Method for extracting salts and temperature-regenerated extracting composition

Abstract

A temperature-regenerated hydrophobic liquid composition includes an extracting molecule of a non-alkaline cationic species, a solvating molecule of a complimentary anionic species and a fluidizing agent. The extracting molecule of a non-alkaline cationic species is a macrocycle of which the ring is formed from 24-32 carbon atoms and has the following formula (I) or (II): wherein -n is an integer ranging from 5 to 8, -p is 1 or 2, -m is 3 or 4, -q and t, which may be identical or different, are 0, 1 or 2, —R is a tert-butyl, tert-octyl, O-methyl, O-ethyl, O-propyl, O-isopropyl, O-butyl, O-isobutyl, O-pentyl, O-hexyl, O-heptyl, O-octyl, or OCH.sub.2Phenyl group or a hydrogen atom, and—R′ and R″, which may be identical or different, are chosen from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, heptyl and octyl groups or R′ and R″ together form a pyrrolidine, piperidine or morpholine ring.

Claims

1. A process for deionizing water by extraction in a liquid medium with thermal regeneration, applied to the 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, a liquid hydrophobic organic phase and the saline liquid aqueous solution, in order to subsequently obtain a treated liquid aqueous solution and a liquid hydrophobic organic phase charged with the at least one alkaline cationic species and the complementary anionic species, the liquid hydrophobic organic phase comprising an extracting molecule of the at least one alkaline cationic species, a solvating molecule of the complementary anionic species; b) separating the treated liquid aqueous solution and the liquid hydrophobic organic phase charged with the at least one alkaline cationic species and the complementary anionic species; and c) mixing in a second reactor, the liquid hydrophobic organic phase, charged with the at least one 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 at least one 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 the at least one alkaline cationic species is a macrocycle, the cycle of which is formed from 16 to 24 atoms and functionalized with ester or ketone groups.

2. The process according to claim 1, wherein the extracting molecule of the at least one alkaline cationic species is selected from the compounds of formulae (V) or (VI): ##STR00059## 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, OCH.sub.2-Phenyl groups in order to make an ester-type binding group.

3. The process according to claim 1, wherein the extracting molecule of the 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: TABLE-US-00020 R R′ n H O-ethyl 4 H O-isopropyl 4 H O-tert-butyl 4 tert-butyl O-ethyl 4 tert-butyl O-isopropyl 4 tert-butyl O-tert-butyl 4 tert-octyl O-ethyl 4 tert-butyl O-ethyl 5 tert-butyl tert-butyl 4 tert-butyl O-ethyl  6.

4. The process according to claim 1, wherein the extracting molecule has a complexing constant Log K, in methanol at 25° C., of the at least one alkaline cationic species to be extracted, higher than 3 and less than 11.

5. The process according to claim 1, wherein the at least one alkaline cationic species is selected from lithium, sodium, potassium, rubidium and cesium.

6. The process according to claim 1, wherein the process consists in a selective extraction of alkaline salts with hydrophilic anions.

7. The process according to claim 1, wherein the liquid hydrophobic organic phase comprises a fluidizing agent.

8. The process according to claim 7, wherein the fluidizing agent is selected from the aromatic polar solvents derived from dichlorobenzenes, dichlorotoluenes, derivatives thereof and mixtures thereof.

9. The process according to claim 1, wherein the solvating molecule of the complementary anionic species is a hydrophobic compound and, the pKa of which in water at 25° C. is at least 9, and is lower than the pKa of water at 25° C.

10. Process according to claim 1, wherein the solvating molecule of the complementary anionic species is a molecule of formula: ##STR00060## in which R is R=n-C.sub.7H.sub.15, n-C.sub.9H.sub.19, n-C.sub.11H.sub.23 or n-C.sub.13H.sub.27.

Description

DESCRIPTION OF THE FIGURES

(1) The invention will be better understood upon reading the accompanying figures, which are provided by way of examples and are not limiting in nature, in which:

(2) FIG. 1 is a graph showing the evolution of the concentration in mMol/L of the five ions Na.sup.+, K.sup.+, Mg.sup.2+, Ca.sup.2+ and Cl.sup.− in a salt water which was initially at 180 g/L after 4 contacts in series with a composition which contains 0.4 Mol/L of CEM1 and 1.2 Mol/L of ASM9, the whole dissolved in 1,2-dichlorobenzene according to the invention, wherein the extraction equilibrium is expected to be achieved at each step before carrying out the next one, as described in example 2.

(3) FIG. 2 is a graph showing the extraction rates in molar %, at room temperature, of 7 salts, LiCl, NaCl, KCl, MgCl.sub.2, CaCl.sub.2, SrCl.sub.2 and BaCl.sub.2 individually extracted from a salt water the initial concentration of which was 0.1 Mol/L by using a composition containing 0.1 Mol/L of CEM2 and 3.5 Mol/L of ASM2, the whole dissolved in dichloromethane according to the invention, expressed according to the cation ionic radius, as described in example 3.

(4) FIG. 3 is a graph showing the absorption isotherms of CaCl.sub.2) at room temperature and at 80° C. of a composition containing 0.1 Mol/L of CEM2 and 1 Mol/L of ASM9, the whole dissolved in 1,2-dichlorobenzene according to the invention, as described in example 4.

(5) FIG. 4 is a graph showing a comparison of two regeneration phases at 20° C. and at 80° C. of a composition containing 0.1 Mol/L of CEM2 and 1 Mol/L of ASM9, the whole dissolved in 1,2-dichlorobenzene according to the invention, which was charged with up to 80 mMol/L of CaCl.sub.2) before initiating several successive back-extraction phases with distilled water, as described in example 5.

(6) FIG. 5 is a table showing the extraction rates in molar %, at room temperature, of 7 salts, LiCl, NaCl, KCl, MgCl.sub.2, CaCl.sub.2, SrCl.sub.2 and BaCl.sub.2 individually extracted from a salt water the initial concentration of which was 0.1 Mol/L by using a composition containing 0.1 Mol/L of CEM1 to CEM8 and 3.5 Mol/L of ASM2 for CEM1 and CEM2, or 1 Mol/L of ASM9 for CEM3 to CEM8, the whole dissolved in dichloromethane for CEM1 and CEM2 or in 1,2-dichlorobenzene for CEM3 to CEM8 according to the invention, expressed according to the cation ionic radius, as described in part in examples 1 and 3.

(7) FIG. 6 shows the NMR spectrum of ASM11 compound.

EXAMPLES

(8) Description of the CEMs Used in the Implementation of the Invention

(9) Different ion extracting compositions according to the invention are illustrated. The 12 CEMs used in these compositions are as follows:

(10) TABLE-US-00006 Name Nomenclature Structural formula CEM 1 4-tert-butyl-Calix[4]arene tetrakis(N,N-diethylacetamide), CAS #114155-16-7, C.sub.68H.sub.100N.sub.4O.sub.8, MW = 1101.5 g/mol, MP = 223-226° C., Log K(Li.sup.+, MeOH, 25° C.) = 4.0 Log K(Na.sup.+, MeOH, 25° C.) = 7.9 Log K(K.sup.+, MeOH, 25° C.) = 5.8 Log K(Rb.sup.+, MeOH, 25° C.) = 3.8 Log K(Cs.sup.+, MeOH, 25° C.) = 2.5 Log K(Mg.sup.++, MeOH, 25° C.) < 1.2 Log K(Ca.sup.++, MeOH, 25° C.) > 9.0 Log K(Sr.sup.++, MeOH, 25° C.) > 9.0 Log K(Ba.sup.++, MeOH, 25° C.) = 7.2 CEM 2 4-tert-butyl-Calix[6]arene hexakis(N,N-diethylacetamide), CAS #111786-95-9, C.sub.102H.sub.150N.sub.6O.sub.12, MW = 1650 g/mol, Log K(Li.sup.+, MeOH, 25° C.) = 2.6 Log K(Na.sup.+, MeOH, 25° C.) = 2.8 Log K(K.sup.+, MeOH, 25° C.) = 3.3 Log K(Rb.sup.+, MeOH, 25° C.) = 2.6 Log K(Cs.sup.+, MeOH, 25° C.) = 2.8 Log K(Mg.sup.++, MeOH, 25° C.) = 1.3* Log K(Ca.sup.++, MeOH, 25° C.) = 8.2* Log K(Sr.sup.++, MeOH, 25° C.) = 8.1* Log K(Ba.sup.++, MeOH, 25° C.) = 8.3* *Calculated CEM 3 4-tert-butyl-Calix[4]arene tetrakis(N- piperidinylacetamide), CAS #353236-41-6 C.sub.72H.sub.100N.sub.4O.sub.8, MW = 1148.6 g/mol, MP = 272-276° C. CEM 4 4-tert-butyl-Calix[4]arene tetrakis(N- pyrrolidinylacetamide), CAS #133801-01-1 C.sub.68H.sub.94N.sub.4O.sub.8, MW = 1094 g/mol, Log K(Li.sup.+, MeOH, 25° C.) = 3.0 Log K(Na.sup.+, MeOH, 25° C.) = 7.2 Log K(K.sup.+, MeOH, 25° C.) = 5.4 Log K(Rb.sup.+, MeOH, 25° C.) = 3.0 Log K(Cs.sup.+, MeOH, 25° C.) = 1.0 Log K(Mg.sup.++, MeOH, 25° C.) = 1.2 Log K(Ca.sup.++, MeOH, 25° C.) = 7.8 Log K(Sr.sup.++, MeOH, 25° C.) = 8.1 Log K(Ba.sup.++, MeOH, 25° C.) = 6.8 CEM 5 4-tert-butyl-Calix[4]arene tetrakis(N,N-di-n- propylacetamide), CAS #162714-60-5 C.sub.76H.sub.116N.sub.4O.sub.8, MW = 1212.46 g/mol, MP = 191-194° C. CEM 6 4-tert-butyl-Calix[4]arene tetrakis(N,N-ethyl-n- propylacetamide), C.sub.72H.sub.108N.sub.4O.sub.8, MW = 1156 g/mol, 0 CEM 7 4-tert-butyl-Calix[4]arene tetrakis(N,N-di-iso- butylacetamide), C.sub.84H.sub.132N.sub.4O.sub.8, MW = 1324.46 g/mol, MP = 164-167° C. CEM 8 4-tert-butyl-Calix[4]arene tetrakis(N,N-di-iso- propylacetamide), C.sub.76H.sub.116N.sub.4O.sub.8, MW = 1212 g/mol, CEM 9 4-tert-butyl-Calix[8]arene octakis(N,N-diethylacetamide), CAS #315191-66-1, C.sub.136H.sub.200N.sub.8O.sub.16, MW = 2100 g/mol, Log K(Li.sup.+, MeOH, 25° C.) = 2.1* Log K(Na.sup.+, MeOH, 25° C.) = 2.2* Log K(K.sup.+, MeOH, 25° C.) = 2.2* Log K(Rb.sup.+, MeOH, 25° C.) = 1.9* Log K(Cs.sup.+, MeOH, 25° C.) = 2.0* Log K(Mg.sup.++, MeOH, 25° C.) = 1.3* Log K(Ca.sup.++, MeOH, 25° C.) = 7.2 Log K(Sr.sup.++, MeOH, 25° C.) = 7.2* Log K(Ba.sup.++, MeOH, 25° C.) = 8.6* *Calculated CEM 10 4-tert-Butylcalix[4]arene- tetraacetic acid tetraethyl ester, CAS #97600-5-8, C.sub.60H.sub.80O.sub.12, MW = 993.27 g/mol, Log K(Li.sup.+, MeOH, 25° C.) = 2.6 Log K(Na.sup.+, MeOH, 25° C.) = 5.0 Log K(K.sup.+, MeOH, 25° C.) = 2.4 Log K(Rb.sup.+, MeOH, 25° C.) = 3.1 Log K(Cs.sup.+, MeOH, 25° C.) = 2.7 CEM 11 4-tert-Butylcalix[5]arene- pentaacetic acid pentaethyl ester, CAS #152495-34-6, C.sub.75H.sub.100O.sub.15, MW = 993.27 g/mol, Log K(Li.sup.+, MeOH, 25° C.) = 1.0 Log K(Na.sup.+, MeOH, 25° C.) = 4.4 Log K(K.sup.+, MeOH, 25° C.) = 5.3 Log K(Rb.sup.+, MeOH, 25° C.) = 5.6 Log K(Cs.sup.+, MeOH, 25° C.) = 5.5 CEM 12 4-tert-Butylcalix[6]arene- hexaacetic acid hexaethyl ester, CAS #92003-62-8, C.sub.90H.sub.120O.sub.18, MW = 1489.93 g/mol,

(11) The whole of these CEMs are solids which are completely insoluble in water.

(12) Generic Description of the Illustrated Embodiments

(13) Extracting Composition

(14) The extracting composition is obtained by solubilizing an amount of CEM and ASM in the selected fluidizing agent, dichloromethane CH.sub.2Cl.sub.2, dichlorobenzene or dichlorotoluene or any other fluidizing agent able to well solubilize the mixture CEM/ASM in order to obtain the searched final concentrations after solubilizing CEMs and ASMs in a minimum of 3 milliliters of fluidizing agent. If the selected fluidizing agent is also an ASM compound, so the selected ASM volume is at least 3 milliliters. The given concentrations of ASM2 and ASM9 are related to the added fluidizing agent volume and the concentrations of CEM are related to the added fluidizing agent+ASM volume. The extracting organic composition is then lightly heated so as to promote the solubilization of the organic compounds by means of a heat gun (temperature around 50 to 60° C.) for a few seconds (10 to 30 seconds) until a clear solution is obtained. The composition is thus left for 24 hours at room temperature so as to make sure that the obtained formulation is stable.

(15) These sealed formulations are then orbitally stirred at 500 revolutions/minute for two hours after adding an equivalent volume of water which was distilled twice so as to allow a water saturation of the whole formulation and a pH control at the inlet and at the outlet (pH close to 7, or at least maintained after contact with the saturation water).

(16) The extracting composition is thus left for decantation. All the compositions are stable and are decanted quickly (a few minutes at most) in two distinct phases.

(17) Salt Water—Brine Especially Containing Salts to be Extracted

(18) An aqueous solution of the one or more considered chloride salts (NaCl or others) is prepared from a water which was distilled twice. The chloride salts which are used are as follows: LiCl, NaCl, KCl, MgCl.sub.2, CaCl.sub.2), SrCl.sub.2 et BaCl.sub.2.

(19) Extraction/Back-Extraction

(20) 3 mL of the prepared extracting organic composition are then taken from the lower phase of the decanted diphasic mixture and transferred to a vial containing 3 mL of the water containing the one or more considered chloride salts (NaCl or others), then the vial is sealed and orbitally stirred (at 500 revolutions per minute) for 2 hours at room temperature (RT), that is to say between 20 and 25° C.

(21) Concerning the extraction or back extraction assays at a higher temperature, in particular at 60° C. or at 80° C., a magnetic stirring (at 500 revolutions per minute), for 2 hours, is carried out with an indirect thermostatically-controlled heating in a metal mold on a hotplate.

(22) A verification is made to make sure that droplets in the range of 1-2 mm are really present during these stirrings in order to be sure that an equilibrium in the distribution of the considered chloride salt (NaCl or other) is achieved between both liquid phases at the end of stirring. The aspect of the organic and aqueous phases is clear and colorless or slightly turbid.

(23) Once the 2-hour stirring is carried out, the stirring is stopped and the whole is left for decantation for about 10 minutes, at least until both phases are completely separated, at the temperature of the assay. Then, the upper aqueous phase is taken then stirred and diluted in order to analyze its salinity by a ion chromatography (a Metrohm™ device including a cation analyzing column and an anion analyzing column suitable for the ions and for the concentration of the salts which are searched for). Likewise, the chloride salt (NaCl or other) initial aqueous solution is also analyzed by this ion chromatography to determine its cation and chloride molar relative concentration before the extraction. All the extractions and analyses were duplicated.

Example 1: Extractions at Room Temperature of Mono-Salt Saline Solutions with CEM1

(24) In this example, the CEM used is 4-tert-butyl-Calix[4]arene tetrakis(N,N-diethylacetamide) (CEM1 of CAS #: 114155-16-7).

(25) It was synthesized from 4-tert-Butylcalix[4]arene of molecular formula C.sub.44H.sub.56O.sub.4 and of CAS #60705-62-6, bought at 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 ».

(26) ##STR00047##

(27) The ASM used is ASM2 of CAS #32707-89-4, C.sub.9H.sub.6F.sub.6O, MW=244.13 g/mol, a white solid which is available for purchase from several distributors. Its characteristics are as follows:

(28) ##STR00048##

(29) TABLE-US-00007 Parameters Values Units Density (1.433) kg/L Viscosity — mPa .Math. s BP 255    ° C. MP 55   ° C. FP 97   ° C. Log P 3.0  — (estimated) Solubility 2.29 mMol/L pKa 14.7 +/− 1 —
The considered extracting composition comprises 0.1 mol/L of CEM1 and 3.52 mol/L of ASM2 in dichloromethane CH.sub.2Cl.sub.2, which was obtained as described above. The initial concentration of the considered salt in water, whether it is LiCl, NaCl, KCl, MgCl.sub.2, CaCl.sub.2), SrCl.sub.2 or BaCl.sub.2, is 0.1 mol/L.

(30) After carrying out these 7 specific extractions (duplicated) of salts, the amounts of extracted cations in relative molar percentage before and after extraction at room temperature and at water/extracting formulation iso-volume are indicated in table I:

(31) TABLE-US-00008 TABLE I Extraction rate at room temperature (RT) CEM1 0.1M (Org./Water = 1) ASM2 3.52M LiCl NaCl KCl MgCl.sub.2 CaCl.sub.2 SrCl.sub.2 BaCl.sub.2 Fluidizing CH.sub.2Cl.sub.2 73.7% 85.8% 75.8% 5.4% 59.4% 64.0% 46.1% agent

(32) The extraction of cations from a brine consisting of only one alkaline or alkaline-earth chloride thus varies from 5.4% to 85.8% depending on the cation. In these mono-salt solutions, and for this CEM1, the salt extraction level is very good except for magnesium, which, with its 76-pm ionic radius and its high hydrophily, does not fit the extracting envelope of this 16-atom macrocycle, being still too large. Thus, this formulation seems to be well suitable for a massive desalination of a saline water, even of a brine (a water whose salinity is higher than 50 g/Liter).

Example 2: Extraction of Salts from a Brine by Using CEM1

(33) The extracting composition is as follows: 0.4 Mol/L of CEM1 (cf example 1, of CAS #: 114155-16-7), completed with 1.2 Mol/L of ASM9 of formula:

(34) ##STR00049##
where R is the heptyl radical: n-C.sub.7H.sub.15.

(35) This compound was synthetized by the method described in example 9 below.

(36) The fluidizing agent used to solubilize these two compounds is 1,2-dichlorobenzene, of CAS #95-50-1 bought at TCI-Chemicals and identified by the initials 12ClPh.

(37) The brine is a water having a high salinity, at 180 g/Liter (that is to say 5.6 Mol/L), composed of sodium, potassium, calcium, magnesium and chloride ions in the proportions of table II below. The saline water to be treated was contacted with a triple relative volume of this extracting composition in order to get close to the operating conditions.

(38) It is shown in table II below 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 (RT).

(39) TABLE-US-00009 TABLE II CEM1 0.4M Salinity progression at RT, in mMol/Liter ASM9 1.2M Na K Mg Ca Cl Total Fluidizing 12ClPh Initial 1650 20.8 77.1 447 3432 5626 agent Org./Water 3 Extract 1162 22.5 83.4 495 2703 4466 1 Extract 429 23.4 86.4 492 2292 3322 2 Extract 8.54 13.9 87.6 360 1083 1553 3 Extract 3.70 3.65 94.2 114 469 685 4 Equivalent4 g/Liter 0.09 0.14 2.29 4.57 16.62 23.70

(40) This data is illustrated by FIG. 1. It clearly appears that the first salt to be extracted is NaCl, then from the third extraction step, calcium and potassium chlorides start to be extracted while NaCl continues its decrease in concentration in water. Not surprisingly, magnesium is not extracted. In the end, after 4 contacting and mixing phases between liquid phases, the total salinity of water transitioned from 180 g/Liter to 23.7 g/Liter. A fifth extraction would have allowed to achieve a complete desalination, except for MgCl.sub.2.

Example 3: Extractions at Room Temperature of Mono-Salt Saline Solutions with CEM2

(41) This example 3 is carried out in the same conditions as example 1 except that CEM1 is replaced with CEM2.

(42) The CEM used is 4-tert-butyl-Calix[6]arene hexakis(N,N-diethylacetamide (CEM2 of CAS #: 111786-95-9).

(43) It was synthesized internally from 4-tert-Butylcalix[6]arene of molecular formula C.sub.66H.sub.84O.sub.6 and of CAS #78092-53-2, bought at 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 ».

(44) ##STR00050##

(45) The ASM used is ASM2 of CAS #32707-89-4, C.sub.9H.sub.6F.sub.6O, MW=244.13 g/mol, a white solid which is available for purchase from several distributors.

(46) ##STR00051##

(47) After carrying out the 7 specific extractions (duplicated) of salts, the amounts of extracted cations in relative molar percentage before and after extraction at room temperature and at water/extracting formulation iso-volume are indicated in table III:

(48) TABLE-US-00010 TABLE III Extraction rate at room temperature (RT) CEM2 0.1M (Org./Water = 1) ASM2 3.52M LiCl NaCl KCl MgCl.sub.2 CaCl.sub.2 SrCl.sub.2 BaCl.sub.2 Fluidizing CH.sub.2Cl.sub.2 21.9% 22.7% 25.4% 13.5% 57.8% 63.8% 63.2% agent

(49) The extraction of cations from a brine composed of only one alkaline or alkaline-earth chloride thus varies from 13.5% to 63.8% depending on the cation. In these mono-salt solutions, the divalent cations are extracted in an amount which is twice to three times as high as that of the monovalent cations, except for Mg.sup.2+ magnesium ion, which is much more hydrophilic and much smaller, and which is extracted with difficulty as shown in FIG. 2.

(50) The composition according to the invention thus demonstrates a particularly interesting specificity of this formulation for many industrial applications in which calcium, although it is more hydrophilic than sodium ((ΔG°hyd=−1515 kJ/mol versus−406 kJ/mol), in spite of their ionic radius being very close to each other (102 and 100 pm), is extracted from water 2.54 times more in their respective chloride forms.

Example 4: Characterization of an Extracting Composition Including CEM2 for the Extraction of CaCl.SUB.2.)

(51) This series of examples aims to establish two extraction isotherms of CaCl.sub.2 at 20° C. and at 80° C. for an extracting composition including 0.1 Mol/L of CEM2, combined with 1 Mol/L of ASM9; the whole dissolved in 1,2-dichlorobenzene.

(52) After carrying out the 7 specific extractions (duplicated) of salts, the amounts of extracted cations in relative molar percentage before and after extraction at room temperature and at water/extracting formulation iso-volume are indicated in table IV:

(53) TABLE-US-00011 TABLE IV Extraction rate at room temperature (RT) CEM2 0.1M (Org./Water = 1) ASM9 1M 0.01M 0.02M 0.03M 0.04M 0.1M 0.2M 0.4M Fluidizing agent 12ClPh 39% 42% 41% 40% 34% 27% 16%

(54) The same series of extractions was then carried out at 80° C. to give table V as follows:

(55) TABLE-US-00012 TABLE V CEM2 0.1M Extraction rate at 80° C. (Org./Water = 1) ASM9 1M 0.01M 0.02M 0.03M 0.04M 0.1M 0.2M 0.4M Fluidizing agent 12ClPh 11% 16% 18% 17% 18% 16% 10%

(56) The extraction temperature has a high influence over the extraction performance. From these studies, and from the collected data, it was possible to plot these absorption isotherms in FIG. 3 as a function of concentrations in Mol/Liter. The axis of abscissa shows the concentration of NaCl in water and the axis of ordinates shows the concentration of NaCl in organic phase, at the absorption equilibrium.

(57) The liquid-liquid extraction process of salt according to the invention is exothermic in terms of absorption and endothermic in terms of regeneration, which allows a thermal regeneration, with hot water, of the extracting organic composition.

Example 5: Extracting Process Including Thermal Regeneration of the Extracting Composition Comprising CEM2 and Related Impacts on the Desorption of CaCl.SUB.2.)

(58) Two samples of the extracting composition of example 4 with the highest content of CaCl.sub.2 at 20° C. were contacted with a saline water at 1 Mol/L of CaCl.sub.2 at room temperature to increase the salt charging level of the dissolved CEM2 cation extracting molecules, and thus to get close to their salt saturation level (0.1 Mol/L). Then, these two samples were contacted with an iso-volume of distilled water at 20° C. and stirred. One of the two diphasic samples was then heated up to 80° C. and kept under stirring. The initial salt charging level being assessed at 80 mMol/L, it appears that the latter drops to 15.27 mMol/L from the first regeneration step at 80° C. whereas, during regeneration at 20° C., the salt residual concentration is 29.3 mMol/L. FIG. 4 illustrates the results obtained throughout several serial steps of contacting the hydrophobic organic liquid phase charged with salts with an iso-volume of distilled water. The hot regeneration of the extracting composition is much more effective because of a 2-fold reduction in the number of necessary regeneration steps to achieve the same CaCl.sub.2 overall back-extraction rate. In use, this advantage seems to be even more significant when a resin with a high CEM content, and thus a high salt content, is implemented.

(59) Increasing the regeneration temperature allows to reduce the number of successive steps for contacting a distilled water at iso-volume while allowing a larger back-extraction of salts each time. It also allows to access regeneration waters with a higher concentration of back-extracted salts because of the use of a lesser regeneration water volume.

Example 6: Comparative Examples: Selective Extractions, at Room Temperature, of Cations from a Binary Mixture of Salts NaCl/CaCl.SUB.2.)

(60) A brine containing an equimolar mixture of salts, 0.05 mol/L of NaCl and CaCl.sub.2 each, which was made as described above, was contacted with two extracting compositions, one of which according to the invention.

(61) ##STR00052##
These compositions only differ from each other by the CEM compound used which is still from the disubstituted primary amide family but whose macrocycle size is changed, thereby being 16 carbon atoms (CEM1) and 24 carbon atoms (CEM2) in size, respectively. These compositions are obtained according to the process as described above.

(62) Each extracting composition comprises 0.1 mol/L of CEM

(63) ##STR00053##
and 2.4 mol/L of ASM9 in 1,2-dichlorobenzene.

(64) 1,2-dichlorobenzene (CAS #: 95-50-1), having a purity higher than 99%, comes from TCI Chemicals.

(65) The amounts of cations, in molar percentage, which were extracted from the mixture are indicated in table VI:

(66) TABLE-US-00013 TABLE VI CEM1/CEM2 Cations Na.sup.+ Ca.sup.++ 4-tert- % E 88.0% 10.0% ButylCalix[4]CH.sub.2C(═O)NEt.sub.2 4-tert- % E  4.0% 56.0% ButylCalix[6]CH.sub.2C(═O)NEt.sub.2

(67) Depending on the selected CEM, in a mixture of salts, the extraction of these cations experiences an increased selectivity where the cation which is the most extracted as a pure substance becomes mostly extracted as a mixture of salts. Here, the co-absorption is favorable to the extraction which was initially the best. In particular, the formulation including CEM2 the carbon ring of which has 24 units, has a calcium to sodium extraction rate which is 14 times higher in a mixture with an iso-concentration of cations compared to a rate of 2.54 for solutions containing only one of these salts (cf examples 1 & 3). Such extraction capacities have many industrial applications in water descaling.

Example 7: Selective Extractions, at Room Temperature, of Cations from a Binary Mixture of Salts NaCl and CaCl.SUB.2 .at Differentiated Initial Concentrations

(68) A brine containing a mixture of NaCl and CaCl.sub.2 is made as described above to obtain the following initial saline concentrations in a mixture: 0.2 Mol/L of NaCl and 0.03 Mol/L of CaCl.sub.2. The extracting resin, is composed of 0.1 Mol/L of CEM2, 3.52 Mol/L of ASM2 and a complement of liquid ASM1, which is also used as a fluidizing agent.

(69) The amounts of cations, in molar percentage, which were extracted from the mixture are indicated in table VII:

(70) TABLE-US-00014 TABLE VII CEM2 Cations Na.sup.+ Ca.sup.++ 4-tert- % E 5.0% 88.0% ButylCalix [6] CH.sub.2C (═O) NEt.sub.2
Here, it appears that the ratio of the Ca/Na extraction rates is 17.6, which accredits one of the objects of the invention because of an improvement of the differences during the extraction of multiple salts, in the presence of a common anion.

Example 8: Selective Extractions, at Room Temperature, of Cations from a Mixture of Four Salts NaCl, CaCl.SUB.2., SrCl.SUB.2 .and BaCl.SUB.2

(71) A brine containing a mixture of NaCl, CaCl.sub.2, SrCl.sub.2 and BaCl.sub.2 is made as described above. The dissolved salt concentrations are indicated in table VIII in mMol/L. The extraction was carried out a second time with changed divalent salt concentrations. The dissolved salt concentrations are indicated in table IX in mMol/L.
The extracting composition consists of 0.1 Mol/L of CEM2 and of a mixture of two ASMs. This mixture is composed of ASM2 which is usually referred to as [3,5-Bis(Trifluoromethyl)benzyl Alcohol](35TFMBnOH) of CAS #: 32707-89-4, up to 60% by volume, and of ASM1, referred to as [3-(Trifluoromethyl)benzyl Alcohol](3TFMBnOH), of molecular formula C.sub.8H.sub.7F.sub.3O of MW=176.14 g/Mol and of CAS #: 349-75-7, up to 40% by volume, both serving as a fluidizing agent and as an ASM given its liquid form.
The extraction is carried out as described in example 1 and at room temperature.
The amounts of extracted cations, in molar percentage, are indicated in tables VIII and IX, respectively for initial and final ionic concentrations expressed in mMol/L.

(72) TABLE-US-00015 TABLE VIII CATIONS (mMol/L) ANIONS CI− (mMol/L) Initial Final Initial Final Concen- Concen- % Concen- Concen- Cations tration tration extraction tration tration Na.sup.+ 193.52 199.4775  0% 257.74 213.38 Ca.sup.2+ 29.13 0.4916  98% Sr.sup.2+ 4.29 0 100% Ba.sup.2+ 4.69 0 100%

(73) TABLE-US-00016 TABLE IX CATIONS ANIONS CI− Initial Final Initial Final Concen- Concen- % Concen- Concen- Cations tration tration extraction tration tration Na.sup.+ 196.04 195.9835  0% 245.4 203.16 Ca.sup.2+ 9.25 0 100% Sr.sup.2+ 9.17 0 100% Ba.sup.2+ 9.32 0 100%

(74) Here, it appears that, for high relative concentrations of sodium with respect to these scaling divalent cations, an extraction selectivity of 100% can be achieved.

(75) The selective extraction of the divalent cations demonstrates the capacity of these compositions according to the invention to efficiently fight against scale deposit and to purify water, because of a selective extraction of calcium Ca.sup.++, strontium and barium.

Example 9: Synthesis of ASM9, ASM10, ASMC11 and ASM12 Compounds

(76) Synthesis Diagram

(77) ##STR00054##
R=n-C.sub.7H.sub.15 (ASM9), n-C.sub.9H.sub.19 (ASM10), n-C.sub.11H.sub.23 (ASM11), n-C.sub.13H.sub.27 (ASM12).

(78) Protocol

(79) 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.), the acid chloride (56.29 mmol, 1.0 eq.) is added dropwise under stirring. The temperature is controlled during the addition and should not exceed 38° C. (boiling point of dichloromethane). The reaction mixture is stirred for 5 h at room temperature. A solution of 1M HCl (50 mL) is added and then the organic phase is washed. The successive washes are carried out with a 1M HCl solution (50 mL) and a saturated NaCl solution (50 mL). The organic phase is dried over Na.sub.2SO.sub.4, filtered and the solvent is then evaporated under reduced pressure. The solid residue is then taken back with petroleum ether (cold or at room temperature), washed, filtered and then dried under vacuum to give the desired amide. The petroleum ether used is a mixture of hydrocarbons mainly composed of n-pentane, 2-methyl pentane of CAS #64742-49-0 from VWR, where it is sold under the name Petroleum Ether 40-60° C. GPR RECTAPUR. The characteristics of the compounds obtained are shown in table X.

(80) TABLE-US-00017 Molar Table Com- mass T° petroleum Melting XR pound (g/mol) ether Yield Aspect point n-C.sub.7H.sub.15 ASM9 355.3 Cold 91% White 43-44° C. (−20° C.) solid n- C.sub.9H.sub.19 ASM10 383.3 Room 92% White 79-81° C. temperature solid n-C.sub.11H.sub.23 ASM11 411.4 Room 92% White 60-61° C. temperature solid n-C.sub.13H.sub.27 ASM12 439.5 Room 90% White 53-54° C. temperature solid

(81) The compounds ASM9, ASM10, ASMC11 and ASMC12 have the 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 were furthermore identified by NMR spectrometry. FIG. 6 shows the NMR spectrum (CDCl.sub.3, 300 MHz) of the ASM11 compound, the peaks of which are as follows: 1H NMR (CDCl.sub.3, 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: Extractions at Room Temperature of Mono-Salt Saline Solutions with CEM10

(82) This example 10 is carried out in the same conditions as examples 1 and 3 except that the CEM in question is CEM10.

(83) The CEM used is 4-tert-butyl-Calix[4]arene acid tetraethyl ester (CEM10 of CAS #: 97600-39-0).

(84) ##STR00055##
It was synthesized internally from 4-tert-Butylcalix[4]arene of molecular formula C.sub.44H.sub.56O.sub.4 and of CAS #60705-62-6, and from ethyl bromoacetate of CAS #105-36-2, products bought at Sigma-Aldrich for the implementation of a conventional addition procedure on an alcohol, in a mixture THF/DMF at 5/1 by volume.
The ASM used is ASM2 of CAS #32707-89-4, C.sub.9H.sub.6F.sub.6O, MW=244.13 g/mol, a white solid which is available from several distributors.

(85) ##STR00056##
After carrying out the 7 specific extractions (duplicated) of salts, the amounts of extracted cations in relative molar percentage before and after extraction at room temperature and at water/extracting formulation iso-volume are indicated in table XI:

(86) TABLE-US-00018 TABLE XI Extraction rate at room temperature (RT) CEM10 0.1M (Org./Water = 1) ASM2 3.52M LiCl NaCl KCl MgCl.sub.2 CaCl.sub.2 SrCl.sub.2 BaCl.sub.2 Fluidizing agent CH.sub.2Cl.sub.2 5.5% 66.2% 14.4% 5.1% 4.7% 5.9% 3.7%

(87) The extraction of cations from a brine composed of only one alkaline or alkaline-earth chloride thus varies from 3.7% to 66.2% depending on the cation. In these mono-salt solutions, it appears that CEM10 is selective for sodium chloride among the alkaline cations and that the divalent cations are poorly extracted with a Na/Ca selectivity of 14.

(88) The composition according to the invention thus demonstrates a particularly interesting specificity of this formulation for industrial applications in relation to chlorine chemistry where NaCl can be extracted from a seawater or from a brine in a selective way in order to supply the electrolysers for producing NaOH, HCl, or even Cl.sub.2.

Example 11: Extractions at Room Temperature of Mono-Salt Saline Solutions with CEM12

(89) This example 11 is carried out in the same conditions as examples 1, 3 and 10 except that the CEM in question is CEM12.

(90) The CEM used is 4-tert-butyl-Calix[6]arene acid hexaethyl ester (CEM12 of CAS #: 92003-62-8).

(91) ##STR00057##
It was synthesized internally from 4-tert-Butylcalix[6]arene of molecular formula C.sub.66H.sub.84O.sub.6 and of CAS #78092-53-2, and from ethyl bromoacetate of CAS #105-36-2, products bought at Sigma-Aldrich for the implementation of a conventional addition procedure on an alcohol, in a mixture THF/DMF at 5/1 by volume.

(92) The ASM used is ASM2 of CAS #32707-89-4, C.sub.9H.sub.6F.sub.6O, MW=244.13 g/mol, a white solid which is available from several distributors.

(93) ##STR00058##
After carrying out the 7 specific extractions (duplicated) of salts, the amounts of extracted cations in relative molar percentage before and after extraction at room temperature and at water/extracting formulation iso-volume are indicated in table XII:

(94) TABLE-US-00019 TABLE XII Extraction rate at room temperature (RT) CEM12 0.1M (Org./Water = 1) ASM2 3.52M LiCl NaCl KCl MgCl.sub.2 CaCl.sub.2 SrCl.sub.2 BaCl.sub.2 Fluidizing agent CH.sub.2Cl.sub.2 9.0% 29.6% 55.7% 5.4% 5.5% 4.6% 11.8%

(95) The extraction of cations from a brine composed of only one alkaline or alkaline-earth chloride thus varies from 4.6% to 55.7% depending on the cation. In these mono-salt solutions, it appears that CEM12 is selective for the alkaline chloride salts having a larger diameter and that the divalent cations are poorly extracted with a K/Ca selectivity of 10.2, and which must be even better for Rb+ and Cs+ because this CEM12 is known as being a good cesium ionophore. The invention is not limited to the embodiments presented and other embodiments will become apparent to those skilled in the art. In particular, it is possible to combine several CEMs within an extracting formulation so as to allow to associate the specific performance of each CEM to obtain optimal overall performance.