METHOD FOR THE EXTRACTION OF SALTS AND TEMPERATURE-REGENERATED EXTRACTION COMPOSITION

Description

Technical field of the invention

[0001] The technical field of the invention is the ionic extraction of salts, particularly hydrophilic salts, applied for the treatment of industrial or natural saline waters. Previous art

[0002] Mining, oil, and industrial activities can generate wastewater that is highly saline, very scale-forming, and / or contaminated with toxic metals, requiring treatment before discharge into the environment, or even before recycling within an industrial process. In either of these cases, industries currently only have access to very expensive solutions that are poorly adapted, or not adapted at all, to their specific environment.

[0003] There are also cases, particularly for highly scaling saline waters rich in alkaline-earth cations and / or containing trace metals, where there is currently no sustainable and / or economical treatment technology for these waters, which necessitates storing these waters in settling basins while awaiting a solution.

[0004] In the case of mixtures of water from different or highly scale-forming sources, it is common for equipment to become scaled by the precipitation of salts with low water solubility, such as certain carbonate salts (MgCO3, CaCO3, SrCO3, BaCO3, CdCO3, CoCO3, MnCO3, PbCO3, NiCO3, FeCO3, ZnCO3, etc.), sulfate salts (CaSO4, SrSO4, BaSO4, PbSO4, etc.), fluoride salts (MgF2, CaF2, SrF2, BaF2, CdF2, FeF2, PbF2, etc.), and metal hydroxide salts (Mg(OH)2, Ca(OH)2, Cd(OH)2, etc.). 2, Co(OH) 2, Fe(OH) 2, Ni(OH) 2, Zn(OH) 2 ...), and many others that may be present in large quantities.Furthermore, if the technology used is associated with thermal vaporization of this water, the operating temperature, generally exceeding 80°C, then generates a decrease in the precipitation threshold of certain salts (for example, carbonate salts such as CaCO3 by evaporation of carbon dioxide) and salts with reverse solubility (such as CaSO4), which can further limit the maximum level of water extraction from the salt water or generate an even greater volume of solid waste to manage.

[0005] To extract an ion or salt present in dissolved form from industrial or natural water, the common approach is to use chemical methods, for example, by ensuring its precipitation through the addition of a reagent, such as a base (NaOH...), which allows the precipitation of metal hydroxides, insoluble in water. This method is non-selective with respect to the precipitated metals and corresponds to an exchange of cations (Na+ for metal in this case) or anions. It also generates other drawbacks, such as the introduction of new contaminants requiring downstream treatment and a decrease in efficiency due to a reduction in the concentration of the target compounds.

[0006] Another extraction method using solvents, known as hydrometallurgical extraction, can also be employed when capturing metals such as nickel and cobalt in higher concentrations, via a cation exchange of Mn+ / nH+. These processes use cationic extractants dissolved in a solvent, employing acid-base chemistry where extraction and solvent regeneration occur at pH levels that differ by several orders of magnitude. This method is therefore costly in terms of bases (NaOH, etc.) and acids (H2SO4, etc.), resulting in the introduction of new contaminants associated with the co-production of salts (Na2SO4, etc.) that must be managed downstream.

[0007] Another approach, also implemented for over 50 years, involves using selective electrodialysis membranes, meaning membranes that are permeable to cations or anions but impermeable to water and neutral molecules in general. In this case, the electrical energy consumed is proportional to the salt displaced, which limits its use to high-value applications such as brine treatment. This technology is non-selective towards ions of the same charge and therefore non-selective towards the metals or anions to be extracted, while also carrying a risk of membrane fouling.

[0008] Other methods exist, such as ion exchange where selectivity is dependent on the charge of the ion, limited by the concentration of the ion being treated, and also generating an input of new contaminants from the chemical regeneration of the resins.

[0009] More recently, the applicant disclosed in application WO2010 / 086575 the use of fluorinated compounds in a direct contact heat exchanger comprising a liquid, hydrophobic fluorinated phase associated with ion exchangers. However, the liquid organic fluorinated phase described in this application involves the use of ionic and non-ionic organofluorinated compounds in a process poorly suited to achieving high water desalination rates or selective salt desalination, and in particular, to descaling due to an unsuitable regeneration procedure.

[0010] US patent application US2008 / 179568A1 describes a liquid-liquid extraction process for low concentrations of cesium and strontium using two types of cationic extractant molecules: crown ethers at medium concentrations and calixarenes at very low concentrations (0.0025 to 0.025 mol / L), and at least one modifier dissolved in a diluent such as a C12-C15 isoparaffinic hydrocarbon. The modifier may be an alcohol, trioctylamine (TOA), tri-n-butyl phosphate (TBP), or mixtures thereof. This compound is intended to improve the performance of the cationic extractant and / or its ability to remain solubilized during processing.

[0011] US patent application US2008 / 0014133 describes a liquid-liquid extraction process for low concentrations of cesium and strontium using low concentrations (0.04 to 0.095 mol / L) of cationic extractants from the crown ether family, combined with a high proportion (>80% vol) of a fluorinated alcohol (called Fluoroheptanol n°3) and a glycol ether. The use of calix[4]arene compounds for strontium extraction is disclosed by Norato et al. ("Demonstration of the caustic-side solvent extraction process for the removal of 137Cs from Savannah River site high-level waste," Separation Science and Technology, vol. 38, no. 12-13, pages 2647-2666).

[0012] US patent 6566561B1 describes a liquid-liquid extraction process for low concentrations of Cesium by using solvation agents and phase modifiers of the phenoxy fluoro-alcohol type stable in basic medium, in the presence of cationic extractant molecules of the calixarene-crown ether family in low concentrations (0.001 to 0.20 Mol / L, 0.01 Mol / L preferred).

[0013] A very extensive bibliography exists in this field, among which we can cite the article by TG Levitskaia, et al. Anal. Chem. 2003, 75, 405-412, which demonstrates that it is possible to extract sodium hydroxide (NaOH) from an aqueous solution using a neutral sodium extractant, of the crown ether type, with a weak, lipophilic, deprotonable acid to allow the formation of a hydrophobic sodium alkoxide. [DC18C6] (org) + [RCOH] (org) + [Na+] (aq) + [OH-] (aq) ↔ [RCO-] Na+ DC18C6] (org) + H2O (aq)

[0014] This document also presents examples of the extraction of NaF, NaCl, NaBr, NaNO₃, and NaClO₄ at 1 M salinity by combining 0.02 M DC₁₈C₆, first without, then with, seven weak acids (from the alcohol family) present at a concentration of 0.04 M, all dissolved in nitrobenzene. Two of these alcohols are fluorinated aromatic alcohols with a pKa of approximately 8.8. The salt extraction rate for hydrophobic ions such as picrate is relatively high. However, for hydrophilic anions, such as the chloride ion Cl⁻, the recalculated salt extraction rates are between 0.06% and 0.16%, which confirms the significant difficulty in extracting hydrophilic NaCl from water and the limited influence of the alcohols, at this concentration, on the extraction performance.

[0015] Liquid compositions comprising a calix[4]arene amide or ester are disclosed by Makrlik et al. ("Solvent Extraction of Some Divalent Metal Cations into Nitrobenzene by Using a Synergistic Mixture of Strontium Dicarbollylcobaltate and p-tert-Butylcalix[4]arene-tetrakis (N,N-Diethylacetamide)", Acta Chim. Slov, vol. 59, pages 934-938).

[0016] It therefore appears that the industry is currently waiting for a brine treatment solution, whether or not it is polluted by metals, that is effective for extracting salts over a wide salinity range and much less costly in terms of investment and implementation.

[0017] It is also often expected that it will be possible to separate the combinations of scale-forming ions, to remove them or to reduce the presence of specific salts, particularly those that cause scaling of equipment by these waters, and / or to recover some of the inorganic compounds present in these waters, in order to finance all or part of this treatment.

[0018] The purpose of this patent application is therefore to describe a new technology for treating saline water and water contaminated by metals, capable of addressing these problems through its ability to extract salts of varying economic value from water, either selectively or in large quantities, for the treatment of industrial or natural saline water. This technology can be widely applied to allow the discharge of this water into the environment while respecting ecosystems, for its reuse as process water, and to provide new or additional economic value in the context of mining, oil extraction, or the recycling of high-value salts and / or metallic cations.This new technology also has the advantage of not generating new contaminants because the ions are extracted from the water in the form of salts of electrically neutral compound bodies which are then extracted from the extraction solvent via the implementation of a regeneration of the extracting active by thermal and not chemical means. Description of the invention

[0019] To perform the extraction of salts from an aqueous medium, this application describes a process for the deionization of water by thermally regenerated liquid-liquid extraction using a liquid hydrophobic organic phase comprising or being essentially composed of, or consisting of, at least one electrically neutral organic and hydrophobic compound capable of extracting (e.g., solvating, complexing or chelating) a cation from the salts to be extracted from the aqueous phase, called MEC for Cation Extracting Molecule, at least one second electrically neutral organic and hydrophobic compound capable of solvating the anions from the salts to be extracted from the aqueous medium, called MSA for Anion Solvating Molecule; and, optionally, a fluidifier, preferably hydrophobic.

[0020] Surprisingly, the association of MSA and MEC according to the invention allows the synergistic extraction of neutral salts composed of hydrophilic cations and anions that are particularly difficult to transfer into an organic phase.

[0021] The term "hydrophobic" refers to a compound, or mixture of compounds, whose solubility in water at 25°C is at least less than 0.1 mol / L. Preferably, hydrophobic compounds are chosen whose solubility in water at 25°C is less than 0.01 mol / L, preferably less than 0.0001 mol / L, and advantageously less than 1 x 10⁻⁵ mol / L. The hydrophobicity or water solubility of a compound can be measured by standard methods, including UV-visible spectroscopy. DUDE

[0022] A compound MEC as described in this application, its mixtures and uses in a process for extracting a cationic species from water containing said species as a process for deionizing water by thermally regenerated liquid-liquid extraction for the extraction of at least one divalent cationic species and at least one complementary anion, are also part of the invention.

[0023] The ECM, which allows the extraction of at least one cation, can advantageously be chosen from molecules with a good capacity for extracting alkaline earth ions, such as calcium, strontium, or barium ions, or other divalent cations depending on the separation requirement. Extraction is possible due to the replacement of the solvation of cations and anions by water with their solvation by the extracting composition, which then allows interaction with the ECM and the MSA. The nature of the interactions encompasses phenomena such as ion-dipole interactions, accompanied by the formation of hydrogen bonds and electrostatic interactions, and even van der Waals forces. Preferably, the ECM is a compound that allows for complexing, and in particular chelating, the cation. The "chelate" is distinguished from the simple " complex » by the fact that the cation is attached to the chelating ligand by at least two bonds / interactions.

[0024] The appropriate microelectrolytic cells (MECs) for the selective extraction of divalent cations from monovalent alkali metal cations are macrocycles of the metacyclophane (MCP) family, which possess a hydrophobic cavity defined by n phenol-type aromatic rings. The macrocycle size varies from 24 to 32 carbon atoms. Preferably, the macrocycle size is 24 to 28 carbon atoms.

[0025] These phenol-type aromatic rings can be linked together at the ortho position of the hydroxyl group, either directly or by 1-carbon methylene bridges (-CH₂-), 2-carbon bridges (-CH₂CH₂-), or 3-carbon bridges (-CH₂CH₂CH₂). If only direct bonds are involved, the common name for these macrocycles is Spherand, of the [0n] type. If only 1-carbon methylene bridges (-CH₂-) are involved, the common name for these macrocycles is Calixarene, of the [1n] type. If only 2-carbon bridges (-CH₂CH₂-) are involved, the common name for these macrocycles is all-homocalixarene, of the [2n] type. The size of the bridges can also vary within the same macrocycle and range from 0 to 3 carbon atoms. The nomenclature specifies this variety by naming them for example [1.3.1.3]MCP or [1.3] 2 MCPs for a macrocycle with 4 aromatics linked ortho by successively a methylene bridge then by a 3-carbon bridge then again by a methylene bridge and finally by a 3-carbon bridge to close the ring.

[0026] The macrocycles of interest are then functionalized with non-hydrogenated amide groups for the selective extraction of alkaline earth metals, without being equally selective for the extraction of divalent transition metals.

[0027] Thus, an ECM allowing the selective extraction of non-alkaline cations, particularly divalent ones, from alkali cations, particularly monovalent ones, is a macrocycle, whose ring is formed of 24 to 32 carbon atoms, functionalized by amide groups, and of the following formula (I) or (II): Or n is an integer from 5 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, or a hydrogen atom, R' and R", identical or different, are chosen from the group consisting of the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, heptyl and octyl groups, or R' and R" together form a pyrrolidine, piperidine or morpholine ring.

[0028] Thus, for compounds of formula (I), the integers n and p must be chosen such that 24 ≤ (3+p) xn ≤ 32. For compounds of formula (II), the integers m, q, and t must be chosen such that 24 ≤ (7+q+t) xm ≤ 32.

[0029] Such molecules belong to the Metacyclophane family.

[0030] Advantageously, the ECM is a molecule with the following formula: (of the Calix[6]arene family, of type [1 6 ]), where R, R' and R" are as defined previously for formulas (I) and (II). When R' and R" are both ethyl groups, the selective extraction of divalent cations is particularly strong, especially when the R radical is tert-butyl, OCH2 Ph, H or O-methyl.

[0031] Advantageously, the ECM is a molecule with the following formula: (of the AII-homocalix[5]arene family, of type [2 5 ]), where R, R' and R" are such as defined previously for formulas (I) and (II).

[0032] Advantageously, the ECM is a molecule with the following formula: (of the family of All-homocalix[6]arenes, of type [2 6 ]), where R, R' and R" are such as defined previously for formulas (I) and (II).

[0033] Advantageously, the ECM is a molecule with the following formula: (of the Calix[7]arenes family, of type [1 7 ]), where R, R' and R" are as defined previously for formulas (I) and (II).

[0034] Advantageously, the ECM is a molecule with the following formula: (of the Calix[8]arene family, of type [1 8 ]), where R, R' and R" are as defined previously for formulas (I) and (II). When R' and R" are both ethyl groups, the selective extraction of divalent cations is particularly interesting, especially when the R radical is tert-butyl, OCH2 phenyl, H or O-methyl.

[0035] Advantageously, the ECM is a molecule with the following formula: (of type [2.1.2.1.2.1]MCP or [2.1] 3 MCP), where R, R' and R" are as defined previously for formulas (I) and (II).

[0036] Advantageously, the ECM is a molecule with the following formula: (of type [3.1.3.1.3.1]MCP or [3.1] 3 MCP), where R, R' and R" are as defined previously for formulas (I) and (II).

[0037] Advantageously, the ECM is a molecule with the following formula: (of type [2.0.2.0.2.0]MCP or [2.0] 3 MCP), where R, R' and R" are as defined previously for formulas (I) and (II).

[0038] Advantageously, the ECM is a molecule with the following formula: (of type [3.0.3.0.3.0]MCP or [3.0] 3 MCP), where R, R' and R" are as defined previously for formulas (I) and (II).

[0039] Advantageously, the ECM is a molecule with the following formula: (of type [1.0.1.0.1.0.1.0]MCP or [1.0] 4 MCP), where R, R' and R" are as defined previously for formulas (I) and (II).

[0040] Advantageously, the ECM is a molecule with the following formula: (of type [2.0.2.0.2.0.2.0]MCP or [2.0] 4 MCP), where R, R' and R" are as defined previously for formulas (I) and (II).

[0041] In formulas (I) and (II): Particularly advantageously, the R group is tert-butyl.

[0042] Particularly advantageously, the R' and R" groups are both ethyl groups.

[0043] Particularly advantageously, the R group is tert-butyl or a hydrogen atom.

[0044] Particularly advantageously, MEC is the compound with the following formula: (of the Calix[6]arene family, type [1 6], and CAS number: 111786-95-9). This MEC2 is particularly effective for the selective extraction of hydrophilic alkaline earth salts, especially chloride salts, from an aqueous solution when combined with at least one MSA and optionally a fluidizer in a liquid-liquid extraction process with thermal regeneration of the liquid resin, according to the invention. Molecules belonging to these formula families (I) are already identified by a CAS number; in particular, these are the following Cation Extracting Molecules: CAS NO. R Macrocycle p n R' R" 136534-29-7 tert-Butyl Calixarena 1 6 Pyrrolidinyl 111786-95-9 tert-Butyl Calixarena 1 6 Ethyl Ethyl 385376-74-9 O-Octyl Calixarena 1 6 Ethyl Ethyl 327154-32-5 OCH2Phenyle Calixarena 1 6 Ethyl Ethyl 185330-54-5 H Calixarena 1 6 Ethyl Ethyl 327154-34-7 O-methyl Calixarena 1 6 Ethyl Ethyl 315191-66-1 tert-Butyl Calixarena 1 8 Ethyl Ethyl 327154-36-9 O-Octyl Calixarena 1 8 Ethyl Ethyl 193743-58-7 OCH2Phenyle Calixarena 1 8 Ethyl Ethyl 327154-37-0 H Calixarena 1 8 Ethyl Ethyl 315191-06-1 O-methyl Calixarena 1 8 Ethyl Ethyl

[0045] The composition according to the invention may also comprise more than one MEC compound allowing the extraction of at least one cation, this cation being advantageously chosen from the compounds described in the present application.

[0046] Another object of the invention relates to the use of these MEC compounds for the extraction of salts and / or ions from an aqueous medium. In particular, these compounds can be used, individually or in mixtures, in a composition or in a process according to the invention as described in this application.

[0047] Another object of the invention relates to the use of macrocyclic MEC compounds with ring sizes between 16 and 22 carbon atoms, functionalized with amide groups, for salt extraction, particularly salts with hydrophilic anions such as chloride salts. Specifically, these compounds, combined with the MSA according to the invention, allow for the large-scale extraction of a solution containing a mixture of such salts, for example, chloride salts comprising various cations with ionic radii between 55 pm and 180 pm, advantageously between 70 pm and 167 pm, more particularly from 75 pm to 167 pm. Such cations include, in particular, monovalent lithium, sodium, potassium, rubidium, or cesium cations, or divalent calcium, strontium, or barium cations, or even transition metal cations.Note that magnesium, which is a divalent cation with an ionic radius of 72 pm, is an exception and is not considered sufficiently extractable for these ECMs to be used industrially for its extraction from water. These compounds have generic formulas (III) and (IV): Or n is 4 or 5, -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, O-methyl, O-ethyl, O-propyl, O-isopropyl, O-butyl, O-isobutyl, O-pentyl, O-hexyl, O-heptyl, O-octyl, OCH2 Phenyl, or a hydrogen atom, R' and R", identical or different, are chosen from the group consisting of the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, heptyl and octyl groups, or R' and R" together form a pyrrolidine, piperidine or morpholine ring.

[0048] Thus, for compounds of formula (III), the integers n and p must be chosen such that 16 ≤ (3+p) xn ≤ 22. For compounds of formula (IV), the integers m, q, and t must be chosen such that 16 ≤ (7+q+t) xm ≤ 22.

[0049] In particular, the macrocycle MEC1 of formula III, where n=4, R = tert-butyl and R'=R"=ethyl, and CAS No. 114155-16-7, in its cone configuration, is particularly effective for the bulk or overall extraction of hydrophilic salts, especially chloride salts, from an aqueous solution when combined with at least one MSA and optionally a fluidizer in a thermally regenerated liquid-liquid extraction process of the liquid resin, according to the invention. Molecules belonging to these families of formulas (III) and (IV) are also already identified by a CAS number; in particular, these are the following MECs: CAS NO. R Macrocycle p n R' R" Configuration 150588-24-2 H Calixarena 1 4 Ethyl Ethyl cone 412334-02-2 H Calixarena 1 4 Butyl Butyl cone 1558817-92-7 H Calixarena 1 4 Morpholidinyl cone 149635-98-3 H Calixarena 1 4 piperidinyl cone 145237-45-2 tert-Butyl Calixarena 1 4 Methyl Methyl cone 114155-16-7 tert-Butyl Calixarena 1 4 Ethyl Ethyl cone 162714-60-5 tert-Butyl Calixarena 1 4 Propyl Propyl cone 116906-60-6 tert-Butyl Calixarena 1 4 Butyl Butyl cone 162714-61-6 tert-Butyl Calixarena 1 4 Pentyle Pentyle cone 162714-62-7 tert-Butyl Calixarena 1 4 Hexyle Hexyle cone 162714-63-8 tert-Butyl Calixarena 1 4 Octyl Octyl cone 162714-67-2 tert-Butyl Calixarena 1 4 Ethyl CH2-Ph cone 353236-42-7 tert-Butyl Calixarena 1 4 Methyl Heptyle cone 171800-66-1 tert-Butyl Calixarena 1 5 Ethyl Ethyl cone 133801-01-1 tert-Butyl Calixarena 1 4 pyrrolidinyl cone 353236-41-6 tert-Butyl Calixarena 1 4 piperidinyl cone 353236-67-6 tert-Butyl Calixarena 1 4 morpholinyl cone For calixarenes, cone-type and even partial cone-type ring configurations are preferred over 1,2-alternating or 1,3-alternating configurations, without these alternating configurations being excluded. Other 20-carbon metacyclophane-type rings have been identified: CAS NO. R Macrocycle t q m R' R" Configuration 353742-72-0 tert-Butyl MCP[1.3]2 1 2 2 Ethyl Ethyl 1,4-alternating 352742-73-1 tert-Butyl MCP[1.3]2 1 2 2 Methyl Methyl 1,4-alternating 353742-74-2 tert-Butyl MCP[1.3]2 1 2 2 Butyl Butyl 1,4-alternating

[0050] A preferred aspect of the invention is that the MEC of formula (III) or (IV) has a Log K complexation constant, in methanol at 25°C, of ​​the cationic species to be extracted, of a value greater than 3 and less than 11, preferably greater than 5 and less than 9.

[0051] These amide-type MECs are particularly well suited to the liquid-liquid extraction process by temperature difference according to the invention.

[0052] Another object of the invention relates to the use of MEC compounds functionalized with ester or ketone groups for the selective extraction of alkali cations from alkaline earth cations, without being selective for the extraction of monovalent transition metals (Silver Ag⁺). In particular, these compounds can be used, individually or in mixtures, in a composition or process according to the invention as described in this application.

[0053] Another object of the invention relates to the use of macrocyclic ECM compounds with ring sizes between 16 and 24 carbon atoms, functionalized with ester or ketone groups, for the selective extraction of alkali salts, and in particular alkali salts with hydrophilic anions, such as chloride salts. Specifically, these compounds, combined with the MSA according to the invention, allow the selective extraction of one or more alkali salts from a solution containing a mixture of such salts, for example, chloride salts comprising various cations with ionic radii between 55 pm and 180 pm, advantageously between 70 pm and 167 pm. Such cations include, in particular, monovalent lithium, sodium, potassium, rubidium, and cesium cations, or divalent calcium, strontium, and barium cations, or even transition metal cations. These compounds have the generic formulas (V) and (VI): Or 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, pentyl, hexyl, heptyl and octyl groups, for the realization of a ketone-type bonding group or, R' is chosen 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.

[0054] Thus, for compounds of formula (V), the integers n and p must be chosen such that 16 ≤ (3+p) xn ≤ 24. For compounds of formula (VI), the integers m, q, and t must be chosen such that 16 ≤ (7+q+t) xm ≤ 24.

[0055] In particular, the MEC10 macrocycle of formula (V) where n=4, R=tert-butyl and R'=O-ethyl and of CAS No. 97600-39-0, in its cone configuration, is particularly effective for the selective extraction of sodium salts, especially as sodium chloride salt, from an aqueous solution when combined with at least one MSA and optionally a fluidizer within a thermally regenerated liquid-liquid extraction process of the liquid resin, according to the invention.

[0056] In particular, macrocycles MEC11 of formula (V) where n=5, R=tert-butyl and R'=O-ethyl and CAS No. 152495-34-6, and MEC12 of formula (V) where n=6, R=tert-butyl and R"=O-ethyl and CAS No. 97600-45-8, in their cone configurations, are particularly effective for the selective extraction of alkali salts from alkali-earth salts, especially as alkali chloride salts, from an aqueous solution when combined with at least one MSA and optionally a fluidizer in a thermally regenerated liquid-liquid extraction process of the liquid resin, according to the invention. MEC11 is suitable for extracting alkali chloride salts more generally (except lithium), while MEC12, with a larger ring diameter of 24, has an extraction capacity alkali metals with a larger diameter (cesium, rubidium, or even potassium).

[0057] Molecules belonging to these families of formulas (V) and (VI) are also already identified by a CAS number, in particular the following ECMs: CAS NO. R Macrocycle p n R' Configuration 97600-43-6 H Calixarena 1 4 O-Ethyl cone 144508-85-0 H Calixarena 1 4 O-Isopropyl cone 144508-84-9 H Calixarena 1 4 O-Tert-butyl cone 97600-39-0 tert-Butyl Calixarena 1 4 O-Ethyl cone 160617-97-0 tert-Butyl Calixarena 1 4 O-Isopropyl cone 94530-27-5 tert-Butyl Calixarena 1 4 O-Tert-butyl cone 149775-74-6 Tert-Octyle Calixarena 1 4 O-Ethyl cone 152495-34-6 tert-Butyl Calixarena 1 5 O-Ethyl cone 123311-70-6 tert-Butyl Calixarena 1 4 Tert-butyl cone

[0058] For calixarenes, cone-type cycle configurations and even partial cone-type cycle configurations are preferred over 1,2 alternating or 1,3 alternating type configurations, but are not exclusive.

[0059] According to a preferred embodiment, the composition does not include an ECM of formula (V) or (VI) allowing the extraction of calcium ions, i.e., whose complexation constant Log K(Ca ++< ) in methanol at 25°C is greater than 3. A preferred aspect of the invention is that the ECM of formula (V) or (VI) has a complexation constant Log K, in methanol at 25°C, of ​​the alkali cationic species to be extracted, of a value greater than 3 and less than 11, preferably greater than 5 and less than 9. Moreover, in the case of ECMs selective for the extraction of alkali cationic species, it may have a Log K value, in methanol at 25°C, of ​​less than 5, preferably less than 3 for alkaline earth cations, and in particular for calcium.

[0060] These ester or ketone-type ECMs, of formula (V) or (VI), are particularly well suited to the liquid-liquid extraction process by temperature difference according to the invention. MSA compound

[0061] Of the MSAs described below, only those compounds falling under the definition as understood in the claims are part of the present invention.

[0062] MSA can be a compound comprising from 6 to 50 carbon atoms, advantageously from 7 to 30 carbon atoms, and in particular from 8 to 20 carbon atoms, and incorporating at least one aromatic ring and at least one halogen atom or an electron-withdrawing group, in particular fluorinated.

[0063] Advantageously, MSA is a compound with formula B: in which at least one of the radicals RA, RB, RC, RD, and RE, whether identical or different, is a halogen atom or an electron-withdrawing group, in particular a halogen radical, of the following group: F, Cl, Br, C, m, F, 2m+1 with m ≤ 4, where m is a non-zero integer; CF, CF, 2Cp, H, 2p+1 with p ≤ 4, where p is an integer; CF, 2Cp, H, 2p+1 with p ≤ 4, where p is an integer; CH, 2Cp, F, 2p+1 with p ≤ 4, where p is an integer; OCH, 2CF, 3, C(=O)CF, 3, C, m, H, n, Fp, 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, and C(=O)C m H 2m+1 with m ≤ 4, where m is an integer, the remaining radical(s) RA , RB , RC , RD and RE are chosen, identical or different, from among the following non-electro-withdrawing radicals: H, CH 3 , CH 2 CH 3 , CH 2 CH 2 C p F 2p+1 with p ≤ 4, where p is an integer, C m H 2m-1 with 3 ≤ m ≤ 10, where m is an integer, and C m H 2m+1 with 3 ≤ m ≤ 10, where m is an integer;where only one of the radicals RA to RE can be one of these last two radicals C m H 2m-1 and C m H 2m+1 ; and in which X is chosen from the following radicals: OH, NH-R', ; or R' and R", identical or different, are chosen from the following radicals: H, C n H 2n-1 with 3 ≤ n ≤ 4, where n is an integer, C n H 2n+1 with n ≤ 4, where n is a non-zero integer, CH 2 CH 2 C p F 2p+1 with p ≤ 2, where p is an integer, CH 2 C p F 2p+1 with p ≤ 2, where p is an integer, and an aryl radical of formula b: where RA, RB, RC, RD and RE, whether identical or different, are as previously defined in formula B; and in which R"' is chosen from the following radicals: C m H 2m+1 with m ≤ 20, preferably ≤ 15, where m is an integer, C m H 2m-1 with 3 ≤ m ≤ 20, where m is an integer, C m H n F p Cl q Br s with m ≤ 10, where n, p, q, s are integers of which at least p, q or s is non-zero, CH 2 CH 2 C p F 2p+1 with p ≤ 4, where p is an integer, CH 2 C p F 2p+1 with p ≤ 4, where p is an integer, CF 2 C p H 2p+1 with p ≤ 4, where p is an integer, CF 2 CF 2 C p H 2p+1 with p ≤ 4, where p is an integer, C m F 2m+1 with m ≤ 4, where m is a non-zero integer, and an aryl radical of formula b: where RA, RB, RC, RD and RE, identical or different, are such as previously defined in formula B. MSA compound - alcohol

[0064] Such a compound is advantageously chosen from the group of fluorinated aromatics with an alcohol function and their derivatives. For example, this compound may be an alcohol derived from a methanolic phenyl, such as 3-(Trifluoromethyl)benzyl alcohol (CAS No. 349-75-7).

[0065] Preferably, this first compound is a methanolic phenyl compound advantageously comprising more than 3 fluorine atoms. Advantageously, this compound comprises at least two -CF3 radicals.

[0066] According to one embodiment of the invention, this first compound MSA has the radical X in formula B: which corresponds to a compound with formula A: in which R1, R2, R3, R4 and R5, identical or different, but where any one of R1, R2 and R3 is a fluorinated radical, are chosen from the following radicals: H, F, Cm F2m+1 with m ≤ 4, where m is a non-zero integer, CF2 CF2 Cp H2p+1 with p ≤ 4, where p is an integer, and CF2 Cp H2p+1 with p ≤ 4, where p is an integer; and in which R' and R", identical or different, are chosen from the following radicals: HC n H 2n-1 with 3 ≤ n ≤ 4, where n is an integer, C n H 2n+1 with n ≤ 4, where n is a non-zero integer, CH 2 C p F 2p+1 where p ≤ 2, where p is an integer, CH 2 CH 2 C p F 2p+1 where p ≤ 2, where p is an integer, and an aryl radical of formula a: where R 1 , R 2 , R 3 , R 4 and R 5 , identical or different, are chosen from the group HFC m F 2m+1 with m ≤ 4, CF 2 CF 2 C p H 2p+1 with p ≤ 4, where p is an integer, CF 2 C p H 2p+1 with p ≤ 4, where p is an integer. MSA Compounds - Alcohol

[0067] Advantageously, the said first compound is chosen from the group consisting of the compounds described in the following Table I: Tableau I : MSA Alcohol. Semi-developed formula Raw formula CAS number Molar mass (g / mol) Density (g / cm3) [MSA] maximum Mole / L Water solubility (mmol / L) pKa C8H7F3O 176,14 1,29 7,32 32 14.6 + / -1.0 (estimated) 349-75-7 Liquid C9H6F6O 244,13 1,43 5,86 2,29 14.5 + / -1.0 (estimated) 32707-89-4 Solid C15H6F1O 544,18 1,62 2,98 0,0005 14,01 + / -0,1 916975-23-0 C10H5F9O 312,13 1,53 4,90 0,39 13,59 + / -0,1 1010101-84-4 MSA5 C11H9F7O 290,18 1,39 4,70 0,42 14,5 + / -1,0 131608-30-5 (estimated) C12H12F6O 286,21 1,30 4,54 0,48 13.9 + / -1.0 (estimated) 742097-71-8 Liquid C15H10F6O 320,23 1,37 4,28 0,07 13.3 + / -1.0 (estimated) 1598-89-6 Liquid

[0068] According to one aspect of the invention, the hydrophobic organic liquid composition comprises at least one compound enabling the solvation of at least one anion. Preferably, these compounds are selected from the (MSA) type compounds described in this application.

[0069] In particular, the liquid composition according to the invention may comprise a solid form of MSA, such as [3,5-Bis(Trifluoromethyl)phenyl]methanol (CAS No. 32707-89-4) combined with a hydrophobic liquid fluidizer or diluent.

[0070] Alternatively, the liquid composition according to the invention may comprise a solid MSA (at operating temperatures), such as [3,5-Bis(Trifluoromethyl)phenyl]methanol (CAS No. 32707-89-4), combined with a liquid MSA (at operating temperatures) such as [(Trifluoromethyl)phenyl]methanol (CAS No. 349-75-7). In this case, the liquid MSA1 has a dual function as an MSA and as a fluidizer / diluent. The relative volume proportions of these compounds may vary, but are advantageously within a ratio of 30 / 70 to 60 / 40 volume / volume (v / v). Preferably, this ratio is approximately 40 / 60 v / v, particularly for the MSA1 / MSA2 combination. MSA compounds - amide

[0071] Such a compound is advantageously chosen from the group of fluorinated aromatics with an amide function and their derivatives. The compound MSA of formula B can also be an amide compound. In this case, the radical X in formula B is: where R"' is as described previously. Preferably, the amide has the formula: in which R"' is chosen from the following radicals: -C m H 2m+1 with m ≤ 20, preferably ≤ 15 where m is an integer, -C m H 2m-1 with 3 ≤ m ≤ 20, where m is an integer, and an aryl radical of formula b: in which at least one of the radicals RA, RB, RC, RD, and RE, whether identical or different, is a halogen atom or an electron-withdrawing group, in particular a halogen radical, of the following group: F, Cl, Br, C, m, F, 2m+1 with m ≤ 4, where m is a non-zero integer; CF, CF, 2Cp, H, 2p+1 with p ≤ 4, where p is an integer; CF, 2Cp, H, 2p+1 with p ≤ 4, where p is an integer; CH, 2Cp, F, 2p+1 with p ≤ 4, where p is an integer; OCH, 2CF, 3, C(=O)CF, 3, C, m, H, n, Fp, 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, and C(=O)C m H 2m+1 with m ≤ 4, where m is an integer, the remaining radical(s) RA , RB , RC , RD and RE are chosen, identical or different, from among the following non-electro-withdrawing radicals: H, CH 3 , CH 2 CH 3 , CH 2 CH 2 C p F 2p+1 with p ≤ 4, where p is an integer, C m H 2m-1 with 3 ≤ m ≤ 10, where m is an integer, and C m H 2m+1 with 3 ≤ m ≤ 10, where m is an integer,where only one of the radicals RA to RE can be one of these last two radicals C m H 2m-1 and C m H 2m+1 . ,

[0072] Preferably the radical R"' is an alkyl chain, linear or non-linear, and in particular an nC7H15, nC9H19, nC11H23 or nC13H27 radical.

[0073] These amide-type compounds are particularly well-suited to the thermally regenerated liquid-liquid extraction process according to the invention. Other compounds of this type that can be used as MSAs for extraction compositions according to the invention include, for example: N-[3,5-Bis(trifluoromethyl)phenyl]acetamide (CAS No. 16143-84-3), N-[3,5-Bis(trifluoromethyl)phenyl]-2-chloroacetamide (CAS No. 790-75-0), N-[3,5-Bis(trifluoromethyl)phenyl]-2-bromoacetamide (CAS No. 99468-72-1), N-[3,5-Bis(trifluoromethyl)phenyl]-2-chlorobenzamide (CAS No. 56661-47-3), N-[3,5-Bis(trifluoromethyl)phenyl]-4-chlorobenzamide (CAS No. 56661-30-4), N-[3,5-Bis(trifluoromethyl)phenyl]-4-bromobenzamide (CAS No. 56661-31-5), N-[3,5-dichlorophenyl]acetamide (CAS No. 31592-84-4), N-[4-methyl-3,5-dichlorophenyl]acetamide (CAS No. 39182-94-0), N-[3-fluoro-5-(trifluoromethyl)phenyl]acetamide (CAS No. 402-02-8), N-[2-fluoro-5-(trifluoromethyl)phenyl]acetamide (CAS No. 349-27-9), N-[4-chloro-3-(trifluoromethyl)phenyl]acetamide (CAS No. 348-90-3), N-[4-bromo-3-(trifluoromethyl)phenyl]acetamide (CAS No. 41513-05-7), N-[2,5-difluoro-3-(trifluoromethyl)phenyl]acetamide (CAS No. 1994-23-6), N-[3-(trifluoromethyl)phenyl]acetamide (CAS No. 351-36-0),N-[2-methyl-3-(trifluoromethyl)phenyl]acetamide (CAS No. 546434-38-2), N-[2-amino-3-(trifluoromethyl)phenyl]acetamide (CAS No. 1579-89-1), N-[3-(trifluoromethyl)phenyl]-2,2,2-trifluoroacetamide (CAS No. 2946-73-8), N-[3-(trifluoromethyl)phenyl]-2,2-dichloroacetamide (CAS No. 2837-61-8), N-[3-(trifluoromethyl)phenyl]-2,2,2-trichloroacetamide (CAS No. 1939-29-3), N-[4-chloro-3-(trifluoromethyl)phenyl]-2,2,2-trichloroacetamide (CAS No. 13692-04-1), N-[3-(trifluoromethyl)phenyl]-2-bromoacetamide (CAS No. 25625-57-4), N-[3-(trifluoromethyl)phenyl]propanamide (CAS No. 2300-88-1), N-[2-chloro-5-(trifluoromethyl)phenyl]propanamide (CAS No. 721-57-3), N-[3-(trifluoromethyl)phenyl](2,2-dimethylpropanamide) (CAS No. 1939-19-1), N-[2-methyl-3-(trifluoromethyl)phenyl](2,2-dimethylpropanamide) (CAS No. 150783-50-9), N-[4-chloro-2-methyl-3-(trifluoromethyl)phenyl](2,2-dimethylpropanamide) (CAS No. 112641-23-3),N-[3-(trifluoromethyl)phenyl](2-chloropropanamide) (CAS No. 36040-85-4), N-[3-(trifluoromethyl)phenyl]butanamide (CAS No. 2339-19-7), N-[3-(trifluoromethyl)phenyl]isobutanamide (CAS No. 1939-27-1), N-[3-(trifluoromethyl)phenyl]cyclopentanecarboxamide (CAS No. 13691-84-4), N-[3-(trifluoromethyl)phenyl](2-methylpentanamide) (CAS No. 1939-26-0), N-[3-(trifluoromethyl)phenyl](2,2-Dimethylpentanamide) (CAS No. 2300-87-0), N-[3-(trifluoromethyl)phenyl](2-(4-bromophenyl)acetamide) (CAS No. 349420-02-6), N-[3-(Trifluoromethyl)phenyl]-1-adamantanecarboxamide (CAS No. 42600-84-0), N-[2-chloro-5-(trifluoromethyl)phenyl]octanamide (CAS No. 4456-59-1).

[0074] These molecules, used as MSAs, through their integration into a formulation combining at least one ECM and optionally a fluidizer, allow the extraction of ionic species, and in particular hydrophilic salts, from water to the extracting organic phase. An MSA particularly suitable for use in an extraction process according to the invention is a molecule of the formula in which R = nC 7 H 15 , nC 9 H 19 , nC 11 H 23 or nC 13 H 27 , respectively called MSA9; MSA10, MSA11 and MSA12.

[0075] By hydrophilic salt, we mean a salt soluble in water at more than 1 g / L at 20°C, more particularly at more than 20 g / L at 20°C, and advantageously at more than 100 g / L of water at 20°C. FLUIDIFIER

[0076] Since some of the MECs and MSAs are solid or viscous compounds at the operating temperatures of the extraction process, the use of a fluidizer is advantageous. As the process according to the invention allows, in particular, the extraction of relatively high concentrations of salts, a fluidizer capable of dissolving at least 0.1 mol / L of combined MECs and MSAs must be identified. Indeed, conventional solvents such as acetone, ethyl acetate, heptane, dimethyl formamide, nitromethane, methanol, ethanol, diethyl ether, or acetonitrile, for example, do not solubilize many known MECs at these concentration levels, and in particular the 16- to 32-atom macrocycles described above.

[0077] However, it appears that solvents or diluents such as dichloromethane, and more specifically polar aromatic solvents, have the capacity to be good candidates as solubilizers for this application. This can be explained by the similar nature of MSAs (methyl aromatic surfactants), which are themselves generally aromatic compounds. For example, 1,3-bis(trifluoromethyl)benzene (CAS No. 402-31-3) and, more preferably, benzyl benzoate (CAS No. 120-51-4), composed of two aromatic rings, meet this solubilization criterion in the exemplified formulations. The presence of at least one electron-withdrawing group of the trifluoromethyl or chloride type on one or two aromatic rings allows for the production of particularly advantageous fluidizing compounds.Dichlorobenzene-type compounds (e.g., 1,2-dichlorobenzene (CAS No. 95-50-1)) and dichlorotoluene-type compounds (e.g., 2,4-dichlorotoluene (CAS No. 95-73-8)), their derivatives, and mixtures thereof are particularly suitable diluents for diluting the MECs according to the invention. By derivatives, we mean aromatic compounds substituted with the aforementioned trifluoromethyl group, such as, for example, a solvent with mixed groups like 2,4-dichloro-(trifluoromethyl)benzene (CAS No. 320-60-5), but also di-aromatic compounds such as diphenyl ether (CAS No. 101-84-8).

[0078] It is also possible to choose an MSA in such a way that it combines the functions of MSA and diluent of MEC and / or other MSAs.

[0079] According to a preferred aspect of the invention, the composition consists only of the MSA and MEC compounds, and possibly in association with a fluidizing compound, thus constituting a composition consisting of MSA and MEC and a fluidizing compound.

[0080] Another object of the invention relates to the use of these MSA compounds, and in particular MSA amides, for the extraction of salts and / or ions from an aqueous medium. Specifically, these compounds can be used, individually or in mixtures, in a composition or in a process according to the invention as described in this application. Concentration of MSA in the organic liquid composition

[0081] According to a preferred aspect of the invention, the molar concentration of MSA (or a mixture of such compounds) in the composition according to the invention is at least 0.1 M. Preferably, this concentration is higher, at least 1 M, to allow for optimized extraction, particularly of hydrophilic anions. Depending on the anionic solvation efficiency of the chosen MSA, it can also be at least 2 M, advantageously at least 3 M, for example, at least 4 M. The concentration of MSA to be used depends on its efficiency as an anion solvator. An excess of MSA that does not improve extraction performance is not desirable. Similarly, a lack of fluidity in the extraction composition due to a high concentration of MSA is also not optimal.In certain embodiments of the invention, MSA, or a mixture of MSA, can be used pure in its liquid form (molar concentration of 7.32 M for [(Trifluoromethyl)phenyl]methanol (CAS No. 349-75-7) or 6.41 M for 3,5-bis(trifluoromethyl)aniline (CAS No. 328-74-5)). The final MSA concentration depends on the intended application and the relative cost between MSA and a fluidizer to obtain the best technical and economic solution for water deionization. Density, solubility and viscosity

[0082] According to an advantageous aspect of the invention, the MSA enabling the solvation of anions, in the organic liquid composition, and particularly the extracted organic liquid composition, of at least one anion, has a solubility in water, in its free or complexed form, of less than 0.1 Mol / L, preferably less than 0.01 Mol / L, preferably less than 0.0001 Mol / L and more particularly less than 1x10 -5< Mol / L.

[0083] According to another advantageous aspect of the invention, the MSA of at least one extracted anion has a density greater than 1 kg / L, advantageously greater than 1.1 kg / L, ideally greater than 1.2 kg / L. This design choice is closely linked to the choice of the fluidizer, which, by having a higher density, can compensate for a lack of density in the MSA.

[0084] According to yet another advantageous aspect of the invention, the liquid MSA or the MSA + fluidifier mixture has a viscosity at 25 °C of less than 100 mPa.s, preferably less than 50 mPa.s, for example less than 20 mPa.s. Relative concentration of MSA and MEC in the organic liquid composition

[0085] To ensure maximum extraction of ionic species, the concentrations of MSA and MEC are chosen according to the concentration of the ionic species to be extracted in the aqueous solution. An aqueous solution is defined as a liquid containing more than 50 moles of water.

[0086] Thus, with the same volume of salt water and extraction formulation, the concentration of the MEC compound is advantageously equimolar or greater than the concentration of the cation to be extracted. A concentration approximately twice as high generally constitutes a limit beyond which cation extraction is not substantially improved. The actual MEC concentration is primarily limited by the solubilization capacity of the MEC in the MSA alone or the MSA+thinning agent mixture, and / or by the viscosity of the overall formulation obtained, and / or by the optimal overall techno-economic balance.

[0087] Surprisingly, a molar concentration of MSA significantly higher than that of the anion to be extracted may be required for optimal extraction. Thus, at least double, preferably triple, or even quadruple, quintuple, or sextuple, or more, the concentration of the anion to be extracted may be necessary to obtain satisfactory results, particularly when the anion is chloride. The actual MSA concentration used is primarily limited by the solubilization capacity of MSA in the MEC+thinning agent mixture and / or by the viscosity of the overall formulation obtained and / or by the optimal overall techno-economic balance.

[0088] Thus, the relative molar ratio of MSA / MEC in a composition according to the invention for extracting a salt consisting of an anion and a cation is advantageously greater than or equal to 1, 2, 3, 4, 5, or 6. The choice of the relative molar ratio of MSA / MEC to be retained for an industrial application depends on the relative cost of these compounds, the techno-economic data of the project, and the solvation activity of the anions of the chosen MSA. Preferably, this ratio is at least 4 for an alcohol-based MSA and between 1 and 4 for an MSA-based MSA-Amid.

[0089] The ECM concentrations given in the examples are relative to the volume of the MSA+thinning agent mixture and therefore do not take into account the increase in the overall formulation volume caused by the dilution of a macromolecule such as these ECMs. The actual ECM concentration is therefore generally 10 to 25% lower, although this range is not limiting. Use of the composition according to the invention

[0090] The composition according to the invention can advantageously be used to extract hydrophilic ions (cations, anions) from an aqueous phase. It should be noted that this ion extraction is not compensated by the transfer of chemical species, ionic or otherwise, from the organic phase to the aqueous phase or vice versa. This composition is particularly well-suited for the selective extraction of ionic species from an aqueous solution containing several salts and / or ionic species. Thus, it is particularly well-suited for the selective extraction of at least one non-alkaline cationic species from an aqueous saline solution. Anions and cations to be extracted

[0091] The MEC and MSA compounds included in the composition according to the invention are compounds enabling the extraction and solvation of at least two, and preferably several, ionic species. The two ionic species may, in particular, constitute one or more hydrophilic salts. According to one aspect of the invention, the MEC and MSA are chosen so as to be able to extract more than one salt, and preferably several salts, from a saline solution containing them. Preferably, these salts comprise or are chloride salts. According to another aspect of the invention, these ions are the constituents, for example, of one or more alkaline earth salts as well as salts of certain metals, such as salts of cadmium (Cd²⁺), lead (Pb²⁺), or silver (Ag⁺).

[0092] By "salt" we mean an ionic compound composed of cations and anions forming a neutral product with no net charge. These ions can be inorganic (chloride Cl-, calcium Ca++, etc.), organic (acetate CH3COO-, ammonium R3NH+, etc.), and monatomic (fluoride F-, magnesium Mg2+, etc.) as well as polyatomic (nitrates NO3-, hydrogen carbonate HCO3-, sulfate SO42-, etc.).

[0093] In a particularly preferred manner, compositions comprising a mixture of MEC and MSA, with or without a fluidifier, according to the invention, can extract from a solution comprising: at least one alkali metal cationic species, at least one non-alkaline cationic species, in particular a divalent one, and at least one complementary anionic species, in a much larger quantity of said non-alkaline cationic species than of the alkali metal cationic species. Alternatively or additionally, the quantity of alkali metal cationic species extracted by this composition is very small.

[0094] By "significantly greater relative quantity" and "very low extraction," it is understood that the extraction rate (in mole percentage) of the cation(s) to be extracted is at least twice as high as the extraction rate of the alkali cations from the treated aqueous solution. This ratio may advantageously be at least 5, or even more than 10. Certain compositions according to the invention make it possible to achieve ratios of 13 at the initial iso-concentration of cations to be extracted and not extracted, or even to extract all the ions to be extracted (for example, Ca) while extracting virtually no alkali cations (for example, Na), especially when the alkali cations are predominant.

[0095] The cation(s) to be extracted are preferably chosen from the alkaline earth metal group, and more specifically Calcium, Strontium, and / or Barium. Extracting such divalent cations, and in particular Calcium, which is the most common in water, helps prevent scaling caused by its combination with specific anions.

[0096] An alkali metal is a chemical element in the first column (group 1, excluding hydrogen) of the periodic table. Lithium, sodium, potassium, rubidium, cesium, and francium are alkali metals. They have a single positive charge.

[0097] The extraction of alkaline earth cation salts is done by complexation of the ECM for this cation and by following anions from the aqueous phase to the organic phase in order to ensure neutralization of the + / - charges.

[0098] The follower anions solvated by the MSAs are primarily the least hydrophilic anions, that is, the anions with the highest free energy of hydration. Thus, the preferential order of extraction of current anions from the aqueous phase to the organic formulations according to the invention is: BF₄⁻, I⁻, Br⁻, NO₃⁻, Cl⁻, HCO₃⁻, CH₃COO⁻, F⁻, SO₄²⁻, CO₃²⁻. Therefore, in the case of alkaline earth salts extracted, iodide, bromide, nitrate, and / or chloride salts will be the primary extractors. Since these salts are very soluble in water, even at high water temperatures (CaCl2 is soluble in water at more than 40% by weight), they can be rendered as concentrated brine during the solvent temperature regeneration step.The alkaline earth or metallic salts extracted according to the invention thus make it possible to separate the cations from the anions that cause scale and are potentially constitutive of scale-forming salts, in order to deliver them to two separate aqueous effluents. The partially deionized water according to the invention then consists of the most hydrophilic anions, namely fluorides, sulfates, and carbonates, and the unextracted alkali cations. This water has therefore lost all capacity to form scale. It is softened. This is also the case for the water resulting from the thermal regeneration of the process according to the invention, which is mainly composed of alkaline earth and metallic chloride salts. Thus, the objective of the invention is to be able to eliminate the scale barrier in many industrial applications by avoiding the combined presence in the same effluent of cations and anions which, when combined, are insoluble or only slightly soluble in water.The salts to be separated are therefore mainly carbonate salts (MgCO3, CaCO3, SrCO3, BaCO3, CdCO3, CoCO3, MnCO3, PbCO3, NiCO3, FeCO3, ZnCO3, ...), sulfate salts (CaSO4, SrSO4, BaSO4, PbSO4, ...) and fluoride salts (MgF2, CaF2, SrF2, BaF2, CdF2, FeF2, PbF2, ...). The control of the precipitation of metallic hydroxide salts (Mg(OH) 2 , Ca(OH) 2 , Cd(OH) 2 , Co(OH) 2 , Fe(OH) 2 , Ni(OH) 2 , Zn(OH) 2 ...) is controlled by an adjustment of the pH of the water or by a release of the extracted divalent cations into water of neutral or even slightly acidic pH.

[0099] The cations that are preferably extracted according to the invention are Ca2+, Sr2+, Ba2+, Pb2+, Cd2+ and silver Ag+. This list is not exhaustive with regard to transition metals.

[0100] Also, the compositions according to the invention can be used in methods according to the invention to extract Ca++, Sr++ and / or Ba++ in an organic phase.

[0101] For more hydrophobic anions such as perchlorates ClO 4 -< , permanganates MnO 4 -< , picrates, lower concentrations of MSA are sufficient to effect their transfer to the organic phase in combination with at least one cation extracted by an ECM.

[0102] The composition according to the invention is therefore particularly suitable for use in an extraction process as described in this application, and in particular a thermally regenerated liquid-liquid extraction process for water deionization. According to a preferred embodiment, the composition does not include an ECM (Extractive Chemical Material) for the extraction of sodium chloride, i.e., one whose complexation constant of sodium in methanol at 25°C, Log K(Na+) < 3, is greater than 3. According to a particular aspect of the invention, magnesium chloride salts are extracted only slightly or not at all due to the use of an ECM whose complexation constant of magnesium in methanol at 25°C, Log K(Mg2+) < 3, is less than 3. LIQUID-LIQUID EXTRACTION PROCESS

[0103] The invention also relates to a liquid-liquid extraction method for a non-alkaline cationic species from a saline aqueous solution, said saline aqueous solution comprising at least one non-alkaline cationic species, one cationic species of an alkali metal, and one complementary anionic species, said method comprising the following steps: a) the mixing in a first reactor, at a first temperature, of a liquid hydrophobic organic phase and said liquid saline aqueous solution, for the subsequent obtaining of a treated liquid aqueous solution and a hydrophobic liquid organic phase charged with said non-alkaline cationic species and complementary anionic species, said liquid hydrophobic organic phase comprising an extracting molecule of said non-alkaline cationic species, a solvating molecule of said complementary anionic species and, optionally, a fluidifier; b) the separation, on the one hand, of the treated liquid aqueous solution and, on the other hand, of said liquid organic phase charged with said non-alkaline cationic species and complementary anionic species; said process being characterized in that said extracting molecule of the non-alkaline cationic species is an ECM as described above and said solvating molecule of the complementary anionic species is advantageously an MSA as described above, in particular an amide-type MSA

[0104] Preferably, a subsequent step c) is carried out in which, at a second temperature preferably higher than the first, in liquid phase, in a second reactor, said liquid organic phase charged with said non-alkaline cationic and complementary anionic species, is mixed with a liquid aqueous regeneration solution, for the subsequent obtaining of a regenerated liquid organic phase and a liquid aqueous regeneration solution charged with said non-alkaline cationic and complementary anionic species, the difference between said first and second temperatures varying from 30 °C to 150 °C, preferably varying from 50 °C to 100 °C.

[0105] The term "non-alkaline cation" or "non-alkaline cationic species" is intended to exclude cations derived from alkali metals. Preferably, non-alkaline cationic species are divalent cations, such as alkaline earth cations. The process according to the invention is particularly suitable for the extraction of one of the following cations: calcium, strontium, and barium. It can also be applied to monovalent metallic cations such as silver (Ag+), or to divalent metallic cations such as lead (Pb2+) and cadmium (Cd2+). According to a preferred aspect of the invention, the cationic species of an alkali metal is the sodium ion (Na+). Advantageously, this ion is extracted only slightly or not at all from the saline solution.

[0106] Non-alkaline cation salts consist of the aforementioned cations and a complementary anionic species, or anions. The term "complementary anionic" indicates that the charge of the anionic species or species corresponds to that of the cationic species, thus neutralizing it and forming a neutrally charged salt.

[0107] The MEC and MSA, as well as the possible thinning agent, are as described above.

[0108] MSA is a hydrophobic, protic compound, whose pKa in water at 25°C is at least 9, preferably at least 10.5 and is preferably lower than the pKa of water at 25°C, or at least lower than 15 at 25°C.

[0109] The MEC can also be an organic and hydrophobic compound having a complexation constant of the non-alkaline cationic species to be extracted of Log K value, in methanol at 25°C, greater than 3 and less than 11, preferably greater than 5 and less than 9. In addition, in the case of MECs selective for the extraction of non-alkaline cationic species, it can have a Log K value, in methanol at 25°C, less than 5, preferably less than 3 for alkali cations, and in particular for sodium.

[0110] The pKa (or acidity constant) is defined by pKa = -log 10 Ka, where Ka is the acid dissociation constant, which is measured in a standard manner for such pKa values. The recommended standard measurement method for high, basic pKa values ​​is preferably that described by Popov et al., IUPAC - Guidelines for NMR measurements for determination of high and low pKa, Pure Appl. Chem., Vol. 78, No. 3, pp. 663–675, 2006.

[0111] K is the complexation constant of an ECM and a non-alkaline cation in methanol, at 25°C, which is measured according to the standard isothermal titration calorimetric method.

[0112] According to a particular aspect of the invention, the non-alkaline cationic species is selectively extracted with respect to the cationic species of an alkali metal. This selection can reach the levels described above.

[0113] Unlike many known ion extraction processes, the process according to the invention is not based on a change in pH to enable either the absorption or the release of captured ions, particularly via the acid-base mobility of the hydrogen ion H+. Thus, a preferred aspect of the invention is that the process does not include a step where the pH of the regenerating aqueous liquid solution is significantly altered, i.e., beyond a pH variation of + / - 2, for example, ± 1 relative to the water being treated. According to a preferred aspect of the invention, the process does not include, during the regeneration step of the ion-extracting solvent, the addition, use, or presence of compounds intended to modify the pH of the regenerating aqueous liquid solution, such as acids or bases, particularly inorganic acids such as sulfuric, hydrochloric, or nitric acids, or bases such as sodium hydroxide or potassium hydroxide.

[0114] Furthermore, this process advantageously allows the extraction from the water to be treated of at least one alkaline earth cationic species, as well as anionic species such as Br⁻ or Cl⁻ ions. It should be noted that such anionic species are hydrophilic and particularly difficult to extract from an aqueous medium. A particularly advantageous aspect of the process according to the invention is that it allows the simultaneous extraction from an aqueous phase of cations, and in particular of Ca²⁺-type cations, and of anions, and particularly of Cl⁻-type anions, and for extracted salt concentrations that may exceed 0.1 mol / L. STEP a)

[0115] The mixing step a) of the liquid saline aqueous solution and the hydrophobic organic phase can be carried out by stirring the two liquid phases, for example by mechanical or orbital stirring, by developing highly turbulent flows, and / or by vertical interpenetration (static or agitated gravitational column) when these two phases have different densities. The technological choice associated with the implementation of the process of the invention depends on the salt transfer kinetics associated with the process and the operating temperatures considered.

[0116] It may be necessary to repeat these mixing steps a) to achieve the desired salt extraction performance. In this case, the mixing reactors will allow the flow of the saline solution to be treated and the organic phase to flow in counter-current directions for maximum deionization performance.

[0117] It is also preferred that the mixing step a) not be carried out under conditions resulting in a microemulsion or a stable emulsion and that in all cases the chosen MSA does not have surfactant-type activity. STEP b)

[0118] Step b) of separating the aqueous and organic phases can advantageously be a simple gravity settling of the organic phase and the liquid aqueous phase. This settling can take place in the reactor where the mixing occurs. Alternatively, the separation can be achieved by applying an external means, for example, centrifugation, possibly in a centrifuge separate from the reactor where the aqueous and organic phases are mixed. The settling time of the two phases is an important parameter of the process due to the volume of organic phase immobilized. Therefore, a density difference between immiscible liquid phases of more than 0.1 kg / L, or even more than 0.2 kg / L, is preferred. The organic phase is then advantageously chosen to have a higher density than the water to be treated, the treated water, and the produced regeneration saline water.Alternatively, the organic phase can be chosen to have a lower density than both the water to be treated and the treated water. In both cases, the density difference must be sufficient to allow effective settling of the two phases when this type of mixture is used. In both cases, if the density difference between the immiscible liquid phases used in the process is less than 0.1 kg / L, a centrifugal settling system capable of separating liquid phases with a density difference of only 0.05 kg / L may be considered. STEP c)

[0119] Once the phases are separated, the liquid organic phase, now rich in ionic species, is advantageously directed to one or more secondary reactors where, after being heated, it is brought into contact with liquid water, or regeneration water, at a second temperature higher than the first. This "hot" water regeneration of the organic phase allows for the deextraction of the salts absorbed in step a), which is all the more efficient as the regeneration water is warmer. This makes it possible to reduce the volume of regeneration water and / or increase the productivity of the liquid organic phase and / or reduce the number of desorption reactors required and / or produce regeneration water with a high concentration of extracted salts.With the exception of temperature, this mixing step enabling salt deextraction (c) can be carried out under operating conditions similar to those described for mixing step (a) which enables salt extraction. However, some conditions, such as pressure, may vary to, for example, prevent the water or fluidizer from boiling. Furthermore, performing this regeneration step of the extractant composition at a higher temperature impacts the hydrodynamics of the flows, with a decreased viscosity of the organic phase. This promotes phase settling and alters the salt transfer kinetics between phases, potentially leading to the selection of a technology other than that used in step (a).The water or liquid aqueous regeneration solution will be chosen to be compatible with the extracted salts, in particular to avoid any scaling problems, especially in the heat exchangers cooling the hot water from this step. TEMPERATURE

[0120] According to an advantageous aspect of the invention, step a) is carried out at ambient temperature. It is also advantageous that the saline solution not be subjected to a pre-heating or pre-cooling step. Alternatively, a pre-heating or pre-cooling step may be carried out. In this case, it is preferable that the saline solution not be heated or cooled by more than 5 °C, advantageously by more than 2 °C, relative to the saline solution being treated.

[0121] According to another advantageous aspect of the invention, the first temperature is below 50°C and above 0°C. This temperature can advantageously be chosen from ranges of 10°C to 40°C, preferably from 15°C to 30°C, and particularly from 19 to 26°C (for example 25°C).

[0122] A temperature range of 10°C to 50°C includes temperatures of 10°C, 11°C, 12°C, 13°C, 14°C, 15°C, 16°C, 17°C, 18°C, 19°C, 20°C, 21°C, 22°C, 23°C, 24°C, 25°C, 26°C, 27°C, 28°C, 29°C, 30°C, 31°C, 32°C, 33°C, 34°C, 35°C, 36°C, 37°C, 38°C, 39°C, 40°C, 41°C, 42°C, 43°C, 44°C, 45°C, 46°C, 47°C, 48°C, 49°C or 50°C.

[0123] According to another particularly advantageous aspect of the invention, the second temperature is a temperature above 60°C, preferably above 85°C. This temperature can be chosen from ranges from 60°C to 150°C, preferably from 85°C to 125°C, and particularly from 90°C to 120°C (for example 95°C).

[0124] The temperature range from 60°C to 150°C includes temperatures of 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C, 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, 81°C, 82°C, 83°C, 84°C, 85°C, 86°C, 87°C, 88°C, 89°C, 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, 96°C, 97°C, 98°C, 99°C, 100°C, 101°C, 102°C, 103°C, 104°C, 105°C, 106°C, 107°C, 108°C, 109°C, 110°C, 111°C, 112°C, 113°C, 114°C, 115°C, 116°C, 117°C, 118°C, 119°C, 120°C, 122°C, 124°C, 125°C, 126°C, 127°C, 128°C, 129°C, 130°C, 131°C, 132 °C, 133 °C, 134 °C, 135 °C, 136 °C, 137 °C, 138 °C, 139 °C, 140 °C, 141 °C, 142 °C, 143 °C, 144 °C, 145 °C, 146 °C, 147 °C, 148 °C, 149 °C or 150 °C.

[0125] The first and second temperatures are necessarily chosen so that the mixture remains in a liquid state at the operating pressure and that the technical and economic performance of the invention is maximized. It is particularly advantageous for the difference between these temperatures, ΔT, to be chosen within a range of 30 °C to 150 °C, preferably from 50 °C to 100 °C. By ΔT ranging from 50 °C to 100 °C, we mean a ΔT of 50 °C, 51 °C, 52 °C, 53 °C, 54 °C, 55 °C, 56 °C, 57 °C, 58 °C, 59 °C, 60 °C, 61 °C, 62 °C, 63 °C, 64 °C, 65 °C, 66 °C, 67 °C, 68 °C, 69 °C, 70 °C, 71 °C, 72 °C, 73 °C, 74 °C, 75 °C, 76 °C, 77 °C, 78 °C, 79 °C, 80 °C, 81 °C, 82 °C, 83 °C, 84 °C, 85 °C, 86°C, 87°C, 88°C, 89°C, 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, 96°C, 97°C, 98°C, 99°C or 100°C. Also, if the first temperature is 20°C, the second temperature will be more than 50°C, advantageously more than 70°C, for example 80°C.

[0126] Thus, the process of the invention may include a first step a) enabling the transfer of specific ionic species, which are preferably complementary, from the liquid saline aqueous solution to be treated to the organic phase, at ambient temperature, followed by a step c) enabling the regeneration of the organic phase charged with ionic species, preferably complementary, and which takes place at a temperature higher than ambient temperature but relatively low so as to be derived from renewable energies geothermal, solar or other (for example less than 150 °C).

[0127] According to one preferred aspect of the process, it includes the subsequent steps of: d) separation of said regenerated liquid organic phase and water, or aqueous regeneration liquid charged with said ionic species which are preferably complementary, e) indirect thermal contact, for example by heat exchanger, of said liquid organic phase charged with ionic species and of said regenerated liquid organic phase.

[0128] According to one particular aspect of the invention, it is advantageous for the process to include heating and / or cooling steps of: the organic phase charged with ionic species, the organic phase, in particular regenerated, not charged with ionic species, of the water, or aqueous solution, of regeneration, and of the water, or aqueous solution, of regeneration charged with discharged ionic species; which precedes the introduction of these various phases or waters into the first and second reactors.

[0129] Such heating steps can be carried out in whole or in part by heat exchanges between at least two of the various phases mentioned above (i.e. between the charged organic phases and in particular regenerated, not charged with ionic species, or between the aqueous phases which are water, and an aqueous regeneration solution or between water and an aqueous regeneration solution charged with discharged ionic species).

[0130] In particular, the process according to the invention includes a step of heating the water, or aqueous solution, of regeneration carried out before step c) and / or includes a step of heating the organic phase charged with ionic species carried out before step c).

[0131] Hot regeneration of the extractant composition, for example, reduces the number of regeneration steps required before recycling it within the process by a factor of 2. This advantage appears to be even more significant when using a resin with a high MEC loading rate, and therefore a high salt content.

[0132] Increasing the regeneration temperature reduces the number of successive contact steps of distilled water or regeneration water while allowing greater salt deextraction each time. PRESSURE

[0133] The mixing steps a) and / or c) are advantageously carried out at atmospheric pressure of about 1 atm at sea level, or without application of pressure means other than the weight of the liquids present in the reactor.

[0134] If pressure is applied, it can be positive or negative. Such pressure can range from 0.8 atm to 80 atmospheres, preferably from 1 to 10 atm. USE OF TREATED WATER

[0135] Advantageously, the water, or aqueous solution, regeneration liquid used in step c) is derived from the treated saline aqueous solution obtained at the outlet of step a) after further treatment to prevent any risk of scaling during steps c), d) or e). Alternatively, it can be from an external source. COMPOSITION

[0136] The organic phase comprises, or is essentially composed of, or consists of, the composition according to the invention described in this application. This composition is particularly effective for carrying out the process. Compositions particularly suitable for carrying out the process according to the invention include compositions combining an MSA Amide with at least one of the MEC-type compounds as described above and optionally with a fluidifier.

[0137] In the description of the invention, this composition may also be referred to as "solvent" or "liquid resin". DEVICE

[0138] The invention also relates to a device for extracting at least one non-alkaline cationic species and at least one complementary anion, present in a liquid aqueous saline solution comprising: a first reactor comprising a liquid hydrophobic organic phase or composition according to the invention as described in this application.

[0139] This system may advantageously include: a first reactor comprising said hydrophobic organic liquid composition and optionally the aqueous saline solution, in liquid form, for the subsequent production of a treated aqueous saline solution and a hydrophobic liquid organic phase charged with said non-alkaline cationic and complementary anionic species, said first reactor comprising furthermoreof the first means for mixing and of the first means for separating, on the one hand, said treated liquid aqueous saline solution and, on the other hand, said charged liquid organic phase, a second reactor comprising a liquid hydrophobic organic phase charged with at least said non-alkaline cationic species and with at least one complementary anion neutralizing its charge and of water, or aqueous regeneration solution for the subsequent obtaining of a liquid aqueous regeneration solution charged with said ionic species and a regenerated organic phase, said second reactor comprising second means for mixing and second means for separating, on the one hand, said regeneration saline solution charged with ionic species and, on the other hand, said regenerated organic phase; optionally means for controlling the temperature in said second reactor;means of communication enabling the transfer between the first and second reactors of: said liquid aqueous regeneration solution that can be extracted from said first reactor; said liquid hydrophobic organic phase extracted from said first reactor; said regenerated liquid hydrophobic organic phase extracted from said second reactor; said liquid regeneration water charged with salts from said second reactor; and, a heat exchanger bringing together, on the one hand, said liquid hydrophobic organic phase extracted from said first reactor and, on the other hand, said regenerated liquid hydrophobic organic phase extracted from said second reactor; and optionally, a heat exchanger bringing together, on the one hand, said regeneration water, or liquid aqueous solution, and, on the other hand, said liquid regeneration water charged with complementary ionic species extracted.

[0140] According to a particular aspect of the invention, the reactors, and more particularly the non-moving parts of these reactors, are not made of stainless steel.

[0141] According to another particular aspect of the invention, the first and / or first reactors do not include means of heating (radiators) or cooling (coolant).

[0142] According to yet another particular aspect of the invention, the organic phase present in the device comprises, or is essentially constituted, or is constituted of the composition according to the invention described in the present application.

[0143] The device according to the invention can advantageously be connected in series to allow successive treatment stages of the water to be treated, so as to reduce the ionic content of the water until pure and / or purified water is obtained, free of the ionic species to be extracted. Such a device is also covered by the present invention.

[0144] Similarly, the device according to the invention can advantageously be mounted in series to allow successive regeneration steps of the liquid hydrophobic organic phase loaded with salt, so as to reduce the ionic species content of the resin until a sufficiently purified resin is obtained, free of extracted ionic species. Such a device is also covered by the present invention. The invention also relates to a liquid-liquid extraction process for a salt or a mixture of salts composed of at least one hydrophilic anion, such as chloride (see Examples 1 and 2). The extracted cations may have an ionic radius between 55 pm and 180 pm, advantageously between 70 pm and 167 pm. Such cations include, in particular, lithium, sodium, potassium, rubidium, and cesium cations, which are monovalent cations, or calcium, strontium, or barium cations, which are divalent cations, or even transition metal cations.

[0145] This process includes the following steps: (i) the mixing in a first reactor, at a first temperature, of a liquid hydrophobic organic phase and said liquid saline aqueous solution, for the subsequent obtaining of a treated liquid aqueous solution and a liquid hydrophobic organic phase charged with said complementary cationic and anionic species, said liquid hydrophobic organic phase comprising an extracting molecule of said cationic species of the type as described above, a solvating molecule of said complementary anionic species and, optionally, a fluidifier; (ii) the separation, on the one hand, of the treated liquid aqueous solution and, on the other hand, of said liquid hydrophobic organic phase charged with said complementary cationic and anionic species; said process being characterized in that said extracting molecule of the cationic species is an ECM as previously described for macrocycles of 16 to 22 atoms, in particular of carbon and that said solvating molecule of the complementary anionic species is an MSA advantageously as previously described.

[0146] Advantageously, the process includes a subsequent regeneration step of the hydrophobic organic liquid phase, which may be of the same type as that described previously. Advantageously, the regeneration temperature is between 60°C and 150°C, preferably between 90°C and 120°C.

[0147] The compounds and other conditions of the process may advantageously be those described with reference to the process for extracting non-alkaline cationic species. Similarly, the invention relates to a device for carrying out the process that is substantially equivalent or identical to the device described above. DESCRIPTION OF THE FIGURES

[0148] The invention will be better understood upon reading the accompanying figures, which are provided by way of example and are not intended to be limiting, in which: There figure 1is a graph showing the evolution of the concentration in mMol / L of the five ions Na+, K+, Mg2+, Ca2+ and Cl- in salt water initially at 180 g / L after 4 serial contacts with a composition of 0.4 Mol / L of MEC1 and 1.2 Mol / L of MSA9, all dissolved in 1,2-dichlorobenzene according to the invention, or it is expected at each step that the extraction equilibrium is reached before proceeding to the next, as described in Example 2. The figure 2 is a graph showing the extraction rates in molar %, at room temperature, of 7 salts, LiCl, NaCl, KCl, MgCl₂, CaCl₂, SrCl₂ and BaCl₂, extracted individually from a salt water of initial concentration 0.1 mol / L using a composition of 0.1 mol / L of MEC₂ and 3.5 mol / L of MSA₂ diluted in dichloromethane according to the invention, expressed as a function of the ionic radius of the cation, as described in Example 3. figure 3is a graph showing the absorption isotherms of CaCl₂ at room temperature and at 80°C of a composition of 0.1 mol / L of MEC₂ and 1 mol / L of MSA₂, all dissolved in 1,2-dichlorobenzene according to the invention, as described in Example 4. figure 4 is a graph showing a comparison of two regeneration phases at 20°C and 80°C of a composition of 0.1 mol / L MEC2 and 1 mol / L MSA9, dissolved in 1,2-dichlorobenzene according to the invention, which was loaded with CaCl2 at a concentration of 80 mmol / L before initiating several successive deextraction phases with distilled water, as described in Example 5. The figure 5is a table showing the extraction rates in molar %, at room temperature, of 7 salts, LiCl, NaCl, KCl, MgCl₂, CaCl₂, SrCl₂ and BaCl₂, extracted individually from a salt water of initial concentration 0.1 mol / L by using a composition of 0.1 mol / L of MEC1 to MEC8 and 3.5 mol / L of MSA₂ for MEC1 and MEC2, or 1 mol / L of MSA₂ for MEC3 to MEC8, all diluted in dichloromethane for MEC1 and MEC2 or in 1,2-dichlorbenzene for MEC3 to MEC8 according to the invention, expressed as a function of the ionic radius of the cation, as partly described in Examples 1 and 3. The figure 6 represents the NMR spectrum of compound MSA11. EXAMPLES Description of the mechanical components used in the implementation of the invention

[0149] Various ion-extracting compositions according to the invention are exemplified. The 12 ECMs used in these compositions are as follows: Name Nomenclature Formula developed MEC 1 4-tert-butyl-Calix[4]arene tetrakis(N,N-diethylacetamide), CAS No. 114155-16-7, C68H100N4O8, MW= 1101.5 g / mol, MP = 223-226°C Log K(Li +< , MeOH, 25°C) = 4.0 Log K(Na +<, MeOH, 25°C) = 7.9 Log K(K +<, MeOH, 25°C) = 5.8 Log K(Rb +<, MeOH, 25°C) = 3.8 Log K(Cs +<, MeOH, 25°C) = 2.5 Log K(Mg++<, MeOH, 25°C) < 1.2 Log K(Ca++<, MeOH, 25°C) > 9.0 Log K(Sr++<, MeOH, 25°C) > 9.0 Log K(Ba++<, MeOH, 25°C) = 7.2 MEC 2 4-tert-butyl-Calix[6]arène hexakis(N,N-diéthylacétamide), CAS n° 111786-95-9, C 102 H 150 N 6 O 12 , MW= 1650 g / mole, Log K(Li +< , MeOH, 25°C) = 2,6 Log K(Na +< , MeOH, 25°C) = 2,8 Log K(K +< , MeOH, 25°C) = 3,3 Log K(Rb +< , MeOH, 25°C) = 2,6 Log K(Cs +< , MeOH, 25°C) = 2,8 Log K(Mg ++< , MeOH, 25°C) = 1,3* Log K(Ca ++< , MeOH, 25°C) = 8,2* Log K(Sr ++< , MeOH, 25°C) = 8,1* Log K(Ba ++< , MeOH, 25°C) = 8,3* MEC 3 4-tert-butyl-Calix[4]arène tetrakis(N-piperidinylacétamide), CAS n° 353236-41-6 C 72 H 100 N 4 O 8 , MW= 1148,6 g / mole, MP= 272-276°C MEC 4 4-tert-butyl-Calix[4]arène tetrakis(N-pyrrolidinylacétamide), CAS n°133801-01-1 C 68 H 94 N 4 O 8 , MW= 1094 g / mole, Log K(Li +< , MeOH, 25°C) = 3,0 Log K(Na +< , MeOH, 25°C) = 7,2 Log K(K +< , MeOH, 25°C) = 5,4 Log K(Rb +< , MeOH, 25°C) = 3,0 Log K(Cs +< , MeOH, 25°C) = 1,0 Log K(Mg ++< , MeOH, 25°C) = 1,2 Log K(Ca ++< , MeOH, 25°C) = 7,8 Log K(Sr ++< , MeOH, 25°C) = 8,1 Log K(Ba ++< , MeOH, 25°C) = 6,8 MEC 5 4-tert-butyl-Calix[4]arene tetrakis(N,N-di-n-propylacetamide), CAS No. 162714-60-5 C 76 H 116 N 4 O 8 , MW= 1212.46 g / mole, MP= 191–194°C MEC 6 4-tert-butyl-Calix[4]arene tetrakis(N,N-ethyl-n-propylacetamide), C 72 H 108 N 4 O 8 , MW= 1156 g / mole, MEC 7 4-tert-butyl-Calix[4]arene tetrakis(N,N-di-iso-butylacetamide), C 84 H 132 N 4 O 8 , MW= 1324.46 g / mole, MP= 164–167°C MEC 8 4-tert-butyl-Calix[4]arene tetrakis(N,N-di-iso-propylacetamide), C 76 H 116 N 4 O 8 , MW= 1212 g / mole, MEC 9 4-tert-butyl-Calix[8]arene octakis(N,N-diethylacetamide), CAS n° 315191-66-1, C 136 H 200 N 8 O 16 , MW= 2100 g / mole, Log K(Li +< , MeOH, 25°C) = 2.1* Log K(Na +< , MeOH, 25°C) = 2.2* Log K(K +< , MeOH, 25°C) = 2.2* Log K(Rb +< , MeOH, 25°C) = 1.9* Log K(Cs +< , MeOH, 25°C) = 2.0* Log K(Mg ++< , MeOH, 25°C) = 1.3* Log K(Ca ++< , MeOH, 25°C) = 7.2 Log K(Sr ++< , MeOH, 25°C) = 7.2* Log K(Ba ++< , MeOH, 25°C) = 8.6* MEC 10 4-tert-Butylcalix[4]arene-tetraacetic acid tetraethyl ester, CAS n° 97600-5-8, C 60 H 80 O 12 , MW= 993.27 g / mole, Log K(Li +<, MeOH, 25°C) = 2.6 Log K(Na +<, MeOH, 25°C) = 5.0 Log K(K +<, MeOH, 25°C) = 2.4 Log K(Rb +<, MeOH, 25°C) = 3.1 Log K(Cs +<, MeOH, 25°C) = 2.7 MEC 11 4-tert-Butylcalix[5]arene-pentaacetic acid pentaethyl ester, CAS n° 152495-34-6, C 75 H 100 O 15, MW= 993.27 g / mole, Log K(Li +< , MeOH, 25°C) = 1.0 Log K(Na +<, MeOH, 25°C) = 4.4 Log K(K +<, MeOH, 25°C) = 5.3 Log K(Rb +<, MeOH, 25°C) = 5.6 Log K(Cs +<, MeOH, 25°C) = 5.5 MEC 12 4-tert-Butylcalix[6]arene-hexaaacetic acid hexaethyl ester, CAS n° 92003-62-8, C 90 H 120 O 18, MW= 1489.93 g / mole,

[0150] All of these ECMs are solids that are completely insoluble in water. Generic description of the exemplified implementation methods Extraction composition

[0151] The extraction composition is obtained by solubilizing a quantity of MEC and MSA in the chosen fluidizer, dichloromethane (CH₂Cl₂), dichlorobenzene, dichlorotoluene, or any other fluidizer capable of effectively solubilizing the MEC / MSA mixture to obtain the desired final concentrations after solubilizing the MEC and MSA in a minimum of 3 milliliters of fluidizer. If the chosen fluidizer is also an MSA compound, then the volume of MSA used must be at least 3 milliliters. The given concentrations of MSA₂ and MSA₂ are relative to the volume of fluidizer added, and the MEC concentrations are relative to the volume of fluidizer + MSA added. The organic extraction composition is then gently heated to promote the solubilization of the organic compounds using a hot air gun (temperature of approximately 50 to 60°C) for a few seconds (10 to 30 seconds) until a clear solution is obtained.The composition is then left to rest for 24 hours at room temperature to ensure the stability of the resulting formulation.

[0152] These sealed formulations are then orbitally shaken at 500 rpm for 2 hours after adding an equivalent volume of distilled water twice to allow water saturation of the entire formulation and control of pH at inlet and outlet (pH close to 7, or at least maintained after contact with saturation water).

[0153] The extraction composition is then left to settle. All compositions are stable and settle rapidly (a few minutes at most) in two distinct phases. Salt water - brine containing, among other things, salts to be extracted

[0154] An aqueous solution of the chloride salt(s) in question (NaCl or others) is prepared from twice-distilled water. The chloride salts used are: LiCl, NaCl, KCl, MgCl₂, CaCl₂, SrCl₂, and BaCl₂. Extraction / Deextraction

[0155] 3 mL of the prepared organic extraction composition are then taken from the lower phase of the decanted two-phase mixture and transferred to a flask containing 3 mL of water containing the chloride salt(s) in question (NaCl or other), then the flask is sealed and placed under orbital shaking (at 500 revolutions per minute) for 2 hours at room temperature (TA), i.e. between 20 and 25°C.

[0156] For the case of extraction or de-extraction tests at higher temperatures, in particular at 60°C or 80°C, magnetic stirring (at 500 revolutions per minute) for 2 hours is carried out with indirect thermostatically controlled heating in a metal mold on a hot plate.

[0157] It is verified that droplets of approximately 1-2 mm are present during these agitations to ensure that equilibrium is reached in the distribution of the chloride salt (NaCl or other) between the two liquid phases at the end of agitation. The appearance of the organic and aqueous phases is clear and colorless or slightly cloudy.

[0158] Once the two hours of stirring were completed, the stirring was stopped and the mixture was allowed to settle for approximately 10 minutes, at least until the two phases had completely separated, at the test temperature. The upper aqueous phase was then collected, stirred, and diluted for salinity analysis by Ion Chromatography (using a Metrohm™ instrument incorporating a cation analysis column and an anion analysis column adapted to the ions and salt concentrations of interest). Similarly, the initial aqueous chloride salt solution (NaCl or other) was also analyzed by this ion chromatography to determine its relative molar concentration of cations and chlorides before extraction. All extractions and analyses were duplicated. Example 1 : Room temperature extractions of saline solutions into single salts with the MEC1.

[0159] In this example the MEC used is 4-tert-butyl-Calix[4]arene tetrakis(N,N-diethylacetamide) (MEC1 of CAS No.: 114155-16-7).

[0160] It was synthesized from 4-tert-Butylcalix[4]arene with the molecular formula C44H56O4 and CAS No. 60705-62-6, purchased from TCI Chemicals, according to the synthesis procedure described in the publication "Selective alkali and alkaline earth cation complexation by calixarene amides, New J. Chem, 1991,15,33-37".

[0161] The MSA used is MSA2, CAS No. 32707-89-4, C9H6F6O, MW = 244.13 g / mol, a white solid available from several distributors. Its characteristics are as follows: Settings Values Units Density (1,433) kg / L Viscosity - mPa.s BP 255 °C MP 55 °C FP 97 °C Log P 3.0 (estimated) - Solubility 2,29 mMole / L pKa 14,7 + / - 1 -

[0162] The extractant composition considered comprises 0.1 mol / L of MEC1 and 3.52 mol / L of MSA2 in dichloromethane CH2Cl2 obtained as previously described. The initial concentration of the salt considered in the water, whether LiCl, NaCl, KCl, MgCl2, CaCl2, SrCl2 or BaCl2, is 0.1 mol / L.

[0163] After carrying out these 7 specific (doubled) salt extractions, the quantities of cations extracted in relative molar percentages before and after extraction at room temperature and at iso-volume water / extracting formulation are indicated in Table I: Tableau I MEC1 0,1 M Extraction rate at TA (Organic / Water = 1) MSA2 3,52 M LiCl NaCl KCI MgCl2 CaCl2 SrCl 2 BaCl 2 Thinner CH2 Cl2 73,7% 85,8% 75,8% 5,4% 59,4% 64,0% 46,1%

[0164] The extraction of cations from a brine consisting of a single alkali or alkaline earth chloride therefore varies from 5.4% to 85.8% depending on the cation. In these single-salt solutions, and for this MEC1, the salt extraction level is very good except for magnesium, which, with its ionic radius of 76 pm and its high hydrophilicity, does not fit within the extraction envelope of this 16-carbon macrocycle, which is still too large. This formulation therefore seems well-suited to the large-scale desalination of saline water, or even brine (water with a salinity greater than 50 g / L). Example 2 : Extraction of salts from a brine by use of MEC1.

[0165] The extractant composition is as follows: 0.4 Mol / L of MEC1 (see example 1, CAS number: 114155-16-7), supplemented with 1.2 Mol / L of MSA9 of formula: where R is the heptyl radical: nC7H15.

[0166] This compound was synthesized by the method described in Example 9 below.

[0167] The fluidizer used to solubilize these two compounds is 1,2-dichlorobenzene, CAS number 95-50-1, purchased from TCl-Chemicals and identified by the abbreviation 12CIPh.

[0168] The brine is a highly saline water, at 180 g / L (or 5.6 mol / L), composed of sodium, potassium, calcium, magnesium, and chloride ions in the proportions shown in Table II below. The saline water to be treated was contacted with three times the volume of this extractant composition to approximate the operating conditions.

[0169] Table II below shows the concentrations in mMol / L of water of each of the ions before and after each of the four extraction steps, carried out at room temperature (TA). Table II MEC1 0,4 M Changes in salinity at ambient temperature, in mmol / litre MSA9 1,2 M N / A K Mg That Cl Total Thinner 12CIPh Initial 1650 20,8 77,1 447 3432 5626 Org. / Water 3 Extract 1 1162 22,5 83,4 495 2703 4466 Extract2 429 23,4 86,4 492 2292 3322 Extract3 8,54 13,9 87,6 360 1083 1553 Extract4 3,70 3,65 94,2 114 469 685 Equivalent 4 g / Liter 0,09 0,14 2,29 4,57 16,62 23,70 This data is illustrated by the figure 1 It is clear that the first salt to be extracted is NaCl, then from the third extraction stage onward, calcium and potassium chlorides begin to be extracted while the NaCl concentration continues to decrease in the water. Unsurprisingly, magnesium is not extracted. Ultimately, after four phases of contact and mixing between liquid phases, the total salinity of the water decreased from 180 g / L to 23.7 g / L. A fifth extraction would have allowed for complete desalination, with MgCl₂ remaining. 2 close. Example 3 : Room temperature extractions of saline solutions into single salts with the MEC2.

[0170] This example 3 is carried out under the same conditions as example 1 except that MEC1 is replaced by MEC2.

[0171] The MEC used is 4-tert-butyl-Calix[6]arene hexakis(N,N-diethylacetamide (MEC2 of CAS No.: 111786-95-9).

[0172] It was synthesized in-house from 4-tert-Butylcalix[6]arene with the molecular formula C66H84O6 and CAS No. 78092-53-2, purchased from TCI Chemicals, according to the synthesis procedure described in the publication "Selective Complexation and Membrane Transport of Guanidinium Salts by Calix[6]arene Amides", Israel J. Chem, 1992, 32, 79-87. The MSA used is MSA2 of CAS No. 32707-89-4, C 9 H 6 F 6 O, MW= 244.13 g / mol, White solid which is available from several distributors.

[0173] After carrying out the 7 specific (doubled) salt extractions, the quantities of cations extracted in relative molar percentages before and after extraction at room temperature and at iso-volume water / extracting formulation are indicated in Table III: Tableau III MEC2 0,1 M Extraction rate at TA (Organic / Water = 1) MSA2 3,52 M LiCl NaCl KCl MgCl2 CaCl2 SrCl 2 BaCl 2 Thinner CH2 Cl2 21,9% 22,7% 25,4% 13,5% 57,8% 63,8% 63,2% The extraction of cations from a brine consisting of a single alkali or alkaline earth chloride therefore varies from 13.5% to 63.8% depending on the cation. In these single-salt solutions, divalent cations are extracted in quantities two to three times greater than monovalent cations, with the exception of the magnesium ion, Mg 2+ much more hydrophilic and small, which is difficult to extract here as illustrated by the figure 2 . The composition according to the invention therefore demonstrates a particularly interesting specificity of this formulation for many industrial applications where Calcium, although more hydrophilic than Sodium (ΔG°hyd = -1515 kJ / mol versus -406 kJ / mol), despite having very close ionic radii (102 and 100 pm), is 2.54 times better extracted from water in their respective chloride forms. Example 4: Characterization of an extractant composition incorporating MEC2 for the extraction of CaCl2

[0174] This series of examples aims to establish two extraction isotherms of CaCl 2 at 20°C and 80°C for an extractant composition incorporating 0.1 Mole / L of MEC2, combined with 1 Mole / L of MSA 9; all dissolved in 1,2-dichlorobenzene.

[0175] After carrying out the 7 specific (doubled) salt extractions, the quantities of cations extracted in relative molar percentages before and after extraction at room temperature and at iso-volume water / extracting formulation are indicated in Table IV: Table IV MEC2 0,1 M Extraction rate at TA (Organic / Water = 1) MSA9 1 M 0,01M 0,02M 0,03M 0,04M 0,1M 0,2M 0,4M Thinner 12CIPh 39% 42% 41% 40% 34% 27% 16% The same extraction series was then carried out at 80°C to give the following table V: Tableau V MEC2 0,1 M Extraction rate at 80°C (Organic / Water = 1) MSA9 1 M 0,01M 0,02M 0,03M 0,04M 0,1M 0,2M 0,4M Thinner 12CIPh 11% 16% 18% 17% 18% 16% 10% Extraction temperature has a strong influence on extraction performance. Based on these studies and the collected data, it was possible to plot these absorption isotherms in figure 3 for concentrations in Mol / Liter. The x-axis represents the concentration of NaCl in water and the y-axis represents the concentration of NaCl in the organic phase, at absorption equilibrium. The liquid-liquid salt extraction process according to the invention is exothermic in absorption and endothermic in regeneration, which allows thermal regeneration, with hot water, of the extracting organic composition. Example 5 : Extraction process including thermal regeneration of the extractant composition incorporating MEC2 and associated impacts on CaCl2 desorption

[0176] Two samples of the extractant composition from Example 4, with the highest CaCl₂ concentration at 20°C, were contacted with a 1 mol / L CaCl₂ saline solution at room temperature to increase the salt loading level of the dissolved MEC₂ cation extractant molecules, thus approaching their salt saturation level (0.1 mol / L). These two samples were then contacted with an equal volume of distilled water at 20°C and stirred. One of the two two-phase samples was then heated to 80°C and kept under stirring. Given an initial salt loading level of 80 mM / L, it appears that this level drops to 15.27 mM / L during the first regeneration step at 80°C, whereas during regeneration at 20°C, the residual salt concentration is 29.3 mM / L. figure 4This illustrates the results obtained over several serial contact steps with an equal volume of distilled water in the hydrophobic organic liquid phase loaded with salts. Hot regeneration of the extractant composition is significantly more efficient due to a 2x reduction in the number of regeneration steps required to achieve the same overall CaCl₂ deextraction rate. In practice, this advantage appears to be even more pronounced when using a resin with a high ECM (Electromagnetic Compound) loading rate, and therefore a high salt content.

[0177] Increasing the regeneration temperature reduces the number of successive contact steps with distilled water of the same volume, while allowing for greater salt extraction with each step. It also enables access to regeneration waters with a higher concentration of extracted salts due to the use of a smaller volume of regeneration water. Example 6 : Comparative examples : Selective extractions at room temperature of cations from a binary mixture of NaCl / CaCl2 salt

[0178] A brine containing an equimolar mixture of salts, 0.05 mol / L NaCl and CaCl₂ each, prepared as previously described, was contacted with two extractant compositions, one of which is according to the invention. These compositions differ only in the MEC compound used, which remains a disubstituted primary amide but whose macrocycle size is modified, being respectively 16 carbons (MEC1) and 24 carbons (MEC2). These compositions are obtained according to the process described previously.

[0179] Each extractant composition comprises 0.1 mol / L of MEC and 2.4 mol / L of MSA9 in 1,2-dichlorobenzene.

[0180] The 1,2-dichlorobenzene (CAS No.: 95-50-1), with a purity greater than 99%, comes from the company TCI Chemicals.

[0181] The quantities of cations, in molar percentage, extracted from the mixture are indicated in Table VI: Table VI MEC1 / MEC2 Cations Na +< That ++< 4-tert-ButylCalix[4]CH 2 C(=O)NEt 2 %E 88,0% 10,0% 4-tert-ButylCalix[6]CH 2 C(=O)NEt 2 %E 4,0% 56,0% Depending on the selected ECM, in a salt mixture, the extraction of these cations sees a Increased selectivity means that the cation most extracted in pure form is predominantly extracted in salt mixtures. Co-absorption here favors the initially best extraction. In particular, the formulation incorporating MEC2 with a 24-unit carbon ring has a calcium extraction rate relative to sodium 14 times higher in mixtures at iso-concentration of cation, compared to a rate of 2.54 for solutions containing only one of these salts (see examples 1 & 3). Such extraction capacities have numerous industrial applications in water descaling. Example 7 : Selective extractions at room temperature of cations from a binary mixture of NaCl and CaCl2 salts at differentiated initial concentrations.

[0182] A brine containing a mixture of NaCl and CaCl2 is prepared as previously described to obtain the following initial salt concentrations in the mixture: 0.2 mol / L NaCl and 0.03 mol / L CaCl2. The extraction resin is composed of 0.1 mol / L MEC2, 3.52 mol / L MSA2 and a supplement of liquid MSA1, also used as a fluidizer.

[0183] The quantities of cations, in molar percentage, extracted from the mixture are indicated in Table VII: Table VII MEC2 Cations Na +< That ++< 4-tert-ButylCalix[6]CH 2 C(=O)NEt 2 %E 5,0% 88,0%

[0184] It appears here that the ratio of extraction rates for Ca / Na is 17.6, which validates one of the objects of the invention due to an improvement in the deviations from extraction in multi-salts, in the presence of a common anion. Example 8 : Selective extractions at room temperature of cations from a mixture of four salts: NaCl, CaCl₂, SrCl₂ and BaCl 2

[0185] A brine containing a mixture of NaCl, CaCl₂, SrCl₂, and BaCl₂ was prepared as previously described. The dissolved salt concentrations are given in Table VIII in mmol / L. The extraction was performed a second time with modified divalent salt concentrations. The dissolved salt concentrations are given in Table IX in mmol / L.

[0186] The extractant composition consists of 0.1 Mol / L of MEC2 and a mixture of two MSAs. This mixture consists of MSA2, generally called [3,5-Bis(Trifluoromethyl)benzyl Alcohol] (35TFMBnOH) of CAS No.: 32707-89-4, at 60% by volume, and MSA1, called [3-(Trifluoromethyl)benzyl Alcohol] (3TFMBnOH), with the molecular formula C 8 H 7 F 3 O, MW = 176.14 g / Mole and CAS No.: 349-75-7, at 40% by volume, which acts as both a fluidizer and an MSA due to its liquid form.

[0187] The extraction is carried out as described in example 1 and at room temperature.

[0188] The quantities of cations extracted in molar percentage are indicated in Tables VIII and IX, respectively for initial and final ionic concentrations expressed in mMoles / L. Table VIII Cations CATIONS (mMol / L) CI- ANIONS (mMol / L) Initial Concentration Final Concentration %extraction Initial Concentration Final Concentration Na +< 193,52 199,4775 0% 257,74 213,38 Ca 2+< 29,13 0,4916 98% Sr 2+< 4,29 0 100% Ba 2+< 4,69 0 100% Tableau IX Cations CATIONS ANIONS CI- Initial Concentration Final Concentration %extraction Initial Concentration Final concentration Na +< 196,04 195,9835 0% 245,4 203,16 Ca 2+< 9,25 0 100% Sr 2+< 9,17 0 100% Ba 2+< 9,32 0 100%

[0189] It appears here that for high relative concentrations of sodium compared to these scaling divalent cations, an extraction selectivity of 100% can be obtained.

[0190] The selective extraction of divalent cations demonstrates the ability of the compositions according to the invention to effectively combat limescale and purify water, due to a selective extraction of Calcium Ca++, Strontium and Barium. Example 9 : Synthesis of compounds MSA9, MSA10, MSAC11 and MSA12 Summary diagram

[0191] R = n-C 7 H 15 (MSA9), n-C 9 H 19 (MSA10), n-C 11 H 23 (MSA11), n-C 13 H 27 (MSA12). Protocol

[0192] To a solution of 3,5-bis(trifluoromethyl)aniline (8.79 mL, 56.29 mmol, 1.0 eq.), dichloromethane (40 mL), and triethylamine (8.63 mL, 61.92 mmol, 1.1 eq.), acid chloride (56.29 mmol, 1.0 eq.) is added dropwise while stirring. The temperature is controlled during addition and must not exceed 38°C (the boiling point of dichloromethane). The reaction mixture is stirred for 5 hours at room temperature. A 1 M HCl solution (50 mL) is added, and then the organic phase is washed. Successive washes are performed with a 1 M HCl solution (50 mL) and a saturated NaCl solution (50 mL). The organic phase is dried over Na₂SO₄, filtered, and then the solvent is evaporated under reduced pressure. The solid residue is then re-treated with petroleum ether (cold or at room temperature), washed, filtered and then vacuum-dried to give the desired amide.The petroleum ether used is a mixture of hydrocarbons composed mainly of n-pentane, 2-methyl pentane and CAS number 64742-49-0, sourced from the company VWR where it is marketed under the name Petroleum Ether 40-60°C GPR RECTAPUR. The characteristics of the compounds obtained are presented in Table X. Table XR Compound Molar mass (g / mol) Petroleum ether temperature Yield Appearance Melting point nC 7 H 15 MSA9 355,3 Cold (-20°C) 91% Solid white 43-44°C nC 9 H 19 MSA 10 383,3 Ambient 92% Solid white 79-81°C nC 11 H 23 MSA11 411,4 Ambient 92% Solid white 60-61°C nC 13 H 27 MSA12 439,5 Ambient 90% Solid white 53-54°C

[0193] The compounds MSA9, MSA10, MSAC11 and MSAC12 have the following respective IUPAC names: N-[3,5-bis(trifluoromethyl)phenyl]octanamide, N-[3,5-bis(trifluoromethyl)phenyl]decanamide, N-[3,5-bis(trifluoromethyl)phenyl]dodecanamide, N-[3,5-bis(trifluoromethyl)phenyl]tetradecanamide and have also been identified by NMR spectroscopy. figure 6, represents the NMR spectrum (CDCl3, 300 MHz) of the compound MSA11 whose peaks are as follows: 1H NMR (CDCl3, 300 MHz): δ (ppm) = 0.87 (t, 3J = 7.0 Hz, 3H), 1.20-1.35 (m, 20H), 1.73 (quint., 3J = 7.0 Hz, 2H), 2.40 (t, , 3J = 7.0 Hz, 2H), 7.58 (s, 1H), 7.77 (bs, 1H), 8.04 (s, 2H). Example 10: Room temperature extractions of saline solutions in mono-salts with the MEC10.

[0194] This example 10 is carried out under the same conditions as examples 1 and 3 except that the MEC considered is MEC10.

[0195] The MEC used is 4-tert-butyl-Calix[4]arene acid tetraethyl ester (MEC10 CAS No.: 97600-39-0).

[0196] It was synthesized in-house from 4-tert-Butylcalix[4]arene, with the molecular formula C44H56O4 and CAS No. 60705-62-6, and ethyl bromoacetate, CAS No. 105-36-2, products purchased from Sigma-Aldrich for the implementation of a standard alcohol addition procedure, in a 5:1 by volume THF / DMF mixture. The MSA used was MSA2, CAS No. 32707-89-4, C9H6F6O, MW = 244.13 g / mol, a white solid available from several distributors.

[0197] After carrying out the 7 specific (doubled) salt extractions, the quantities of cations extracted in relative molar percentages before and after extraction at room temperature and at iso-volume water / extracting formulation are indicated in Table XI: Tableau XI MEC10 0,1 M Extraction rate at TA (Organic / Water = 1) MSA2 3,52 M LiCl NaCl KCl MgCl2 CaCl2 SrCl 2 BaCl 2 Thinner CH2 Cl2 5,5% 66,2% 14,4% 5,1% 4,7% 5,9% 3,7% The extraction of cations from a brine consisting of a single alkali or alkaline earth chloride therefore varies from 3.7% to 66.2% depending on the cation. In these single-salt solutions, it appears that MEC10 is selective for sodium chloride among the alkali cations and that divalent cations are extracted very weakly with a Na / Ca selectivity of 14. The composition according to the invention therefore demonstrates a particularly interesting specificity of this formulation for industrial applications related, for example, to chlorochemistry, where NaCl can be selectively extracted from seawater or brine to supply electrolyzers for the production of NaOH, HCl, or even Cl₂ 2 . Example 11: Room temperature extractions of saline solutions in mono-salts with the MEC12.

[0198] This example 11 is carried out under the same conditions as examples 1, 3 and 10 except that the MEC considered is the MEC12.

[0199] The MEC used is 4-tert-butyl-Calix[6]arene acid hexaethyl ester (MEC12 CAS No.: 92003-62-8).

[0200] It was synthesized in-house from 4-tert-Butylcalix[6]arene of molecular formula C 66 H 84 O 6 and CAS No. 78092-53-2 and ethyl bromoacetate of CAS No. 105-36-2, products purchased from Sigma-Aldrich for the implementation of a classic alcohol addition procedure, in a 5 / 1 by volume THF / DMF mixture. The MSA used is MSA2 of CAS No. 32707-89-4, C 9 H 6 F 6 O, MW= 244.13 g / mol, White solid which is available from several distributors.

[0201] After carrying out the 7 specific (doubled) salt extractions, the quantities of cations extracted in relative molar percentages before and after extraction at room temperature and at iso-volume water / extracting formulation are indicated in Table XII: Table XII MEC12 0,1 M Extraction rate at TA (Organic / Water = 1) MSA2 3,52 M LiCl NaCl KCl MgCl2 CaCl2 SrCl 2 BaCl 2 Thinner CH2 Cl2 9,0% 29,6% 55,7% 5,4% 5,5% 4,6% 11,8%

[0202] The extraction of cations from a brine consisting of a single alkali or alkaline earth chloride therefore varies from 4.6% to 55.7% depending on the cation. In these single-salt solutions, it appears that MEC12 is selective for larger diameter alkali chloride salts and that divalent cations are extracted very weakly, with a K / Ca selectivity of 10.2, which should be even better for Rb+ and Cs+ since MEC12 is known to be a good ionophore of cesium. The invention is not limited to the embodiments presented, and other embodiments will be readily apparent to those skilled in the art. In particular, it is possible to combine several MECs within an extraction formulation to combine the specific performance of each MEC for optimal overall performance.

Claims

1. - A process for deionizing water by extraction in a liquid medium with thermal regeneration, applied to the extraction of a divalent, non-alkaline cationic species and of a complementary anionic species from a saline liquid aqueous solution, the saline liquid aqueous solution comprising: - a salt of the non-alkaline cationic species, and - a salt of a cationic species of an alkaline metal, the process comprising the following steps: a) mixing in a first reactor, at a first temperature, of a liquid hydrophobic organic phase and of the saline liquid aqueous solution, in order to subsequently obtain a treated liquid aqueous solution and a hydrophobic liquid organic phase charged with the non-alkaline cationic species and the complementary anionic species, the liquid hydrophobic organic phase comprising an extracting molecule of the non-alkaline cationic species, a solvating molecule of the complementary anionic species ("MSA"), the solvating molecule of the complementary anionic species being a hydrophobic and protic compound, the pKa of which in water at 25°C being at least 9 and being lower than 15 at 25°C, and optionally a fluidizing agent; b) separating, on one hand, the treated liquid aqueous solution and, on the other hand, the liquid hydrophobic organic phase charged with the non-alkaline cationic species and the complementary anionic species; and c) mixing, at a second temperature, in the liquid phase, in a second reactor, of the liquid hydrophobic organic phase, charged with the non-alkaline cationic species and the complementary anionic species, with a regeneration liquid aqueous solution, in order to subsequently obtain a regenerated liquid hydrophobic organic phase and a regeneration liquid aqueous solution charged with the non-alkaline cationic species and the complementary anionic species, the difference between the first and second temperatures varying from 30°C to 150°C; wherein the extracting molecule of a non-alkaline cationic species is a macrocycle, the cycle of which is formed from 24 to 32 carbon atoms, functionalized with amide groups, having the following formulae (I) or (II): where - n is an integer from 5 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 selected from the group constituted by methyl, ethyl, propyl, isopropyl, butyl and isobutyl, pentyl, hexyl, heptyl and octyl groups, or R' and R" together form a pyrrolidine, piperidine or morpholine ring.

2. - The process according to claim 1, characterized by the fact that the extracting molecule of the at least one non-alkaline cationic species is selected from the compounds of formula (I) with calixarene macrocycle, with p=1, and R, R', R'' and n as defined below: RR'R"ntert-ButylPyrrolidinyl6tert-ButylEthylEthyl6O-OctylEthylEthyl6OCH2-PhenylEthylEthyl6HEthylEthyl6O-methylEthylEthyl6tert-ButylEthylEthyl8O-OctylEthylEthyl8OCH2-PhenylEthylEthyl8HEthylEthyl8O-methylEthylEthyl8 advantageously in their cone or partial cone configuration.

3. - The process according to one of claims 1 or 2, characterized by the fact that the non-alkaline cationic species is at least one of the following cations: calcium, strontium and barium.

4. - The process according to anyone of claims 1 to 3, characterized by the fact that the non-alkaline cationic species is selectively extracted with respect to the cationic species of an alkaline metal.

5. - The process according to anyone of claims 1 to 4, characterized by the fact that the cationic species of an alkaline metal is sodium ion Na+.

6. - A process for deionizing water by extraction in a liquid medium with thermal regeneration, applied to the selective extraction of at least one alkaline cationic species and of a complementary anionic species from a saline liquid aqueous solution, the saline liquid aqueous solution comprising: - a salt of the at least one alkaline cationic species, and - a salt of a cationic species of an alkaline earth metal, the process comprising the following steps: a) mixing in a first reactor, at a first temperature, of a liquid hydrophobic organic phase and of the saline liquid aqueous solution, in order to subsequently obtain a treated liquid aqueous solution and a hydrophobic liquid organic phase charged with the alkaline cationic species and the complementary anionic species, the liquid hydrophobic organic phase comprising an extracting molecule of the alkaline cationic species, a solvating molecule of the complementary anionic species ("MSA"), the solvating molecule of the complementary anionic species being a hydrophobic and protic compound, the pKa of which in water at 25°C being at least 9 and being lower than 15 at 25°C, and optionally a fluidizing agent;; b) separating, on one hand, the treated liquid aqueous solution and, on the other hand, the liquid hydrophobic organic phase charged with the alkaline cationic species and the complementary anionic species; and c) mixing, at a second temperature, in the liquid phase, in a second reactor, of the liquid hydrophobic organic phase, charged with the alkaline cationic species and the complementary anionic species, with a regeneration liquid aqueous solution, in order to subsequently obtain a regenerated liquid hydrophobic organic phase and a regeneration liquid aqueous solution charged with the alkaline cationic species and the complementary anionic species, the difference between the first and second temperatures varying from 30°C to 150°C; wherein the extracting molecule of at least one alkaline cationic species is a macrocycle, the cycle of which is formed from 16 to 24 atoms, in particular of carbon, and functionalized with ester or ketone groups, where the extracting molecule of at least one alkaline cationic species is selected from the compounds of generic formulae (V) or (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 selected from the group constituted by methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, heptyl and octyl groups, in order to make a ketone-type binding group, or R' is selected from the group consisting of O-methyl, O-ethyl, O-propyl, O-isopropyl, O-butyl, O-isobutyl, O-pentyl, O-hexyl, O-heptyl, O-octyl, OCH2-Phenyl groups in order to make an ester-type binding group.

7. - The process according to claim 6, characterized by the fact that the extracting molecule of at least one alkaline cationic species is selected from the compounds of formula (V) with calixarene macrocycle, with p=1, and R, R' and n as defined below: RR'nHO-ethyl4HO-isopropyl4HO-tert-butyl4tert-butylO-ethyl4tert-butylO-isopropyl4tert-butylO-tert-butyl4tert-octylO-ethyl4tert-butylO-ethyl5tert-butyltert-butyl4tert-butylO-ethyl6 advantageously in their cone or partial cone configuration.

8. - The process according to one of claims 6 or 7, characterized by the fact that the extracting molecule has a complexing constant Log K, in methanol at 25°C, of the alkaline cationic species to be extracted, higher than 3 and less than 11, preferably higher than 5 and less than 9.

9. - The process according to anyone of claims 6 to 8, characterized by the fact that the at least one alkaline cationic species is selected from lithium, sodium, potassium, rubidium and cesium.

10. - The process according to anyone of claims 6 to 9, characterized by the fact that the process consists in a selective extraction of alkaline salts with hydrophilic anions, such as chlorides.

11. - The process according to anyone of claims 1 to 10, characterized by the fact that the fluidizing agent is selected from the aromatic polar solvents, for example derived from dichlorobenzenes, dichlorotoluenes, derivatives thereof and mixtures thereof.

12. - The process according to any ne of claims 1 to 11, characterized by the fact that pKa of the solvating molecule of the complementary anionic species is of at least 10.5 and is lower than the pKa of water at 25°C.

13. - A hydrophobic liquid organic composition constituted by the hydrophobic liquid organic phase as defined in point a) of claim 1, and including an extracting molecule of a non-alkaline cationic species as defined in claim 1 or 2, a solvating molecule of a complementay anionic species as defined in point a) of claim 1 or in claim 12, and optionally a fluidizing agent as defined in point a) of claim 1 or in claim 11.

14. - A hydrophobic liquid organic composition constituted by the hydrophobic liquid organic phase as defined in point a) of claim 6, and including an extracting molecule of an alkaline cationic species as defined in claim 6 or 7, a solvating molecule of a complementay anionic species as defined in point a) of claim 6 or in claim 12, and optionally a fluidizing agent as defined in point a) of claim 6 or in claim 11.