representing a cyclohexyl and R 3 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 initial ketone. Evaporate the solvent (and sometimes any residual amine) under reduced pressure. Filter, if necessary, through Fontainebleau sand, then add methanol (12 volumes). Add NaBH4 (30 mmol, 3 eq) in portions. Be careful of gas evolution; an ice bath may be necessary. Stir for 1–15 hours at room temperature or room temperature, as appropriate.

[0157] Add 1M NaOH 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]

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

[0162]

[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. While still hot, introduce triol dissolved in 10 volumes of THF, followed by the synthesized chloroacetamide dissolved 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 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.

[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:

[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, with concentrations of 25, 50, 100, and 250 mmol LiCl / L, respectively, and spiked with 1.5 mol MgCl2 / L using MilliQ water. Meanwhile, the formulations that had been stirred overnight were allowed to settle. The two colorless phases separated completely within a few minutes. Three mL of each of the various organic extraction solutions were then transferred to a flask containing 3 mL of one of the four prepared LiCl / MgCl2 saline solutions (A / O=1). The flask was then sealed and placed under orbital shaking (generally at 800 rpm) for two hours at room temperature. It was verified that droplets of approximately 1–2 mm in size were present in sufficient quantity at the chosen shaking speed (400–900 rpm).

[0170] After two hours of stirring, the mixture was stopped and 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 using a Metrohm ion chromatograph equipped with a suitable cation and anion analysis column. Similarly, the initial aqueous LiCl / MgCl2 solutions were also analyzed by this ion chromatograph to determine their relative concentrations of lithium, magnesium, and chloride.

[0171] To duplicate the measurement and validate the desorbability of LiCl in the studied formulation 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 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 presented on the graph with the lithium concentration 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 asymptote up to this value at very high lithium concentrations 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). Furthermore, the extraction performance generally increases 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 were quantified and are given in the following tables:

[0175] We observe a factor of 8 between the best MSA-8 and the MSA2H-4 for the value of 1000.K H .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 monochlorinated aromatic ring, there is a 52.94% increase in absorption capacity, while between MSA-7 amide and MSA2H-3 urea, both with the same dichlorinated aromatic ring, there is a 23.35% increase in absorption capacity. 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 generally maintained 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, spiked 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 2CBB diluent.

[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 in water before and after extraction) are summarized in the following Table and Figures 4 and 5:

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

[0182] It appears that for the highest-performing MSAs (MSA2H), the standard 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 anion hydrophilicity on extraction performance

[0184] The extraction performance of a lithium salt is evaluated here as a function of the associated anion for both MSA-7 and MSA2H-4, and for the following salts ranked in ascending order of anion hydrophilicity: LiPF6, LiClO4, LiI, LiNO3, LiBr, LiCl, LiOAc, Li2SO4, Li2C2O4, Li2SiO3 and Li2CO3.

[0185] This hydrophilicity is generally characterized by the free enthalpy of hydration of the anion, ΔG° 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] 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 extracted lithium salts 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:

[0190] *Value not measured,x Lowest value not considered a Estimated value.

[0191] 1 Data from various publications by: Yizhak Marcus,

[0192] b Other literature, c Ionic 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 extractant with a higher complexation constant Log K(MeOH, 25°C) further improves the extractability of salts and thus enables the industrial extraction of sulfate salts and, more generally, salts with divalent anions.

[0195] Example 10: Impact of the choice of 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 improves the extraction performance of salts associated with these cations and mono-charged hydrophilic anions (-) and allows, by combination with ECMs with Log K(MeOH, 25°C) > 1.4, the extraction of salts with divalent anion (2-).

[0198] The two isotherms shown here demonstrate that using the extractant MEC-6 (log K(Li + (MeOH, 25°C) = 4.0), associated with MSA2H-4 (0.15 mol / L MEC / 1.0 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 extractant 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] MEC-6 was chosen here because it has the highest lithium complexation constant among 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:

[0204] Magnesium is not indicated because 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 entirety of the absorbed LiCl to be desorbed and that MSA-7, MSA2H-1 and MSA2H-4 all three 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 for the initiation of Li2SO4 extraction, and that this extraction increases with the MSA2H concentration. Thus, a saline solution containing 100 mmol / L of Li2SO4 (200 mmol / L of Li2SO4) was considered. + ), doped with 1.5 mol / L of MgSO4, 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 2CBB diluent.

[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:

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

[0212] Although 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 Li2SO4 via formulations incorporating MEC-6

[0214] This example, through the combination of MSA2H with maximum anion solvation and MEC-6 with a Log K complexation constant of 4.0, demonstrates a very promising performance for enabling industrial application of Li2SO₄ extraction 4.

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

[0216] This example demonstrates that the performance difference in extraction between MSA and MSA2H is generally maintained until extraction saturation is reached, regardless of the relative concentration between MSA and MEC-6. Thus, a saline solution containing Li2SO4 (200 mmol / L of Li) was considered. + ), doped with 1.5 mol / L of MgSO4, 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:

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

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

[0221] Example 14: Measurement of Li2SO4 absorption isotherms 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 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 pure Li2SO4 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:

[0226] The equilibrium isotherms for Li2SO4 extraction at 20°C obtained are presented in the.

[0227] It appears that with this new family of two-hydrogen anionic solvator molecules, the extraction of Li2SO4 becomes industrially possible, even with an extractant, 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 for each formulation). Furthermore, the extraction performance is generally improved at higher MEC-1 concentrations and by increasing the MSA2H-4 / MEC-1 ratio.

[0229] The Langmuir parameters obtained for these isotherms in mg / L were quantified and are given in the following table:

[0230] While the extraction of pure LiCl naturally remains higher than the extraction of Li2SO4, it has been observed that the presence of the anion solvent MSA2H-4 allows for the extraction of Li 2SO4convenable et significative pour sa mise en œuvre au niveau industriel.

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

[0232] Three new formulations according to the invention were 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 was 2-chlorobromobenzene (2CBB, C6H4BrCl, CAS 694-80-4). The cation extractant molecule was MEC-1, and the MSAs considered were MSA2H-6, MSA2H-7, and MSA2H-8, to obtain a formulation with 0.1 mol / L MEC-1 and 0.5 mol / L 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:

[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 MSA2H compounds performed 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 the...

[0237] It appears here that the extraction performance for these MSA families is all the greater when the MSA possesses electron-deficient hydrogen NH groups and when these groups are further activated by the presence of several halogens and / or electron-withdrawing groups in R positions D , RE and / or R F .

[0238] Example 16: Comparative extractions of substituted ortho-phenylenediamine anion-based solvating molecules, MSA2H-9 to MSA2H-12, compared to MSA2H-6 to MSA2H-8 already presented.

[0239] In addition to the three formulations already presented, four new formulations incorporating 0.1 mol / L of MEC-1 and 0.5 mol / L of MSA2H according to the invention were composed and tested for the extraction of LiCl and Li2SO4 from two aqueous saline compositions of LiCl / MgCl2 and Li2SO4 / MgSO4 having respectively 200 mmols of LiCl / L, doped with 1.5 moles of MgCl2 / L and 100 mmols of Li2SO4 / L doped with 1.5 moles of MgSO4 / L.

[0240] The diluent that was selected for these tests is 2-chlorobromobenzene (2CBB, C6H4BrCl, CAS 694-80-4).

[0241] The MSA2H-9 to MSA2H-12 tested in this example are based on orthophenylenediamine and are described according to the following general formula:

[0242] Where R1 and R2 are chosen from hydrogen H or an electron-withdrawing group, here a halogen, and where R A and R C are chosen from a substituted aromatic or a 1-ketone radical for the construction of amide functions, as seen in the previous examples and summarized in the table below: SAR Identifier A R B R c R1R2MSA2H-61-(2-ethylhexanone)HH1-(2-ethylhexanone)MSA2H-71-(2-ethylhexanone)ClH1-(2-ethylhexanone)MSA2H-81-(2-ethylhexanone)ClCl1-(2-ethylhexano) ne)MSA2H-91-(2-ethylhexyl)ClCl1-(2-ethylhexyl)MSA2H-10PhenylHHPhenylMSA2H-11PhenylClClPhenylMSA2H-121-(3,4-dichlorophenyl)HH1-(3,4-dichlorophenyl)

[0243] The volumes and masses of diluent and the masses of MSA2H and MEC-1 in the different formulations (5 mL) are summarized in the following table: Reference SAVol 2CBB (mL)m 2CBB(g)m MSA(g)m MEC-1 (g)MSA2H-63,7516,1850,9010,399MSA2H-73,7216,1360,9870,399MSA2H-83,6916,0861,0740,399MSA2H-93,6776 ,0631,0040,399MSA2H-104,0846,7340,6510,399MSA2H-114,0246,6350,8230,399MSA2H-123,9646,5360,9950,399

[0244] The procedure presented in Example 7 is repeated for the preparation of seven extraction points from salt water composed of 0.2 mol LiCl / L and doped with 1.5 mol MgCl2 / L, produced from MilliQ water. This chloride anion saline water was measured at 1368 mg Li / L and 34030 mg Mg / L.

[0245] Similarly, the procedure presented in Example 7 is repeated for the preparation of seven other extraction points from salt water composed of 0.1 mol Li2SO4 / L and spiked with 1.5 mol MgSO4 / L, produced from MilliQ water. This sulfate anion saline water was measured at 1370 mg Li / L and 34052 mg Mg / L.

[0246] The experimental results of these 14 experiments are summarized in the following table, which includes the extraction of LiCl in the first three rows and the extraction of Li2SO4 in the following three. MSA2H6789101112C(Li)aq (mg / L)954809736135312781023863C(Li)org (mg / L)4145596291590345505MSA2H6789101112C(Li)aq (mg / L)1363135813651365136013601360C(Li)org (mg / L)71255101010

[0247] It appears here that these orthophenylenediamine-based MSA2H exhibit a significantly increased LiCl extraction performance when aromatic groups are substituted by the addition of one or two chlorides, both on the central aromatic R B via a comparison of extraction performance between MSA2H-6, MSA2H-7 and MSA2H-8, or between HSA2H-10 and MSA2H-11, than on the side phenyls R A and / or R C where a disubstituted phenyl is made according to MSA2H-12.

[0248] MSA2H-8 has the best LiCl extraction performance achieved with 629 mg Li / L org., i.e. 90.63 mM or 90.63% of the saturation of the extractant (100 mM of MEC-1), shown here below.

[0249] However, this family of anionic solvents is not suitable for the extraction of Li2SO4, which is too hydrophilic.

[0250] Example 17: Comparative extractions of substituted meta-phenylenediamine anion-based solvating molecules, MSA2H-13 to MSA2H-18.

[0251] Six new formulations incorporating 0.1 mol / L of MEC-1 and 0.5 mol / L of MSA2H according to the invention were composed and tested for the extraction of LiCl and Li2SO4 for the same saline compositions of Example 16.

[0252] The diluent that was selected for these tests is 2-chlorobromobenzene (2CBB, C6H4BrCl, CAS 694-80-4).

[0253] The MSA2H-13 to MSA2H-18 tested in this example are based on metaphenylenediamine and are described according to the following general formula:

[0254] Where R1 is chosen from hydrogen H or an electron-withdrawing group, here a halogen, and where R A and R Care chosen from a substituted aromatic or a 1-ketone radical for the construction of amide functions, as seen in the previous examples and summarized in the table below: SAR Identifier A R B R c R1MSA2H-131-(3-chlorophenyl)Cl1-(3-chlorophenyl)MSA2H-141-(3,4-dichlorophenyl)H1-(3,4-dichlorophenyl)MSA2H-151-(2- ethylhexanone)H1-(2-ethylhexanone)MSA2H-161-(1-hexanone)Cl1-(1-hexanone)MSA2H-17PhenylHPhenylMSA2H-18PhenylClPhenyl

[0255] The volumes and masses of diluent and the masses of MSA2H and MEC-1 of the different formulations (5 mL) are summarized in the following table: Indicative SAVol 2CBB (mL)m 2CBB (g)m MSA(g)m MEC-1 (g)MSA2H-133.9946.5860.9090.399MSA2H-143.9646.5360.9950.399MSA2H-154.6397.6490.9010.399MSA2H-164.6397.6490.8470.399MSA2H-174.0846.7340.6510.399MSA2H-184.0546.6850.7370.399

[0256] Following the same procedure and the same salt water as Example 16, six extraction points were made from salt water composed of 0.2 mole LiCl / L and doped with 1.5 mole MgCl2 / L.

[0257] Similarly, using the same procedure and the same salt water as Example 16, six other extraction points were made from salt water composed of 0.1 mole Li2SO4 / L and doped with 1.5 mole MgSO4 / L.

[0258] The experimental results of these 12 experiments are summarized in the following table, with the first three rows relating to LiCl extraction and the following three rows relating to Li2SO4 extraction. MSA2H Index 13 14 15 16 17 18 C(Li)aq (mg / L) 10 5 8 9 23 13 0 39 5 0 12 8 3 11 68 C(Li)org (mg / L) 3 10 4 4 5 6 5 4 18 8 5 2 0 0 MSA2H Index 6 7 8 9 10 11 C(Li)aq (mg / L) 13 7 0 13 6 5 13 6 8 13 6 0 13 7 0 13 70 C(Li)org (mg / L) 0 5 2 1 0 0

[0259] It appears here that these MSA2H based on metaphenylenediamine can achieve a good level of LiCl extraction performance when the two amines are substituted by a disubstituted phenyl group according to the MSA2H-14 presented below:

[0260] MSA2H-16 also exhibits a good level of LiCl extraction via a double straight-chain amide function below, whereas the branched version shows very low LiCl extraction performance.

[0261] As with example 16, this family of anionic solvatants is not suitable for the extraction of Li2SO4, being too hydrophilic.

[0262] Example 18: Comparative extractions of solvating molecules of anions based on a urea or a thiourea, MSA2H-19 to MSA2H-33 by comparison to MSA2H-1 to MSA2H-4 already presented.

[0263] In addition to the four formulations already presented, fifteen new formulations incorporating 0.1 mol / L of MEC-1 and 0.5 mol / L of MSA2H according to the invention were composed and tested for the extraction of LiCl and Li2SO4 for the same saline compositions of Example 16.

[0264] The diluent that was selected for these tests is 2-chlorobromobenzene (2CBB, C6H4BrCl, CAS 694-80-4).

[0265] The MSA2H-19 to MSA2H-33 tested in this example are urea- or thiourea-based and described according to the following general formula:

[0266] Where R1, R2 and R3 are chosen from hydrogen H or an electron-withdrawing group, here from the halogens F, Cl, Br or I, where X is oxygen O or sulfur S, and where R C is chosen from among the alkyl chains, branched or unbranched, as seen in the previous examples and summarized in the table below: SAR identifier A R B R cR1R2R3XMSA2H-1HHClOoctylMSA2H-2HHClO1-(2-ethylhexyl)MSA2H-3HClClOoctylMSA2H-4HClClO1-(2-ethylhexyl)MSA2H-19HHHOoctylMSA2H-20HHHO1- (2-ethylhexyl)MSA2H-21HHIO1-(2-ethylhexyl)MSA2H-22HHBrO1-(2-ethylhexyl)MSA2H-23HHFO1-(2-ethylhexyl)MSA2H-24HIHO1-(2-ethylhexyl)MSA 2H-25HBrHO1-(2-ethylhexyl)MSA2H-26HClHO1-(2-ethylhexyl)MSA2H-27HFHO1-(2-ethylhexyl)MSA2H-28HBrBrO1-(2-ethylhexyl)MSA2H-29HFFO1-(2- ethylhexyl)MSA2H-30FHFO1-(2-ethylhexyl)MSA2H-31ClClClO1-(2-ethylhexyl)MSA2H-32ClHClS1-(2-ethylhexyl)MSA2H-33HClClS1-(2-ethylhexyl)

[0267] The volumes and masses of diluent and the masses of MSA2H and MEC-1 in the different formulations (5 mL) are summarized in the following table: Reference SAVol 2CBB (mL)m 2CBB (g)m MSA (g)m MEC-1 (g)MSA2H-13.9906.5800.7070.399MSA2H-23.9896.5780.7070.399MSA2H-33.9606.5310.7930.399MSA2H-43.9596.5290.7930.399MSA2H-194.0206.6290.6 210,399MSA2H-204,0196,6280,6210,399MSA2H-213,9646,5360,9360,399MSA 2H-223,9796,5610,8180,399MSA2H-234,0096,6100,6660,399MSA2H-243,9646 ,5360,9360,399MSA2H-253,9796,5610,8180,399MSA2H-263,9896,5780,7070 ,399MSA2H-274,0096,6100,6660,399MSA2H-283,9386,4941,0150,399MSA2H-2 93.9986.5930.7110.399MSA2H-303.9986.5930.7110.399MSA2H-313.9296.47 90,8790,399MSA2H-323,9406,4960,8330,399MSA2H-333,9406,4960,8330,399

[0268] Following the same procedure and the same salt water as Example 16, nineteen extraction points were made from salt water composed of 0.2 mole LiCl / L and doped with 1.5 mole MgCl2 / L.

[0269] Similarly, using the same procedure and the same salt water as Example 16, nineteen other extraction points were made from salt water composed of 0.1 mole Li2SO4 / L and doped with 1.5 mole MgSO4 / L.

[0270] These MSA2H based on urea or thioureas confirm the excellent performance of this family of anionic solvatants for the extraction of salts in general, and in particular of LiCl, and to a lesser extent, of Li2SO4.

[0271] The experimental results of these 38 experiments are summarized in the following two tables, relating respectively to the extraction of LiCl and then Li2SO4. MSA2H indices: 1234192021222324C(Li)aq (mg / L)810786787794902869782792780811C(Li)org (mg / L)560584583576468501588578590559MSA2H indices: 252627282930313233C(Li)aq (mg / L)810812826823810754799758776C(Li)org (mg / L)560558544547560616571612594 MSA2H1234192021222324C(Li)aq (mg / L)1249133712281225134913641354134313281333C(Li)org (mg / L)1213314214521616274237Indices MSA2H252627282930313233C(Li)aq (mg / L)132713281338127812781282121113501361C(Li)org (mg / L)434232929288159209

[0272] It appears here that, compared to non-halogenated MSA2H-19 and MSA2H-2H, the introduction of electron-withdrawing groups allows for a gain of up to 30% in LiCl extraction performance with a high solvate density above 550 mg Li / L in the organic phase, for a maximum performance of 616 mg Li / L org., i.e., 88.76 mM or 88.76% of the extractant saturation (100 mM of MEC-1) for MSA2H-30 incorporating two fluorines in meta as presented below:

[0273] This family is the most efficient for the extraction of Li2SO4, which is much more hydrophilic. MSA2H-31 is the most efficient in this case, with three chlorine atoms in R1, R2, and R3, but remains 3.9 times less efficient in lithium extraction capacity.

[0274] Finally, it should be noted that the two thiourea-type molecules, MSA2H-32 and MSA2H-33, are among the most efficient in LiCl extraction but see their extraction performance collapse for Li2SO4, generating a selectivity of 98% for Chloride anions compared to sulfates with a gain of 22% in LiCl extraction capacity compared to the also very selective NSA2H-20.

[0275] Within the framework of the invention, asymmetric anionic solvatants are preferred due to their improved ability to be dissolved in CBB and other polar hydrophobic aromatic solvents as shown in the following example.

[0276] Indeed, a dozen synthesized MSA2H symmetrical solvatants could not be solubilized at 100 mmole / L in CBB at room temperature.

[0277] Example 19: Comparative extractions using diluents D-1 to D-20 for formulations composed of MEC-1 associated with MSA-7 or MSA2H-4.

[0278] Twenty new formulations incorporating 0.1 mol / L of MEC-1 and 0.5 mol / L of MSA-7 for twenty diluents D-1 to D-20 were composed and tested for the extraction of MgCl2-doped LiCl for the same saline composition of Example 16.

[0279] In addition, seven new formulations incorporating 0.1 mol / L of MEC-1 and 0.5 mol / L of MSA2H-4 for a selection of seven of the twenty diluents were composed and tested for the extraction of MgSO4-doped Li2SO4 for the same saline composition of Example 16.

[0280] The diluents D-1 to D-16 tested in this example are based on an aromatic group and described according to the following general formula:

[0281] Where R1, R2, R3 and R4 are chosen from hydrogen (H) or an electron-withdrawing group, such as halogens (F, Cl, Br or I), or carbonyl-ketone, carbonyl-ester, oxy-ether radicals, or from alkyl chains, branched or unbranched, as summarized in the table below: Indicative DiluentR1R2R3R4D-1BrClHHD-2ClClHHD-3IHHHD-4BrHHn-propoxyD-5BrClHmethylD-61-acetylBrHHD-7ClHHHD-8BrHHpentylD-9ClHClHD-10methylmethylHHD-11BrHHisopropylD-12m ethoxymethoxyHHD-131-methoxy-carbonylHBrmethylD-141-pentanoneHHHD-15CF3H-CH2CNHD-161-butoxy-carbonylHHHD-174-heptanoneD-182,6-Dimethyl-4-heptanoneD-19methyl octanoateD-20Dodecane

[0282] The volumes and masses of diluent and the masses of MSA-7 and MEC-1 for the twenty prepared formulations (5 mL) for the different diluents are summarized in the following table: Indicative Diluent Vol DX(mL)m DX(g)m MSA-7(g)m MEC-1(g)D-14,0236,6500,7210,399D-23,9975,2200,7210,399D-34, 0387,3620,7210,399D-43,9235,3210,7210,399D-54,0116,1770,7210 ,399D-63,9565,8390,7210,399D-74,0384,4660,7210,399D-84,0194, 8620,7210,399D-94,0535,2200,7210,399D-103,9883,5010,7210,399 D-114,0015,1450,7210,399D-123,7324,0460,7210,399D-133,9245,7 680,7210,399D-143,9143,8280,7210,399D-154,2094,9960,7210,399 D-164,0124,0560,7210,399D-173,9833,2540,7210,399D-184,0523,2 700,7210,399D-194,0343,5250,7210,399D-204,0353,0220,7210,399

[0283] The volumes and masses of diluent and the masses of MSA2H-4 and MEC-1 for the seven prepared formulations (5 mL) for the different diluents are summarized in the following table: Indicative Diluent Vol DX(mL)m DX(g)m MSA2H-4 (g)m MEC-1 (g)D-13,9806,5430,7930,399D-43,8615,2360,7930,399D-53,9476,0780,7930,399D-63,8935,7 460,7930,399D-83,9544,7850,7930,399D-113,9375,0630,7930,399D-133,8615,6760,7930,399

[0284] Following the same procedure and the same salt water as Example 16, twenty extraction points were made from salt water composed of 0.2 mole LiCl / L and doped with 1.5 mole MgCl2 / L.

[0285] Similarly, using the same procedure and the same salt water as Example 16, seven other extraction points were made from salt water composed of 0.1 mole Li2SO4 / L and doped with 1.5 mole MgSO4 / L.

[0286] The experimental results of these 27 experiments are summarized in the following two tables, relating respectively to the extraction of LiCl and then Li2SO4. Indices Diluents 12 34 56 78 910 C(Li)aq (mg / L) 875 890 898 90 891 194 4978 1000 997 1009 C(Li)org (mg / L) 492 476 46 846 145 642 53 883 693 693 57 Indices Diluents 11 12 13 14 15 16 17 18 1920 C(Li)aq (mg / L) 10 14 10 14 103 110 30 103 107 71 124 1125 114 313 62 C(Li)org (mg / L)3533523383363362892422412234Diluent Indices145681113C(Li)aq (mg / L)1268126912971261132813391318C(Li)org (mg / L)1129183100324142

[0287] It appears here that dodecane (D-20), a classic diluent for liquid-liquid ion-exchange extraction, does not allow salt extraction even in the presence of an extractant or a solvator. For this to occur, the diluent must have sufficient polarity. Thus, ester D-19 and ketones D-17 and D-18 achieve 223-242 mg Li / L of organic phase in LiCl extraction. Subsequently, replacing one of the alkyl chains with a phenyl group increases the yield to 289-336 mg Li / L via n-butyl benzoate D-16 and valerophenone D-14.

[0288] The highest LiCl extraction performance is obtained with polar aromatic diluents by the presence of one or even two electron-withdrawing groups, ideally positioned in ortho for greater destabilization of the delocalized electron cloud.

[0289] The purpose of this example is to demonstrate that 2-chlorobromobenzene (2CBB, C6H4BrCl, CAS 694-80-4) is not the only diluent with industrial application potential, but that a variety of diluents can be considered within the scope of this invention. For example, diluents from the 1-Bromo-4-propoxybenzene (C9H4BrCl) family could be considered. 11 BrO, CAS 39969-56-7, H317-H319) or 2'-Bromoacetophenone (C8H7BrO, CAS 2142-69-0, H315-H319) and many others can be considered to enable liquid-liquid salt extraction.

Claims

– Hydrophobic organic liquid composition for the extraction, from salt water or brine, of a monovalent or divalent salt, comprising a cation and an anion complementary to the cation, said composition comprising: at least one cation-extracting organic compound having a Log K complexation constant for this cation in methanol at 25°C of at least 1; at least one hydrophobic, diprotic organic compound solvating the anion complementary to the cation; and at least one hydrophobic polar organic diluent having a flash point above 60°C, characterized in that component(s) (B) is or are selected from compounds of formula (I): (I) in which: R A and R C each independently represent one of the following: a monovalent aromatic or heteroaromatic radical, possibly substituted; a radical , where X 1 represents O or S and R A,Crepresents 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 R B represents one of: a divalent aromatic or heteroaromatic radical, possibly substituted; a radical , where X 2 represents O or S; an ethylene radical –CH2-CH2-; and a radical where X 3 represents O or S and Q represents a divalent aromatic or heteroaromatic radical, possibly substituted. – 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. – Composition according to claim 1 and 2, characterized in that, in formula (I), at least one of R A , R B and R C represents 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. – Composition according to any one of claims 1 to 3, characterized in that the radicals constituting R A and R C are chosen independently from: , ,C(=O)C m H 2m+1 with m ≤ 10, where m is an integer, C(=O)C m H 2m-1 with m ≤ 10, where m is a non-zero integer, C(=S)C m H 2m+1 with m ≤ 10, where m is an integer, C(=S)C m H 2m-1 with m ≤ 10, where m is a non-zero integer,C m H 2m+1 with m ≤ 10, where m is a non-zero integer,C m H 2m-1with m ≤ 10, where m is a non-zero integer, (CH2) m C q F 2q+1 with m ≤ 6, where m is a non-zero integer, and where q ≤ 4, (CH2) m C p H q F r Cl s Br t 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 radical constituting R B is a radical chosen from: C(=O), C(=S), -CH2CH2-, , where at least one of the radicals R D , R E and R F is chosen from among the following halogens or electron-withdrawing groups: F, Cl, Br, C m F 2m+1 with m ≤ 4, where m is a non-zero integer, CF2CF2C p H 2p+1 with p ≤ 4, where p is an integer, CF2C p H 2p+1 with p ≤ 4, where p is an integer, CH2C p F 2p+1 with p ≤ 4, where p is an integer, OCF3, OCH2CF3, SCF3, C(=O)CF3, NO2, C m H n F p Cl q Brs with m ≤ 4, where n, p, q, s are integers of which at least p, q or s is non-zero, C(=O)OC m H 2m+1 with m ≤ 4, where m is an integer, C(=O)C m H 2m+1 with m ≤ 4, where m is an integer, and S(=O)C m H 2m+1 with m ≤ 4, where m is an integer, the other radical(s) R D , R E , R F and the radicals R G are chosen, identical or different, from among the following non-electromagnetic-withdrawing atoms or groups: H, CH3, CH2CH3, C3H7, CH2CH2C p F 2p+1 with p ≤ 4, where p is an integer,C m H 2m-1 with m ≤ 10, where m is a non-zero integer, andC m H 2m+1 with m ≤ 10, where m is a non-zero integer; where only one of the radicals R D to R F maybe one of these last two radicals C m H 2m-1 or C m H 2m+1 , for m ≥ 4. – Composition according to any one of claims 1 to 4, characterized in that the alkyl radical included in the definition of R A or R C or R A,C 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 R A or R C or R A,C represents one of cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopentylmethyl or cyclohexylmethyl. – Composition according to any one of claims 4 and 5, characterized in that the compound of formula (I) is selected from: triclocarban, N,N′-bis(3-chlorophenyl)urea, N-(3-bromophenyl)-N′-phenylurea, N-(3-chlorophenyl)-N′-cyclohexylurea, N-cyclohexyl-N′-[4-(trifluoromethoxy)phenyl]urea, N-(4-bromophenyl)-N′-cyclohexylurea, N-(3-chlorophenyl)-N′-(cyclohexylmethyl)urea, N,N′-bis(4-bromophenyl)urea, 4-bromo-N1,N2-diphenyl-1,2-benzenediamine, 4-chloro-N1-(1-methylethyl)-N2-phenyl-1,2-benzenediamine, 4-fluoro-N2-(4-fluorophenyl)-N1-(1-methylethyl)-1,2-benzenediamine, 4,5-dichloro-N1-(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, N,N′-(4-chloro-1,2-phenylene)bis[benzamide], N-[2-(acetylamino)-4-chlorophenyl]benzamide, N-[2-(acetylamino)-4-bromophenyl]benzamide, N,N′-(4,5-dichloro-1,2-phenylene)bis[benzamide], 5-bromo-N1,N3-bis(4-butylphenyl)-1,3-benzenedicarboxamide, 5-bromo-N1,N3-bis[3-(trifluoromethyl)phenyl]-1,3-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-1,2-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: R1 and R2, identical or different, are, regardless of their position on a nitrogen atom, independently chosen from among C1-C alkyl groups 12 linear or branched, aryl, C3-C8 cycloalkyl; or R1 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 C1-C8 alkyl, C3-C8 cycloalkyl, C2-C6 alkoxyalkyl and alkoxyalkylaryl; R4 is chosen from hydrogen, linear or branched C1-C3 alkyl; R5 is chosen from hydrogen, linear or branched C1-C3 alkyl; and R6 is chosen from hydrogen, linear or branched C1-C3 alkyl. – Composition according to any one of claims 1 to 6, characterized in that the cation extractant(s) are selected from compounds of formula (III) or formula (IV): where n is an integer from 4 to 8, p is 1 or 2, m is 3 or 4, q and t, 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 ring, Piperidine or morpholine. – Composition according to any one of claims 1 to 6, characterized in that the cation extractant(s) are selected from compounds of formula (V) or formula (VI): where: n is 4, 5 or 6; p is 1 or 2; m is 2 or 3; q and t, 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. – 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 No. 151460-02-5),2,3,5,6,8,9,11,12-Octahydro-14-pentadecyl-1,4,7,10,13-benzopentaoxacyclopentadecin (3′-pentadecylbenzo-15-crown-5-ether, 88037-72-3),tetradecahydro-7-tetradecyl- 4a,20a:11a,15a-Dibutano-17H-dibenzo[b,k][1,4,7,10,13]-pentaoxacyclohexadecin (tetradecyl-didecalino-16-crown-5-ether, Case no. 172883-31-7),2,2,3,3,11,11,12,12-Octamethyl-6-tetradecyl-1,4,7,10,13-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][1,4,7,10,13,16]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); etun cryptand choisi parmile 5,6,14,15-dicyclohexano-4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane (Dicyclohexylcryptand[2.2.2] Cas n° 84731-60-2),le 5,6,14,15-dibenzo-4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane (Dibenzocryptand 222, Cas n°40471-97-4) etle 5-décyl-4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane (Cas n° 69878-46-2)., – Composition according to any one of claims 1 to 10, characterized in that the hydrophobic polar organic diluent(s) are selected from bromochlorobenzenes, bromochlorotoluenes, bromochlorooxylenes, bromochloroethylbenzenes, bromochloropropylbenzenes, bromochloroisopropylbenzenes, bromochlorobutylbenzenes, bromoalkyloxybenzenes, bromophenyl ketones, bromophenyl esters, 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-1-chloro-4-ethoxybenzene, 2-bromo-4-(2-methylpropyl)-1-(trifluoromethyl)benzene, 1-bromo-3-ethylbenzene, 1-bromo-3,5-dimethylbenzene, 3,4-dichlorotoluene, 1-ethyl-2-nitrobenzene, 1-Bromo-4-propoxybenzene, 2'-Bromoacetophenone and 1-bromo-2-chlorobenzene. – Composition according to any one of claims 1 to 11, characterized in that the cation is selected 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 salt metals. – 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. – 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. – 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. – 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 30 to 150°C, preferably 50 to 100°C, more preferably 60 to 80°C.

Images