Device and method for the desalination of water by means of thermal deionisation and liquid-phase ion extraction liquid

Abstract

Disclosed is a method for treating water, including the extraction of at least two ionic species, the ionic species including an anionic species and a cationic species and being present in the water to be treated, the method especially including a step of mixing a liquid hydrophobic organic phase and the water to be treated, the water to be treated being in the liquid state, in order to subsequently obtain liquid treated water and a hydrophobic liquid organic phase loaded with the ionic species, and a step of thermal regeneration of the organic phase loaded with chemical species. Also disclosed are compounds and compositions that can be used in the method.

Claims

1. A hydrophobic organic liquid composition comprising: at least one first organic compound of Formula (B): ##STR00039## in which at least one of the radicals R.sub.A, R.sub.B, R.sup.C, R.sup.D and R.sub.E, which are identical or differ rent, is a halogen atom or an electron-withdrawing group, of the following group: F, Cl, Br; C.sub.RF.sub.2m+1 with m≤4, where m is a non-zero integer; CF.sub.2CF.sub.2C.sub.pH.sub.2p+1 with p≤4, where p is an integer; CF.sub.2C.sub.pH.sub.2p+1 with p≤4, where p is an integer; CH.sub.2C.sub.pF.sub.2p+1 with p≤4, where p is an integer; OCH.sub.2CF; C(═O) CF.sub.3; C.sub.nH.sub.nF.sub.pCl.sub.qBr.sub.2 with m≤4, where n, p, q, s are integers of which at least p, q or s is non-zero; C(═O) OC.sub.mH.sub.2m+1 with m≤4, where m is an integer; and C(═O)C.sub.mH.sub.2m+1 with m≤4, where m is an integer, the remaining radical (s) R.sub.A, R.sub.B, R.sub.C, R.sub.D and R.sub.E are chosen, identical or different, from the following non-electron withdrawing radicals: H; CH.sub.3; CH.sub.2CH.sub.3; CH.sub.2CH.sub.2C.sub.pF.sub.2p+1 with p≤4, where p is an integer; C.sub.mH.sub.2m−1 with m≤10, where m is a non-zero integer; and C.sub.mH.sub.2m+1 with m≤10, where m is a non-zero integer; where only one of the radicals R.sub.A to R.sub.E may be one of these last two radicals C.sub.mH.sub.2m−1 and C.sub.mH.sub.2m+1; and wherein X is selected from the following radicals: OH; NH—R′; ##STR00040##  where R′ and R′, which may be identical or different, are chosen from the following radicals: H; C.sub.nH.sub.2n−1 with n≤4, where n is a non-zero integer; C.sub.nH.sub.2n+1 with n≤4, where n is a non-zero integer; CH.sub.2CH.sub.2C.sub.pF.sub.2p+1 with p≤4, where p is an integer; CH.sub.2C.sub.pF.sub.2p+1 with p≤4, where p is an integer; CF.sub.2C.sub.pH.sub.2p+1 with p≤4, where p is an integer; CF.sub.2CF.sub.2C.sub.pH.sub.2p+1 with p≤4, where p is an integer; C.sub.mF.sub.2m+1 with m≤4, where m is a non-zero integer; C.sub.mH.sub.nF.sub.pCl.sub.qBr, with m≤4, where n, p, q, s are integers of which at least p, q or s is non-zero; and an aryl radical of formula (b): ##STR00041## where R.sub.A, R.sub.B, R.sub.C, R.sub.D and R.sub.E, which may be identical or different, are as defined above in formula (B); and wherein R′″ is selected from the following radicals: C.sub.nH.sub.2m+1 with m≤20, where m is an integer; C.sub.nH.sub.2n−1 with m≤20, where m is a non-zero integer; C.sub.nH.sub.nF.sub.pCl.sub.qBr.sub.s with m≤10, where n, p, q, s are integers of which at least p, q or s is non-zero; CH.sub.2CH.sub.2C.sub.pF.sub.2p+1 with p≤4, where p is an integer; CH.sub.12C.sub.pF.sub.2p+1 with p≤4, where p is an integer; CF.sub.2C.sub.pH.sub.2p+1 with p≤4, where p is an integer; CF.sub.2CF.sub.2C.sub.pH.sub.2p+1 with p≤4, where p is an integer; C.sub.nF.sub.2n+1 with m≤4, where m is a non-zero integer; and an aryl radical of formula (b): ##STR00042## where R.sub.A, R.sub.B, R.sub.C, R.sub.D and R.sub.E, which may be identical or different, are as defined above in formula (B); at least a second hydrophobic organic compound allowing cation extraction and having a complexing constant of the cationic species whose log K value, in methanol at 25° C., is greater than 2 and less than 11; and, a fluidifying agent.

2. The composition according to claim 1, wherein the second hydrophobic organic compound allowing cation extraction has a complexing constant of the cationic species whose log K value, in methanol at 25° C., is greater than 3 and less than 9.

3. The composition according to claim 1, wherein compound (B) is a compound in which X represents: ##STR00043##

4. The composition according to claim 3, wherein compound (B) is represented by formula: ##STR00044## in which R′″ is chosen from the following radicals: C.sub.mH.sub.2m+1 with m≤20, where m is an integer; C.sub.mH.sub.2m−1 with m≤20, where m is a non-zero integer; C.sub.mH.sub.nF.sub.pCl.sub.qBr.sub.3 with m≤10, where n, p, q, s are integers of which at least p, q or s is non-zero; and an aryl radical of formula (b): ##STR00045## in which at least one of the radicals R.sub.A, R.sub.B, R.sub.C, R.sub.D and R.sub.E, which are identical or different, is an halogen atom or an electron-withdrawing group, of the following group: F, Cl, Br; C.sub.mF.sub.2m+1 with m≤4, where m is a non-zero integer; CF.sub.2CF.sub.2C.sub.pH.sub.2p+1 with p≤4, where p is an integer; CF.sub.2C.sub.pH.sub.2p+1 with p≤4, where p is an integer: CH.sub.2C.sub.pF.sub.2p+1 with p≤4, where p is an integer; OCH.sub.2CF.sub.3; C(═O)CF.sub.3; C.sub.mH.sub.nF.sub.pCl.sub.qBr.sub.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.sub.mH.sub.2m+1 with m≤4, where m is an integer; and C(═O)C.sub.mH.sub.2m+1 with m≤4, where m is an integer, the remaining radical (s) R.sub.A, R.sub.B, R.sub.C, R.sub.D and R.sub.E are chosen, identical or different, from the following non-electron withdrawing radicals: H; CH.sub.3; CH.sub.2CH.sub.3; CH.sub.2CH.sub.2C.sub.pF.sub.2p+1 with p≤4, where p is an integer; C.sub.mH.sub.2m−1 with m≤10, where m is a non-zero integer; and C.sub.mH.sub.2m+1 with m≤10, where m is a non-zero integer, where only one of the radicals R.sub.A to R.sub.E may be one of these last two radicals C.sub.mH.sub.2m−1 and C.sub.mH.sub.2m+1.

5. The composition according to claim 4, wherein radical R′″ is n-C.sub.7H.sub.15, n-C.sub.9H.sub.19, n-C.sub.11H.sub.23 or n-C.sub.3H.sub.27.

6. The composition according to claim 5, wherein compound (B) is chosen among: N-[3,5-bis(trifluoromethyl)phenyl] octanamide; N-[3,5-bis(trifluoromethyl)phenyl] decanamide; N-[3,5-bis(trifluoromethyl)phenyl] dodecanamide; and N-[3,5-bis(trifluoromethyl)phenyl] tetradecanamide.

7. The composition according to claim 3, wherein compound (B) is represented by formula: ##STR00046## in which R′″ is chosen from the following radicals: C.sub.mH.sub.2m+1 with m≤20, where m is an integer; C.sub.mH.sub.2m−1 with m≤20, where m is a non-zero integer; C.sub.mH.sub.nF.sub.pCl.sub.qBr.sub.s with m≤10, where n, p, q, s are integers of which at least p, q or s is non-zero; and an aryl radical of formula (b): ##STR00047## in which at least one of the radicals R.sub.A, R.sub.B, R.sub.C, R.sub.D and R.sub.E, which are identical or different, is an halogen atom or an electron-withdrawing group, of the following group: F, Cl, Br; C.sub.mF.sub.2m+1 with m≤4, where m is a non-zero integer; CF.sub.2CF.sub.2C.sub.pH.sub.2p+.sub.1 with p≤4, where p is an integer; CF.sub.2C.sub.pH.sub.2p+1 with p≤4, where p is an integer: CH.sub.2C.sub.pF.sub.2p+1 with p≤4, where p is an integer; OCH.sub.2CF.sub.3; C(═O) CF.sub.3; C.sub.mH.sub.nF.sub.pCl.sub.qBr, with m≤4, where n, p, q, s are integers of which at least p, q or s is non-zero; C(═O) OC.sub.nH.sub.2m+1 with m≤4, where in is an integer; and C(═O)C.sub.mH.sub.2m+1 with m≤4, where m is an integer, the remaining radical(s) R.sub.A, R.sub.B, R.sub.C, R.sub.D and R.sub.E are chosen, identical or different, from the following non-electron withdrawing radicals: H; CH.sub.3; CH.sub.2CH.sub.3; CH.sub.2CH.sub.2C.sub.pF.sub.2p+1 with p≤4, where p is an integer; C.sub.mH.sub.2m−1 with m≤10, where m is a non-zero integer; and C.sub.mH.sub.2m+1 with m≤10, where m is a non-zero integer, where only one of the radicals R.sub.A to R.sub.E may be one of these last two radicals C.sub.mH.sub.2m−1 and C.sub.mH.sub.2m+1.

8. The composition according to claim 1, wherein the second hydrophobic organic compound is a crown ether having from 14 to 80 carbon atoms.

9. The composition according to claim 8, wherein the second hydrophobic organic compound is chosen from the group consisting of 6,7,9,10,12,13,20,21,23,24-decahydrodibenzo[b,k][1,4,7,10,12,16,19] heptaoxa-cyclohenicosine (DB21C7), benzo[b]-1,4,7,10,13-pentaoxacyclopentadecane (B15C5), perhydrobenzo[b]-1,4,7,10,13-pentaoxacyclopentadecane (C15C5), dicyclohexano-1,4,7,10,13,16-hexaoxacyclooctadecane (DC18C6), dibenzo[b,k]-1,4,7,10,13,16-hexaoxacyclooctadecane (DB18C6) and 6,7,9,10,12,13,20,21,23,24,26,27-dodecahydrodibenzo[b,n][1,4,7,10,13,16,19,22]octaoxa-cyclotetracosine (DB24CB).

10. The composition according to claim 8, wherein the second organic compound is a substituted calixarene.

11. The composition according to claim 10, wherein the calixarene comprises from 32 to 80 carbon atoms.

12. The composition according to claim 11, wherein the calixarene is 4-tert-butylcalix[4]-arene-O,O′,O″,O′″-tetraacetic acid tetraethyl ester.

13. The composition according to claim 1, wherein the fluidifying agent is selected from the group consisting of polar aromatic organic compounds.

14. A method for extracting at least two ionic species from a saline water to be treated, comprising reacting the saline water with the composition of claim 1, wherein the ionic species comprise an anionic species and a cationic species and are present in the saline water to be treated.

15. The method according to claim 14, wherein the anionic species is chloride, sulphate or nitrate.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The invention will be better understood on 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 NaCl extraction rates in % of salt water at various concentrations (abscissa axis) and at temperatures (round: 20° C., square: 40° C., triangle: 60° C. and diamond: 80° C.) using an ASM 4/Calix[4]Est composition according to the invention, for an CEM concentration of 0.4M described in Example 6B.

(3) FIG. 2 is a graph showing, for ASM 4/Calix[4]Est compositions of Example 6B (diamond: 0.2M, round: 0.4M and triangle: 0.8M of CEM), the % loading rates of CEM in NaCl for various initial concentrations of NaCl in Mol/L and at room temperature.

(4) FIG. 3 is a graph showing the extraction rates in % Na.sub.2SO.sub.4 of a water containing it at various initial concentrations and at ambient temperature by using an ASM4/Calix[4]Est composition at various concentrations (triangle: 0.2M, diamond: 0.4M and round: 0.8M) according to the invention described in EXAMPLE 6C.

(5) FIG. 4 is a schematic representation of example 7 with a device according to the invention making it possible to implement the method according to the invention.

(6) FIG. 5 is another schematic representation of the example of FIG. 4 showing an example of the operating temperature of the various parts of the device.

(7) FIG. 6 is a table showing the concentrations of each ionic species in each of the flows identified in the device of Example 7 as well as the total salinity, density, temperature and flow rate of these flows when the water to be treated is seawater.

(8) FIG. 7 is a schematic representation of another example of a device according to the invention described in Example 8.

(9) FIG. 8 is a schematic representation of another example of a device according to the invention described in Example 9.

(10) FIG. 9 shows the NMR spectrum of compound ASMC11

EXAMPLES

Example 1: Description of the Tested CEMs

(11) Various ion-extracting compositions according to the invention have been formulated and tested. The 7 CEMs used in these compositions are the following:

(12) TABLE-US-00003 NAME Nomenclature Formula CrownEther DB21C7 6,7,9,10,12,13,20,21,23,24- Decahydrodibenzo[b,k][1,4,7,10,13,16,19] heptaoxacyclohenicosine (Dibenzo-21- crown-7). CAS n° 14098-41-0, C.sub.22H.sub.28O.sub.7, MW = 404 g/mole, MP = 107° C., S = 1.9 mMole/L (estimated at 25° C.). Log K(Na.sup.+, MeOH, 25° C.) = 2.4 Log K(K.sup.+, MeOH, 25° C.) = 4.19 CrownEther B15C5 Benzo[b]-1,4,7,10,13-pentaoxa- cyclopentadecane (Benzo-15-Crown-5). CAS n° 14098-44-3, C.sub.14H.sub.20O.sub.5, MW = 268.31 g/mole, MP = 80° C., Log P = 0.91 (Exp), S = 11.6 mMole/L (estimated at 25° C.). Log K(Na.sup.+, MeOH, 25° C.) = 3.03 Log K(K.sup.+, MeOH, 25° C.) = 3.93 CrownEther C15C5 Perhydrobenzo[b]-1,4,7,10,′3- pentaoxacyclopentadecane (Cyclohexo- 15-Crown-5). CAS n° 17454-48-7, C.sub.14H.sub.26O.sub.5, MW = 274.35 g/mole, Liquid, FP = 100° C., d = 1.12 g/mL, S = 57 mMole/L (estimated at 25° C.). Log K(Na.sup.+, MeOH, 25° C.) = 3.71-3.9 Log K(K.sup.+, MeOH, 25° C.) = 3.96 CrownEther DC18C6 Dicyclohexano-1,4,7,10,13,16- hexaoxacyclooctadecane (Dicyclohexano- 18-crown-6). CAS n° 16069-36-6, C.sub.20H.sub.36O.sub.6, MW = 372.51 g/mole, MP = 46-53° C., FP = 110° C., S = 36 mMole/L Log K(Na.sup.+, MeOH, 25° C.) = 4.27 Log K(K.sup.+, MeOH, 25° C.) = 5.97 0 CrownEther DB18C6 Dibenzo[b,k]-1,4,7,10,13,16- hexaoxacyclooctadecane (Dibenzo-18- crown-6). CAS n° 14187-32-7, C.sub.20H.sub.24O.sub.6, MW = 360.41 g/mole, MP = 163° C., Log P = 2.20 (Exp), S = 1.1 mMole/L Log K(Na.sup.+, MeOH, 25° C.) = 4.50 Log K(K.sup.+, MeOH, 25° C.) = 5.12 CrownEther DB24C8 6,7,9,10,12,13,20,21,23,24,26,27- Dodecahydrodibenzo[b,n][1,4,7,10,13,16,19,22] octaoxacyclotetracosine (Dibenzo- 24-crown-8). CAS n° 14174-09-5, C.sub.24H.sub.32O.sub.8, MW = 448 g/mole, MP = 104° C., Log P = 2.11 (Exp), 1.865 mg/L (25° C. estimated). Log K(Na.sup.+, MeOH, 25° C.) = 2.35 Log K(K.sup.+, MeOH, 25° C.) = 3.61 Calixarene Calix[4]Est 4-tert-Butylcalix[4]arene-O,O′,O″,O′′′- tetraacetic Acid Tetraethyl Ester (Calix[4]arene tetraesters, Sodium ionophore X). CAS n° 97600-39-0, C.sub.6H.sub.80O.sub.12, MW = 993.27 g/mole, MP = 156-157° C., S < 1.10.sup.−6 mMole/L Log K(Na.sup.+, MeOH, 25° C.) = 5.0 Cryptand DC[2.2.2] C.sub.26H.sub.48N.sub.2O.sub.6 (DiCyclohexanocryptand[222]) 5,6,14,15-DiCyclohexano-4,7,13,16,21,24- hexaoxa-1,10-diazabicyclo[8.8.8] hexacosane MW = 484 g/mole S = 3 mMole/L Log K(Na.sup.+, MeOH, 25° C.) = 6.02 Log K(K.sup.+, MeOH, 25° C.) = 6.92 Cryptand DB[2.2.2] C.sub.26H.sub.36N.sub.2O.sub.6 (Dibenzocryptand[222]) 5,6,14,15-DiBenzo-4,7,13,16,21,24- hexaoxa-1,10-diazabicyclo[8.8.8] hexacosane CAS: 40471-97-4 MW = 472.57 g/mole S = 2.5 mMole/L Log K(Na.sup.+, MeOH, 25° C.) = 7.60 Log K(K.sup.+, MeOH, 25° C.) = 8.74 Cryptand Decyl[2.2.2] C.sub.28H.sub.56N.sub.2O.sub.6 (5-Decylcryptand[222]) 5-Decyl-4,7,13,16,21,24-hexaoxa-1,10- diazabicyclo[8.8.8]hexacosane CAS: 69878-46-2 MW = 516.75 g/mole S = 0.1 mMole/L Log K(Na.sup.+, MeOH, 25° C.) = 7.04 Log K(K.sup.+, MeOH, 25° C.) = 9.0 7 of the 10 CEMs presented above were solubilized in ASM 1, followed by NaCl extraction measurements. The others were solubilized in ASM 2.

Example 2: Description of the Tested ASMs

(13) ASM 1: (3TFMPhOH)

(14) 3-(Trifluoromethyl)phenol

(15) N.sup.∘ CAS: 98-17-9

(16) C.sub.7H.sub.5F.sub.3O,

(17) MW=162.11 g/mole

(18) Colorless liquid

(19) ##STR00027##

(20) TABLE-US-00004 Parameters Values Units Density  1.33 kg/L Viscosity <50 at 25° C. mPa.s BP 177-178 ° C. MP  −1.8 ° C. FP  74 ° C. Log P  2.95 — Solubility  3.83 (estimated) mMole/L pKa  8.68 at 25° C. —
ASM 2: (3TFMPhOH)
[3-(Trifluoromethyl)phenyl]methanol
N.sup.∘ CAS: 349-75-7
C.sub.8H.sub.7F.sub.3O,
MW=176.14 g/mole
Odorless and colorless liquid.

(21) ##STR00028##

(22) TABLE-US-00005 Parameters Values Units Density  1.295 kg/L Viscosity  9.4 at 20° C. mPa.s BP 260 ° C. MP <25 ° C. FP  84 ° C. Log P  1.74 (estimated) — Solubility  32 mMole/L pKa  14.74 +/− 1 —
ASM 3: (35TFMBnOH)
[3,5-Bis(Trifluoromethyl)phenyl]methanol
N.sup.∘ CAS: 32707-89-4
C.sub.9H.sub.6F.sub.6O,
MW=244.13 g/mole
White solid.

(23) ##STR00029##

(24) TABLE-US-00006 Parameters 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 —

(25) TABLE-US-00007 Parameters Values Units Density    1.389 at 20° C. kg/L Viscosity   13.4 at 20° C. mPa.s BP — ° C. MP <15 ° C. FP — ° C. Log P    2.0 (estimated) — Solubility   15 mMole/L pKa   14.7 +/− 1 —
ASM 4=60% vol ASM 3+40% vol ASM 2
White, colorless liquid

(26) ##STR00030##
ASM 5: (3C.sub.4F.sub.9BnOH)
[3-(Perfluorobutyl)phenyl]methanol
N.sub.∘ CAS: Unknown
C.sub.11H.sub.7F.sub.9O,
MW=326.16 g/mole
Odorless and colorless liquid.

(27) ##STR00031##

(28) TABLE-US-00008 Parameters Values Units Density    1.488 kg/L Viscosity   40 at 20° C. mPa.s BP at mmHg ° C. MP <15 ° C. FP — ° C. Log P    4.57 — (estimated) Solubility  <0.077 mMole/L (not detected in UV-visible) pKa   14.7 +/− 1 —
ASM 6: (3,5-C.sub.3F.sub.7BnOH)
[3,5-(Perfluoropropyl)phenyl]methanol
N.sup.∘ CAS: Unknown
C.sub.1H.sub.6F.sub.14O,
MW=444.16 g/mole

(29) ##STR00032##

(30) TABLE-US-00009 Parameters Values Units Density  1.585 kg/L Viscosity — mPa.s BP at mmHg ° C. MP — ° C. FP — ° C. Log P  5.75 — (estimated) Solubility <0.07 mMole/L pKa 14.25 +/− 1 —
In the tables of data above the acronyms BP MP and FP designate: BP=boiling point MP=melting point FP=flash point

Example 3

(31) The compound of formula ASM5 was synthesized as follows:

(32) First Step

(33) ##STR00033##
A solution of ethyl 3-iodobenzoate (207.9 g, 753.2 mmol, 1.0 eq.), Copper powder (239.3 g, 3.766 mol, 5.0 eq.) and 450 mL of DMSO, is degassed and then is put under an argon atmosphere. The mixture is then brought to 130° C. and then a solution of 1-iodoperfluorobutane (181.5 mL, 1.054 mol, 1.4 eq) is added dropwise over 30 minutes. The reaction mixture is stirred at 130° C. for 5 h under an argon atmosphere. After returning to room temperature, 2 L of ethyl acetate and 1 L of water are added. The mixture is then filtered through silica (Celite). The organic phase is washed with water (2×1 L), dried over sodium sulphate, filtered and then concentrated under reduced pressure to give crude ethyl 3-(perfluorobutane)benzoate (269.0 g, 730.6 mmol, 97% light brown liquid).

(34) .sup.1H NMR (CDCl.sub.3, 300 MHz): δ (ppm)=1.42 (t. .sup.3J=7.1 Hz, 3H). 4.44 (q, .sup.3d=7.1 Hz, 4H), 7.61 (t. .sup.2J=8.0 Hz, 1H), 7.78 (d, .sup.3J=7.7 Hz, 1H), 8.24-8.30 (m, 2H).

(35) Second Step

(36) ##STR00034##

(37) To a solution, cooled with an ice bath, of ethyl 3-(perfluorobutane)benzoate (269.0 g, 730.6 mmol, 1.0 eq.) and of 500 mL of ethanol, is added in small portions sodium borohydride (82.9 g, 2.192 mol, 3.0 eq). The temperature is controlled and must be below 20° C. Once the addition is completed, the reaction mixture is stirred at room temperature for 15 h. After stirring is over, a saturated solution of NH.sub.4Cl (2 L) is added at cold temperature and then diluted with 2 L of ethyl acetate. The aqueous phase is extracted with ethyl acetate (1×1 L) and the organic phases are washed with i) a saturated solution of NH.sub.4Cl (1×1 L) and ii) with water (1×1 L). After drying over sodium sulphate and filtration, the organic phase is concentrated under reduced pressure to give crude [(3-perfluorobutyl)phenyl]methanol (228.9 g, 701.8 mmol, 96%, light brown liquid).

(38) The crude compound was purified by vacuum distillation (P=5 mmbars, BP=98-102° C.) to give [(3-perfluorobutyl)phenyl]methanol (162.5 g, 498.2 mmol, 68%, colorless liquid).

(39) .sup.1H NMR (CDCl.sub.3, 300 MHz): δ (ppm)=1.72 (br s, 1H), 4.79 (s, 2H), 7.49-7.53 (m, 2H), 7.56-7.62 (m, 2H).

Example 4

(40) The compound of formula ASM6 was synthesized as follows:

(41) First step

(42) ##STR00035##

(43) A few crystals of iodine are added to a suspension of copper powder (10.32 g, 162.4 mmol, 5.0 eq.) and acetone (50 mL). After stirring for 30 minutes, the liquid phase is removed by filtration and the copper is washed with a solution of gaseous hydrochloric acid in acetone (60 mL) and then with acetone (60 mL). The activated copper is introduced into a solution of ethyl 3,5-dibromobenzoate (10.0 g, 32.5 mmol, 1.0 eq.) and 500 mL of DMSO. The suspension is degassed and then placed under an argon atmosphere. The mixture is then brought to 130° C. A solution of 1-iodoperfluoropropane (13.2 mL, 90.9 mmol, 2.8 eq) is added dropwise over 30 minutes. The reaction mixture is stirred at 130° C. for 5 h under an argon atmosphere. After returning to room temperature, 50 mL of ethyl acetate and 50 mL of water are added. The mixture is then filtered through celite. The organic phase is washed with water (2×50 mL), dried over sodium sulphate, filtered and then concentrated under reduced pressure to give crude ethyl 3,5-bis(perfluoropropane) benzoate (15.46 g, 31.8 mmol, 98%, yellow solid).

(44) .sup.1H NMR (CDCl.sub.3, 300 MHz): δ (ppm)=1.45 (t, .sup.3J=7.1 Hz, 3H), 4.46 (q, .sup.3J=7.1 Hz, 4H), 7.96 (br. s, 1H), 8.48 (br. s, 2H).

(45) Second Step

(46) ##STR00036##

(47) A solution of ethyl 3,5-bis(perfluorobutane) benzoate (15.46 g, 31.8 mmol, 1.0 eq.) and 100 mL of anhydrous THF is added dropwise to a suspension of LiAlH.sub.4 (1.81 g, 47.7 mmol, 1.5 Eq.) and of anhydrous THF (10 mL) under an argon atmosphere and at 0° C. After the addition was complete, the reaction mixture was stirred at room temperature (RT) for 5 h. Then, 10 mL of ethyl acetate is added very slowly. After 15 min, 10 mL of a 10% sulfuric acid solution is cautiously added at 0° C., then the reaction medium is stirred for 20 min. The aqueous layer was extracted with ethyl acetate (3×50 mL). The organic phases are combined, washed with saturated NaCl solution (1×50 mL), dried over magnesium sulphate, filtered and then concentrated under reduced pressure to give a pale yellow solid. This solid is recrystallized from hexane to give [3,5-bis(perfluorobutyl)] phenylmethanol (12.95 g, 29.3 mmol, 92%, liquid).

(48) .sup.1H NMR (CDCl.sub.3, 300 MHz): δ (ppm)=4.88 (s, 2H), 7.70 (br. s, 1H), 7.82 (br. s, 2H).

Example 5: Compositions Comprising a Fluorinated ASM of the Phenolic Type: 3TFMPhOH with Various CEMs

(49) 3-(Trifluoromethyl)phenol was purchased from AlfaAesar, and has a purity of 98+%. It was used as it was.

(50) Dibenzo-18-crown-6 was purchased from TCI Chemicals, and has a purity of >99%, it was used as it was.

(51) To 3 mL of 3-(trifluoromethyl)phenol, was added 217 mg of Dibenzo-18-crown-6 in order to obtain a formulation with 0.2 mole/L of DB18C6. This sealed formulation was then orbitally stirred at 500 rpm overnight after 1 mL of distilled water was added twice to allow water saturation of the whole.

(52) The next morning, an aqueous 0.2 mol/L NaCl solution was prepared from twice distilled water, while the formulation that was stirred overnight was allowed to stand for decantation. A clear decantation of the two colorless phases is obtained in a few minutes. 3 mL of the organic extraction solution is then removed and transferred to a flask containing 3 mL of this salt water containing 0.2 M NaCl, then the flask is sealed and orbitally stirred (usually 500 rpm), for 3 hours and at room temperature. It is verified that droplets of the order of 1-2 mm are present in quantity at the selected stirring speed (400 to 900 rpm).

(53) After stirring for 2 hours, stirring is stopped and the whole is left to stand for decantation for at least 10 minutes until the two phases are completely separated. The upper aqueous phase is then removed and then stirred and diluted for analysis of its salinity by a Metrohm Ion Chromatography Incorporating a suitable cation analysis column and a suitable anion analysis column. Similarly, the initial aqueous solution of 0.2M NaCl is also analyzed by this ion chromatography equipment to determine its relative concentration of sodium and chlorides.

(54) Results:

(55) TABLE-US-00010 CEM: ASM: DB18C6 Mean 3TFMPhOH 0.2M [Na+] mmol/L [Cl−] mmol/L mmol/L Water to be NaCl 0.2M 188.77 193.33 191.05 treated 0 Treated water NaCl 0.125M 130.6  119.4  125.0  Extraction ([NaCl].sub.aq0 − 30.8% 38.8% 34.6% rate at 23° C. [NaCl].sub.aq)/ [NaCl].sub.aq0
This composition is capable of extracting, by direct contact, at iso-volume and at ambient temperature, slightly more than a third of the NaCl present in the water. In addition, slightly more than one-third of the extractant molecules of sodium are in complexed form. Thus, thanks to the presence of the ASM, we observe a 34.6% extraction, where we do not exceed 1.6% extraction by replacing this ASM by dichloromethane.
The same procedure as described above for DB18C6 was applied to the other CEMs described in Example 1. The results of the chromatographic analysis are as follows:

(56) TABLE-US-00011 CEM: ASM: DB21C7 Mean 3TFMPhOH 0.2M [Na+] mmol/L [Cl−] mmol/L mmol/L Water to be NaCl 0.2M 183.77 196.29 190.03 treated 0 Treated water NaCl 0.16M 166.4  155.7  161.1  Extraction ([NaCl].sub.aq0 − rate at 23° C. [NaCl].sub.aq)/ 9.4% 20.7% 15.2% [NaCl].sub.aq0

(57) TABLE-US-00012 CEM: ASM: B15C5 Mean 3TFMPhOH 0.2M [Na+] mmol/L [Cl−] mmol/L mmol/L Water to be NaCl 0.2M 188.77 193.33 191.05 treated 0 Treated water NaCl 0.16M 156.4  169.1  162.7  Extraction ([NaCl].sub.aq0 − rate at 23° C. [NaCl].sub.aq)/ 17.2% 12.5% 14.8% [NaCl].sub.aq0

(58) TABLE-US-00013 CEM: ASM: C15C5 Mean 3TFMPhOH 0.2M [Na+] mmol/L [Cl−] mmol/L mmol/L Water to be NaCl 0.2M 183.77 196.29 190.03 treated 0 Treated water NaCl 0.14M 145.2  136.0  140.6  Extraction ([NaCl].sub.aq0 − rate at 23° C. [NaCl].sub.aq)/ 21.0% 30.7% 26.0% [NaCl].sub.aq0

(59) TABLE-US-00014 CEM: ASM: DC18C6 [Na+] [Cl−] Mean 3TFMPhOH 0.2M mmol/L mmol/L mmol/L Water to be NaCl 0.2M 192.45 182.55 187.50 treated 0 Treated water NaCl 0.13M 136.4 127.2 131.8 Extraction ([NaCl].sub.aq0-  29.1%  30.3%  29.7% rate at 23° C. [NaCl].sub.aq)/ [NaCl].sub.aq0

(60) TABLE-US-00015 CEM: ASM: DB24C8 [Na+] [Cl−] Mean 3TFMPhOH 0.2M mmol/L mmol/L mmol/L Water to be NaCl 0.2M 192.45 182.55 187.50 treated 0 Treated water NaCl 0.12M 124.0 114.9 119.5 Extraction ([NaCl].sub.aq0-  35.5%  37.1%  36.3% rate at 23° C. [NaCl].sub.aq)/ [NaCl].sub.aq0

(61) TABLE-US-00016 CEM: ASM: Calix[4]Est [Na+] [Cl−] Mean 3TFMPhOH 0.2M mmol/L mmol/L mmol/L Water to be NaCl 0.2M 192.45 182.55 187.50 treated 0 Treated water NaCl 0.045M  48.1  41.9  45.0 Extraction rate at ([NaCl].sub.aq0-  75%  77%  76% 23° C. [NaCl].sub.aq)/ [NaCl].sub.aq0

(62) These results show that the extraction rate of the NaCl is strongly dependent on the affinity of the CEM, that is to say of the extractant, for the Na+ cation.

(63) In fact, taking into account the published complexing constants for all of these CEM extractants for sodium, in methanol at 25° C., it is observed a linear correlation in the first part, and then, surprisingly, more strongly growing at the moment when the affinity of the CEM for the sodium in the water exceeds Log K of 1. Moreover this same tendency is also obtained in extraction of KCl or of Na.sub.2SO.sub.4.

(64) TABLE-US-00017 CEM DB21C7 B15C5 C15C5 DC18C6 DB18C6 Calix4Est DB24C8 Log K (Na+) 2.4 3.03 3.71-3.9 4.27 4.36-4.49 5.0-5.7 2.25 MeOH á 25° C. Extraction rate at 15.2% 14.8% 26.0% 29.7% 34.6% 76% 36.3% 23° C.

(65) Only the DB24C8 does not comply with this rule. An explanation could come from the fact that this crown ether is very broad. Indeed, an absorption of two Na.sup.+ cations has already been observed for these macrocycles. However, the complexing constant of 2.25 for this DB24C8 compound could correspond to the case where only one cation is complexed. A complexing constant twice as high as that published for DB24C8 (ie 4.5) would then restore the aforementioned correlation. Thus a CEM presenting at the same time: a complexing constant for sodium, in water at 25° C., greater than or equal to 1, and a complexing constant for sodium, in ethanol at 25° C. greater than or equal to 4, preferably greater than 4.75, makes it possible to have particularly high levels of ion extraction, and in particular for salts such as NaCl, KCl or Na.sub.2SO.sub.4.

Example 6: Compositions Containing a Fluorinated ASM of Methanolic Phenyl Type (ASM 2 and 51 or a Mixture of these Compounds (ASM 4 and 71 with the CEM: Calix[4]Est

Example 6A: Composition ASM 2/Calix[4]Est for Extraction of NaCl

(66) Compound ASM 2 was purchased from Fluorochem (97% purity) and used as it was.

(67) The composition ASM 2/Calix[4]Est is prepared, tested and analyzed according to the same protocol as that described in the preceding Example 5.

(68) Results for composition ASM 2/Calix[4]Est:

(69) TABLE-US-00018 CEM: ASM: 0.2M [Na+] [Cl−] Mean 3TFMBnOH Calix[4]Est mmol/L mmol/L mmol/L Water to be NaCl 0.2M 176.96 208.34 192.65 treated 0 Treated water NaCl 0.08M  80.8  78.8  79.8 Extraction rate at ([NaCl].sub.aq0-  54.3%  62.2%  58.6% 23° C. [NaCl].sub.aq)/ [NaCl].sub.aq0

Example 6B: Composition ASM 41 Calix [4]Est for Extraction of NaCl

(70) ASM 4 is a mixture of ASM 2 and ASM 3 (solid under normal temperature and pressure conditions). 30.4 mL of ASM 4 were formulated by adding 12.16 mL of ASM 2 to 26.14 g of ASM 3. After stirring and dissolving ASM 2, 6.04 g Calix[4]Est is added and solubilized rapidly by means of a slight heating to 40° C. A dilation of the formulation is observed after solubilization of Calix[4]Ester and saturation in water. These compositions were tested and analyzed according to the same procedure as that described in Example 5.

(71) Results for composition ASM 4/Calix[4]Est:

(72) TABLE-US-00019 ASM 4: CEM: 3TFMBnOH + Calix[4]Est [Na+] [Cl−] Mean 35TFMBnOH 0.2M mmol/L mmol/L mmol/L Water to be NaC1 212.71 205.48 209.09 treated 0 0.2M Treated water NaCl 0.04M  42.1  46.5  44.3 Extraction rate at [NaCl].sub.aq0-  80.2%  77.4%  78.8% 23° C. [NaCl].sub.aq)/ [NaCl].sub.aq0
This particular example was reproduced a second time to give an average extraction performance at 78.9%, thus consistent.
The presence of a second trifluoromethyl in the meta position of the alcohol function has a very favorable effect on the extraction of the NaCl by allowing a better solvation of the anions.

(73) The graph of FIG. 1 represents the extraction rates obtained by an ASM 4 and Calix4Est composition (0.4 M) for salt water (NaCl) of various salinities and at variable temperatures ranging from ambient temperature to 80° C. and iso-volume Water/(ASM 4/Calix[4]Est) Composition.

(74) The extraction performance is quite remarkable, with NaCl extraction rates ranging from 90% for the lowest concentrations to 15% for the highest concentrations, all at iso-volume water/solvent with a decrease of Extraction rate of about one third at 60° C. compared to 20° C.

(75) For this ASM 4/Calix[4]Est composition, it is calculated via these results that the enthalpic interactions developed are of the order of 33 kJ/mole of displaced salts. Thus, for a displacement of 36 g NaCl per liter of water (standard seawater concentration), a basic energy of only 21 kJ/kg of desalted water is required. The latent heat of vaporization of water being 2319 kJ/kg at 75° C., the energy consumed during the implementation of the method according to the invention is 100 times less than that required for the evaporation of water.

(76) The graph of FIG. 2 shows the loading rate of the CEM, Calix[4]Est with NaCl, as a function of the concentration of CEM (diamond: 0.2M, round: 0.4M and triangle 0.8M) when it is under extraction with salt water of various concentrations. To obtain an optimum loading rate (close to 100%) at the end of the extraction/absorption phase for salt water at salinities close to the typical salinity of seawater (0.6 M), a concentration between 0.2 M and 0.4 M of Calix[4]Est is to be preferred.

Example 6C: Composition ASM 41 Calix[4] for the Extraction of Na.SUB.2.SO.SUB.4

(77) The extraction of Na.sub.2SO.sub.4 was also carried out with the composition ASM 4/Calix[4]Est previously described for various concentrations of Calix[4]Est (triangle: 0.2M, diamond: 0.4M and round 0.8M). The graph of FIG. 3 represents the extraction rates of this salt which have been obtained for waters of different Na.sub.2SO.sub.4 concentrations following the protocol described above. It appears that a greater concentration of CEM allows improved extraction of Na.sub.2SO.sub.4.
Although the sulphates belong to the most hydrophilic anions, we again observe a good extraction of these salts over all the concentrations tested.

Example 6D: Composition ASM 5/Calix[4]Est for Extraction of NaCl

(78) ASM 5 compound was synthesized according to the method described in Example 3 and used as it was.

(79) The ASM 5/Calix[4]Est composition is prepared, tested and analyzed according to the same protocol as that described in Example 5 except that the orbital stirring used was 900 rpm because of a higher viscosity of this formulation.

(80) Results for composition ASM 5/Calix[4]Est:

(81) TABLE-US-00020 CEM: ASM 5: Calix[4]Est [Na+] [Cl−] Mean 3C4F9BnOH 0.2M mmol/L mmol/L mmol/L Water to be NaCl 0.2M 189.17 191.24 190.20 treated 0 Treated water NaCl 0.086M  86.65  86.44  86.55 Extraction rate at ([NaCl].sub.aq0-  54.2%  54.8%  54.5% 23° C. [NaCl].sub.aq)/ [NaCl].sub.aq0
A slightly lower NaCl extraction rate is obtained when compared to ASM 2 but for a product with a much lower solubility in water (<0.077 vs. 32 mMole/L).

Example 6E: Composition ASM 7/Calix[4]Est for Extraction of NaCl

(82) ASM 7 is a mixture of 70% ASM 5 and 30% ASM 6 v/v. It was obtained with the same process as for ASM 4, after recalculation of the masses of compounds to be brought into contact.

(83) These compositions were synthesized, formulated, tested and analyzed according to the same procedure as that described in Example 5.

(84) Results for composition ASM 7/Calix[4]Est:

(85) TABLE-US-00021 ASM 7: MEC: 3C4F9BnOH + Calix[4]Est [Na+] [Cl−] Mean 35C3F7BnOH 0.2M mmol/L mmol/L mmol/L Water to be NaCl 0.2M 212.7 205.5 209.1 treated 0 Treated water NaCl 0.05M  54.2  50.2  52.2 Extraction rate at ([NaCl].sub.aq0-  74.5%  75.6%  75% 23° C. [NaCl].sub.aq)/ [NaCl].sub.aq0
A slightly lower level of NaCl extraction is obtained when compared to ASM 4 but for a product with a much lower water solubility (<0.07 vs 15 mMole/L).

Example 7 Method and Device

(86) An example of a device according to the invention making it possible to implement the method according to the invention is shown in FIGS. 4 and 5. This example relates to a system for cold extraction/absorption of ions associated to a system of hot de-extraction/desorption of ions, both in liquid phases. FIG. 5 includes an indication of the temperatures of the liquids at each step and for each flow of the device. FIG. 6 is a table showing the concentrations of each ionic species in each of the identified flows as well as the total salinity, density, temperature and flow rate of these flows when the water to be treated is sea water.

(87) Reactor

(88) The device comprises a first reactor (7) and a second reactor (9) allowing mixing of the organic phase and the aqueous phase and the decantation of the liquids. This mixing allows the contact between the two phases and therefore the exchange of ions. The more intimate the contact is, the more important the exchange of ions is.

(89) Such reactors (7) and (9) may comprise liquid-liquid extraction/absorption gravitational columns (as shown in FIG. 4 where reactors (7) and (9) are advantageously of similar construction). Alternatively, the reactor (7) and/or the reactor (9) may be chosen from mixer-settlers and/or centrifugal extractors/settlers.

(90) These reactors (7) and (9) can thus comprise stirring means (for example at least one stirrer) enabling the mixer to ensure better pumping action by axial or radial flow and a turbulence action with more or less shear.

(91) These stirring means integrate moving elements, such as propellers or other rotating elements for shear and/or turbulence. They may also comprise centrifuging means and/or a centrifuge, for example comprising a centrifugal settler.

(92) Alternatively or cumulatively, they may contain static shear means, such as the presence of structured or not structured packing inside the reactor, acting as a stop to oppose the progression of the liquid and resulting in turbulence and/or shear of the liquid present within the reactor.

(93) Method: Water Treatment

(94) In the example shown in FIGS. 4 and 5, the absorption column (7) therefore permits the mixing of a hydrophobic organic liquid phase according to the invention which is chosen so that it has a higher density than the water to be treated and the produced brine.

(95) Thus, when the reactor is a column, the two liquid phases are advantageously introduced into vertically opposite parts of the column (7) where they therefore circulate counter to each other by a simple gravitational effect. The opening allowing the introduction of the denser phase is advantageously positioned in the upper part of the column (7) but below the settling zone constituted by the upper end of the column (7). Similarly, the opening allowing the introduction of the less dense phase is advantageously positioned in the lower part of the column (7) but above the settling zone which constitutes the lower end of the column (7).

(96) Stirring means as described above are advantageously included in the reactor (7) in order to allow the intimate mixing of the two liquid phases.

(97) Saline water to be treated (1) is advantageously sea water and is introduced, for example by means of a pump, to the column (7) where the ions dissolved in the water are transferred totally or partially to the organic phase, namely, in this particular case, calix[4]Est dissolved at a level of 0.3M in ASM 6. The organic phase which is not miscible with water, therefore contains ion solvating molecules, with high affinity for at least some of the ions to be transferred. For this particular example, where the organic phase not charged with ions (10) introduced at the top of the column is denser than the water to be treated (1), the uncharged organic phase (10) flows down the column and gets charged with ions extracted from the saline water to be treated (1) to reach the lower end of the column (7) where it accumulates by decantation after coalescence. Conversely, the water to be treated (1) injected into the lower part of the column (7) flows up by differential density (Archimedes principle) while gradually transferring its ions to the descending organic phase, to reach the upper end of the column (7) as treated water (2) or desalted water. This treated water is desalted and/or deionized in whole or in part, that is to say that it has lost all or at least some of the salts and/or the ions constituting these salts, which where dissolved before its passage into the reactor (7). For example, this water is dechlorinated or decarbonated.

(98) Method: Heating the Organic Phase

(99) The organic phase charged with ions (11) is then pumped to a first heat exchanger (14) in order to be heated to a sufficient temperature (cf. FIG. 5) In order to allow the charged organic phase (11) to be discharged from the ions extracted from the water to be treated (1) in the preceding step in the reactor (7). The charged and heated organic phase (12) is then introduced into the upper part of the second reactor (9) so as to be brought into contact with hot treated water (4).

(100) Second Reactor

(101) As previously described when the reactor is a column, as in this example, the two liquid phases are advantageously introduced into vertically opposite parts of the column (9) where they thus circulate counter to each other by a simple gravitational effect. The opening allowing the introduction of the denser phase is advantageously positioned in the upper part of the column (9) but below the settling zone constituted by the upper end of this column (9). Similarly, the opening allowing the introduction of the less dense phase is advantageously positioned in the lower part of the column (9) but above the settling zone which constitutes the lower end of this column (9).

(102) Stirring means as described above are advantageously included in the reactor (9) in order to allow the intimate mixing of the two liquid phases.

(103) Method: Organic Phase Recycle

(104) The hot treated water (4) advantageously comes from the treated water (2) obtained at the end of its treatment in the reactor (7) and a part of which is directed by the pipe (3) to a second heat exchanger (8) to be heated therein. The other portion of the treated water (15) may be used.

(105) This hot treated liquid water (4) is therefore injected into the lower part of the column (9) and mixed with the charged and hot organic liquid phase (12). This hot liquid water (4) ascends by differential density (Archimedes principle) while gradually charging due to the temperature of the descending organic phase, to reach the upper end of the column (9) as ion-charged water (5). This ion-charged water (5) preferably has an ion concentration higher than that present in the water to be treated (1) and is then referred to as brine (or concentrate). This brine or concentrate (5) is evacuated after settling and is directed to the heat exchanger (8) in order to be cooled as brine (6). The charged organic phase (12) arriving at the top of the column (9) is denser than the hot regeneration water (4), the charged and hot organic phase (12) flows down the column (9) while gradually transferring its extracted ions to the hot liquid treated water (4) to reach the lower end of the column (9) where it accumulates by settling after coalescence. This regenerated organic phase (13) having transferred to the hot regeneration water (4) the salts (or ions) extracted in column (9) is then cooled by passage through the heat exchanger (14) to be redirected (for example by means of a pump) to the upper part of the first reactor (7) in order to be introduced therein and thus recycled as uncharged organic phase (10).

(106) Organic Phase and Operating Temperature

(107) In the method and the device according to the invention, controlling the temperature of the medium of the first and second reactors (7) and (9) is an important factor in ensuring optimized operation thereof. Also, temperature control means are advantageously included in the device according to the invention in order to control and possibly modify the temperature of the latter. These may include temperature measuring means (such as thermometers) and/or heating means (eg a heat source) or cooling means (eg, a cooler).

(108) In the particular example described in FIG. 4, such means may advantageously be disposed in or form part of: 1—a pipe to feed the water to be treated (1) to the first reactor (7), 2—a pipe to feed the hot ion-charged organic phase (12) from the exchanger (14) to the second reactor (9), 3—a pipe to feed the hot regeneration water (4) from the heat exchanger (8) to the second reactor (9), and/or 4—a pipe to feed the regenerated organic phase (10) from the heat exchanger (14) to the first reactor (7).

(109) In the second or third case mentioned above, the control means advantageously comprise heating means. In the fourth of the above mentioned cases, the control means may advantageously comprise cooling means.

(110) Thus, the method according to the invention makes it possible to obtain a brine that is more concentrated in salts (ions) than the water to be treated due to the intrinsic properties for extraction/ion absorption of the non water miscible organic phase, which depend on the considered operating temperature.

Example 8

(111) A variant of the device and the process described in Example 7 is shown in FIG. 7. In this variant, the non water miscible organic phase is less dense than the water to be treated and the brine produced. FIG. 7 shows the same numbering used in FIG. 4. In this variant, the columns operate in reverse flows (“head down”). There is a cold section on the left of the heat exchangers and a hot section on the right of the heat exchangers (8) and (14). The elements of this device are therefore as described with reference to FIG. 4 and to example 7.

Example 9

(112) Another variant of the device according to the invention is shown partially in FIG. 8. In this device, each of the columns (7) and (9) is replaced by the combination of a rotor/stator mixer (20) with an propeller and a settling tank (30). Each of these combinations forms an extraction/de-extraction unit, which can be connected in series in order to carry out a succession of absorption or regeneration steps. The number of steps required to desalinate seawater and obtain water where more than 99% of the sodium will have been extracted, will generally be at least 3, preferably 4 or 5 stages.

Example 10: Synthesis of Compounds ASMC7, ASMC9, ASMC11 and ASMC13

(113) Synthesis Diagram

(114) ##STR00037##
R=n-C.sub.7H.sub.15 (ASMC7), n-C.sub.9H.sub.19 (ASMC9), n-C.sub.11H.sub.22 (ASMC11), n-C.sub.13SH.sub.27 (ASMC13).

(115) Protocol

(116) 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.) is added under stirring and dropwise of acid chloride (56.29 mmol, 1.0 eq.). The temperature is controlled during the addition and must 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 the organic phase is then washed. Successive washes are carried out with 1M HCl solution (50 mL) and 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 up in 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 composed mainly of n-pentane, 2-methyl pentane with CAS No. 64742-49-0 from VWR, where it is sold under the name ON ether 40-60° C. GPR RECTAPUR. The compounds obtained have the following characteristics:

(117) TABLE-US-00022 Molar weight Petroleum Melting R Component (g/mole) ether T ° C. Yield Aspect Point n-C.sub.7H.sub.15 ASMC7 355.3 Cold 91% White 43-44° C. (−20° C.) solid n-C.sub.9H.sub.19 ASMC9 383.3 Ambient 92% White 79-81° C. solid n-C.sub.11H.sub.23 ASMC11 411.4 Ambient 92% White 60-61° C. solid n-C.sub.13H.sub.27 ASMC13 439.5 Ambient 90% White 53-54° C. solid

(118) The compounds ASMC7, ASMC9, ASMC11 and ASMC13 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 further identified by NMR spectrometry. FIG. 9 shows the NMR spectrum (CDCl.sub.3, 300 MHz) of the ASMC11 compound, the peaks of which are as follows: 1 H 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 11: Extraction of Sodium Chloride from an Aqueous Solution by Formulations Comprising an ASM of the Amide Family and the Calix[4]Est CEM in the Presence of a Fluidifying Agent (Chloroform CHCl.SUB.3.) and Comparison with Other ASMs and Compounds

(119) The ASMs of the amide family used are the compounds ASMC7, ASMC9, ASMC11, and ASMC13, the synthesis of which is described in Example 10. By way of comparison, ASM3 and 3,5-Di(trifluoromethyl)aniline (CAS No. 328-74-5) have also been used in the preparation of extracting compositions.

(120) The extraction composition is obtained by solubilizing an amount of 4-tert-butyl Calix[4]arene tetraethyl Ester (CAS No. 97600-39-0) and ASM in chloroform CHCl.sub.3 to obtain a final concentration after solubilization of the CEM and ASM of 0.3 mol/L for Calix[4]Est and of 0.3 mol/L for ASM, respectively. These sealed formulations were then orbitally stirred at 500 rpm for 2 hours after adding an equivalent volume of twice distilled water to allow water saturation of the entire formulation and control of pH output (pH=7). The extraction composition is then put to stand to settle. All the compositions tested are stable and rapidly decanted (a few minutes at the most).

(121) A 0.4 mol/L NaCl aqueous solution was prepared from twice distilled water.

(122) The organic extraction composition is then slightly heated to promote solubilization of the compounds by hot air gun (temperature of about 50 to 60° C.) for a few seconds (10 to 30 seconds) until a clear solution is obtained.

(123) 3 mL of the organic extraction composition is then removed from the lower phase of the settled two-phase mixture and transferred to a vial containing 3 mL of salt water at 0.4 M NaCl and then the flask 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. In the case of extraction at 60° C., magnetic stirring (at 500 revolutions per minute), for 2 hours, is carried out with indirect heating in a metal mold on a heating plate. It is verified that droplets of the order of 1-2 mm are present during these agitations in order to be certain to achieve equilibrium in the NaCl distribution between the two liquid phases at the end of stirring. The appearance of the organic and aqueous phases is clear and colorless or slightly cloudy.

(124) After stirring for 2 hours, stirring is stopped and the solution is put to stand to settle within 10 minutes, at least until the two phases have completely separated off, at the temperature of the test. The upper aqueous phase is then removed and then stirred and diluted for analysis of its salinity by a Metrohm Ion Chromatograph incorporating a suitable cation analysis column and a suitable anion analysis column. Similarly, the initial aqueous solution of NaCl at 0.4M is also analyzed by this ion chromatograph to determine its relative molar concentration in sodium and in chlorides. AN extractions and analyzes were duplicated. The table below shows the results observed for an iso-molar distribution of ASM and CEM:

(125) TABLE-US-00023 Mol % Na+ Mol % Cl- Concentra- Concen- Appearance Extrac- extracted extracted tion of tration after tion from the from the ASM CEM in of ASM saturation T water to be water to be tested Mol/L in Mol/L with water (° C.) treated treated ASMC13 0.300 0.300 Slightly RT 22.7% 26.2% cloudy ASMC13 0.300 0.300 Slightly RT 23.8% 27.4% cloudy ASMC13 0.300 0.300 Slightly 60° C.  5.9%  6.9% cloudy ASMC13 0.300 0.300 Slightly 60° C.  9.0%  9.4% cloudy ASMC11 0.300 0.300 Slightly RT 22.4% 24.5% cloudy, Some crystals ASMC11 0.300 0.300 Slightly RT 23.1% 25.3% cloudy, Some crystals ASMC11 0.300 0.300 Slightly 60° C.  3.4%  4.9% cloudy, Some crystals ASMC11 0.300 0.300 Slightly 60° C.  7.1%  7.7% cloudy, Some crystals ASMC9 0.300 0.300 Slightly RT 25.2% 27.1% cloudy ASMC9 0.300 0.300 Slightly RT 21.7% 23.8% cloudy ASMC9 0.300 0.300 Slightly 60° C.  5.4%  6.9% cloudy ASMC9 0.300 0.300 Slightly 60° C.  5.7%  8.0% cloudy ASMC7 0.304 0.304 Clear RT 23.6% 26.3% ASMC7 0.304 0.304 Clear RT 22.8% 25.9% ASMC7 0.304 0.304 Clear 60° C.  5.5%  7.6% ASMC7 0.304 0.304 Clear 60° C.  5.4%  7.3% ASM3 0.300 0.300 Clear RT  6.8%  8.2% ASM3 0.300 0.300 Clear RT  7.6%  8.8% ASM3 0.300 0.300 Clear 60° C. not not detected detected ASM3 0.300 0.300 Clear 60° C. not not detected detected AnilineF* 0.300 0.295 Clear RT  2.0%  4.3% AnilineF* 0.300 0.295 Clear RT  1.8%  2.9% AnilineF* 0.300 0.295 Clear 60° C. not not detected detected AnilineF* 0.300 0.295 Clear 60° C. not not detected detected

(126) The average results for the molar extraction of sodium chloride can therefore be summarized in the following table:

(127) TABLE-US-00024 Salt, T NaCl - 20° C. NaCl - 60° C. Δ ASM % ext % ext % ext ASMC7 24.6% 6.3% 18.4% ASMC9 24.4% 6.5% 17.9% ASMC11 23.8% 5.8% 18.0% ASMC13 25.0% 7.8% 17.2% ASM3  7.9% 0.0%  7.9% AnilineF*  2.7% 0.0%  2.7%

(128) it therefore appears on the one hand that the anionic solvating agents of the amide family (ASMC7-13) according to the invention are more active than the anionic solvating agents of the alcohols family (ASM3). In particular, they allow an efficient capture at ambient temperature and a sufficient release of the ionic species at a higher temperature but sufficiently low (especially below 150° C.). It also appears that the amine version AnilineF* is even less active than alcohol with identical concentration. However, these compounds can be used in extraction compositions according to the invention simply by increasing its ASM concentration above 2 mol/L (see examples 6).

(129) This overactivity of the amides is also maintained when the alkyl chain of the amide function is extended from C.sub.7H.sub.15 to C.sub.11H.sub.27, which makes it possible to ensure good water non solubility of this family of anionic solvating agents.

Example 12: Extraction of Sodium Chloride from an Aqueous Solution by Formulations Comprising the ASMC7 from the Amide Family at Four Different Concentrations and the CEM Calix[4]Est at Constant Concentration in the Presence of a Fluidifying Agent (CHCl.SUB.3.) and Comparison of the Associated Extraction Performance

(130) Four extraction compositions were obtained by solubilizing a constant amount of 4-tert-butylCalix[4]arene tetraethylEster (CAS No. 97600-39-0) and four increasing amounts of ASMC7 in chloroform CHCl.sub.3 to obtain four final concentrations after solubilization of CEM and ASM, from 0.34 to 0.36 mol/L for Calix[4]Est and 0.36 mol/L, 0.71 mol/L, 1.09 mol/L and 1.49 mol/L for ASMC7, respectively. These four sealed formulations were then orbitally stirred at 500 rpm for 2 hours after adding an equivalent volume of twice distilled water to allow water saturation of the entire formulation and control of pH at the output (pH=7). The extraction composition is then put to stand for settling. All the compositions tested are stable and rapidly decanted (a few minutes at the most).

(131) An 0.3 mol/L NaCl aqueous solution was prepared from twice distilled water.

(132) 3 ml of each organic extraction composition are then removed in the lower phase of the settled two-phase mixture and transferred to four vials, each containing 3 ml of the salt water at 0.3M NaCl, then the flasks are 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. In the case of extraction at 60° C., a magnetic stirring (at 500 revolutions per minute), for 2 hours, is carried out with indirect heating in a metal mold on a heating plate. It is verified that droplets of the order of 1-2 mm are present during these agitations in order to be certain to reach equilibrium in the NaCl distribution between the two liquid phases at the end of stirring. The appearance of the organic and aqueous phases is clear and colorless for these 4 formulations tested.

(133) After stirring for 2 hours, stirring is stopped and the solution is put to stand for settling within 10 minutes, at least until the two phases have completely separated off, at the test temperature. Then, the four upper aqueous phases are separately taken and then stirred and diluted for analysis of their salinity by a Metrohm Ion Chromatograph incorporating a suitable cation analysis column and a suitable anion analysis column. Similarly, the initial aqueous solution of 0.3M NaCl is also analyzed by this ion chromatograph to determine its relative molar concentration of sodium and chlorides. All extractions and analyzes were duplicated. The below table shows the results observed for four molar distributions between ASM and CEM:

(134) TABLE-US-00025 Mol % Mol % Concen- Concen- of Na+ of Cl− tration tration Concen- Aspect extracted extracted of of tration after Ex- from from CEM ASMC7 ratios water traction water water in in [ASMC7]/ satu- T to be to be Mol/L Mol/L [ASM] ration (° C.) treated treated 0.345 0.358 1.04 Clear RT 27.9% 27.9% 0.345 0.358 1.04 Clear RT 21.7% 27.2% 0.345 0.358 1.04 Clear 60° C.  9.9% 13.0% 0.345 0.358 1.04 Clear 60° C. 13.1% 14.1% 0.341 0.708 2.08 Clear RT 44.2% 44.4% 0.341 0.708 2.08 Clear RT 45.1% 44.4% 0.341 0.708 2.08 Clear 60° C. 28.1% 26.6% 0.341 0.708 2.08 Clear 60° C. 28.2% 27.4% 0.349 1.088 3.12 Clear RT 60.0% 51.2% 0.349 1.088 3.12 Clear RT 59.8% 52.9% 0.349 1.088 3.12 Clear 60° C. 37.7% 31.0% 0.349 1.088 3.12 Clear 60° C. 39.5% 30.4% 0.358 1.488 4.16 Clear RT 71.2% 64.6% 0.358 1.488 4.16 Clear RT 65.0% 65.6% 0.358 1.488 4.16 Clear 60° C. 48.4% 45.6% 0.358 1.488 4.16 Clear 60° C. 46.9% 39.9%
The average results for the extraction of sodium chloride can thus be summarized in the following table:

(135) TABLE-US-00026 Salt, T NaCl - 20° C. NaCl - 60° C. Δ [ASMC7]/[CEM] % ext % ext % ext 1.04 26.2% 12.5% 13.6% 2.08 44.5% 27.6% 16.9% 3.12 55.9% 34.5% 21.3% 4.16 66.6% 45.1% 21.4%

(136) It appears a regular and almost linear rise of the NaCl extraction rate with an increase of the relative concentration of ASMC7, at ambient temperature or at 60° C., showing the importance of poly-solvation of the Chloride anion ASM to allow a good NaCl extraction. It should also be noted that not all CEMs are used for 0.3 M NaCl initial salinity, leaving room for extra extraction for higher salinity.

(137) 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 use this method to upgrade water from many sources of natural or industrial salt water. It is also possible to employ this method in order to allow salt reconcentration by increasing the regeneration temperature or to selectively extract certain salts having, for example, a certain economic value or promoting scale formation. In addition, with certain improvements, this method will be able to treat produced water or industrial water for the production of process water, in order to limit environmental impacts associated with salt water discharges into natural environments.

(138) The invention may also incorporate embodiments where several ECMs will be dissolved in an ASM, a mixture of ASMs or an ASM and a fluidifying agent or a mixture of ASMs and fluidifying agents in order to allow the extraction of a larger panel of Cations and anions; their associated counter-ions.