US-12623942-B2 - 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 2 Phenyl 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.

Inventors

• Guillaume De Souza
• Jacky Pouessel
• Bastien DAUTRICHE

Assignees

• ADIONICS

Dates

Publication Date

20260512

Application Date

20230804

Priority Date

20160722

Claims (11)

1. 1 . A process for deionizing water by extraction in a liquid medium with thermal regeneration, applied to the extraction of a divalent, non-alkaline cationic species and of a complementary anionic species from a saline liquid aqueous solution, the saline liquid aqueous solution comprising: a salt of the divalent non-alkaline cationic species, and a salt of a cationic species of an alkaline metal, the process comprising the following steps: a) mixing in a first reactor, at a first temperature, 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 divalent non-alkaline cationic species and the complementary anionic species, the liquid hydrophobic organic phase comprising an extracting molecule of the divalent non-alkaline cationic species and a solvating molecule of the complementary anionic species, b) separating the treated liquid aqueous solution and the liquid hydrophobic organic phase charged with the divalent non-alkaline cationic species and the complementary anionic species; and c) mixing, at a second temperature in the liquid phase, in a second reactor, the liquid hydrophobic organic phase, charged with the divalent non-alkaline cationic species and the complementary anionic species, with a regeneration liquid aqueous solution, in order to subsequently obtain a regenerated liquid hydrophobic organic phase and a regeneration liquid aqueous solution charged with the divalent non-alkaline cationic species and the complementary anionic species, the difference between the first and second temperatures being in a range from 30° C. to 150° C., the second temperature being higher than the first temperature; wherein the extracting molecule of a non-alkaline cationic species is a macrocycle, the cycle of which is formed from 24 to 32 carbon atoms, functionalized with amide groups, having the following formulae (I) or (II): where n is an integer from 5 to 8, p is 1 or 2, m is 3 or 4, q and t, identical or different, are 0, 1 or 2, R is a tert-butyl, tert-pentyl, tert-octyl, O-methyl, O-ethyl, O-propyl, O-isopropyl, O-butyl, O-isobutyl, O-pentyl, O-hexyl, O-heptyl, O-octyl, OCH 2 -Phenyl group, or a hydrogen atom, R′ and R″, identical or different, are selected from the group constituted by methyl, ethyl, propyl, isopropyl, butyl and isobutyl, pentyl, hexyl, heptyl and octyl groups, or R′ and R″ together form a pyrrolidine, piperidine or morpholine ring.
2. 2 . The process according to claim 1 , wherein the extracting molecule of the at least one non-alkaline cationic species is selected from the compounds of formula (I) with calixarene macrocycle, with p=1, and R, R′, R″ and n as defined below: R R' R'' n tert-Butyl Pyrrolidinyl 6 tert-Butyl Ethyl Ethyl 6 O-Octyl Ethyl Ethyl 6 OCH 2 -Phenyl Ethyl Ethyl 6 H Ethyl Ethyl 6 O-methyl Ethyl Ethyl 6 tert-Butyl Ethyl Ethyl 8 O-Octyl Ethyl Ethyl 8 OCH 2 -Phenyl Ethyl Ethyl 8 H Ethyl Ethyl 8 O-methyl Ethyl Ethyl 8.
3. 3 . The process according to claim 1 , wherein the extracting molecule has a complexing constant Log K, in methanol at 25° C., of the divalent non-alkaline cationic species to be extracted, higher than 3 and less than 11.
4. 4 . The process according to claim 1 , wherein the divalent non-alkaline cationic species is at least one of the following cations: calcium, strontium and barium.
5. 5 . The process according to claim 1 , wherein the divalent non-alkaline cationic species is selectively extracted with respect to the cationic species of an alkaline metal.
6. 6 . The process according to claim 1 , wherein the cationic species of an alkaline metal is sodium ion Nat.
7. 7 . The process according to claim 1 , wherein the liquid hydrophobic organic phase comprises a fluidizing agent.
8. 8 . The process according to claim 7 , wherein the fluidizing agent is an aromatic polar solvent selected from the group consisting of dichlorobenzenes, dichlorotoluenes, derivatives thereof and mixtures thereof.
9. 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. 10 . The process according to claim 1 , wherein the solvating molecule of the complementary anionic species is a molecule of formula: in which R is R=n-C 7 H 15 , n-C 9 H 19 , n-C 11 H 23 or n-C 13 H 27 .
11. 11 . The process according to claim 1 , wherein the solvating molecule of the complementary anionic species is a molecule of formula:

Description

CROSS REFERENCE TO RELATED APPLICATIONS This application is a Divisional of application Ser. No. 16/319,748, filed on Jan. 22, 2019, which is the National Phase under 35 U.S.C. § 371 of International Application No. PCT/FR2017/052021, filed on Jul. 21, 2017, which claims the benefit under 35 U.S.C. § 119(a) to Patent Application No. 1657078, filed in France on Jul. 22, 2016, all of which are hereby expressly incorporated by reference into the present application. TECHNICAL FIELD OF THE INVENTION The technical field of the invention is the ionic extraction of salts, particularly of hydrophilic salts, applied to the treatment of industrial or natural saline waters. PRIOR ART Mining, oil or industrial activities may produce highly salty, very scaling and/or toxic metal-contaminated waste waters which need to be treated before being discharged into the environment, or even before being recirculated within an industrial process. In either case, nowadays, manufacturers only have very expensive solutions which are poorly or not adapted to their specific environment. There are also cases, in particular for very scaling saline waters which are rich in alkaline-earth cations and/or which incorporate trace metals, for which, today, there is no technology for treating these waters sustainably and/or economically, thereby forcing to store these waters in settling tanks while waiting for a solution. In the case of mixtures of waters from different springs or of very scaling waters, equipment is often scaled because of the precipitation of salts having a low solubility in water, such as some carbonate salts (MgCO3, CaCO3, SrCO3, BaCO3, CdCO3, CoCO3, MnCO3, PbCO3, NiCO3, FeCO3, ZnCO3 . . . ), sulfate salts (CaSO4, SrSO4, BaSO4, PbSO4 . . . ), fluoride salts (MgF2, CaF2, SrF2, BaF2, CdF2, FeF2, PbF2 . . . ), metallic hydroxide salts (Mg(OH)2, Ca(OH)2, Cd(OH)2, Co(OH)2, Fe(OH)2, Ni(OH)2, Zn(OH)2 . . . ), and many others which can be present in high amount. Furthermore, if the technology used is associated with a thermal vaporization of this water, the temperature of use, which is generally greater than 80° C., then causes the lowering of precipitation threshold of some salts (for example, carbonate salts such as CaCO3 through carbon dioxide evaporation) and of the salts having an inverse solubility (such as CaSO4), which can limit the maximum water extraction level of salt water all the more or produce an even more abundant volume of solid waste to be managed. In order to extract an ion or a salt which is present in a dissolved form in an industrial or natural water, the common approach consists in using the chemical way, for example, by ensuring the precipitation thereof, through adding a reagent, such as, for example, a base (NaOH . . . ), allowing the precipitation of metallic hydroxides, which are not soluble in water. This way is non-selective with respect to the precipitated metals and corresponds to a cation (Na+ versus metal here) or anion exchange and causes other disadvantages, such as the addition of new contaminants to be treated downstream and a decrease in efficiency with a decrease in the concentration of the target compounds. Another way through solvent extraction, known as a hydrometallurgical way, can also be implemented when it comes to entrapping metals such as Nickel, Cobalt . . . in higher concentration, through an exchange of cations Mn+/nH+. These processes use cationic extracting agents which are dissolved in a solvent, implementing an acid-base chemistry or the extraction and the regeneration of the solvent occur at pHs differing by several orders of magnitude. Such a way thus uses expensive bases (NaOH . . . ) and acids (H2SO4 . . . ), resulting in the addition of new contaminants associated with the co-production of salts (Na2SO4 . . . ) to be managed downstream. Another way which has also been implemented for more than 50 years consists in using selective electrodialysis membranes, that is to say membranes which are permeable to cations or to anions and not permeable to water and to neutral molecules in general. In this case, the consumed electrical energy is proportional to the salt which is moved, thereby limiting its use to high value-added applications in the case of brine treatment. This technology is not selective with respect to ions with the same charge and is thus not selective with respect to the metals or anions to be extracted, while being risky concerning membrane fouling. Other ways exist, such as, for example, ion exchange where selectivity depends on the ion charge, is limited by the concentration of the ion which is treated, and producing there also a supply of new contaminants resulting from the chemical regeneration of the resins. More recently, the applicant disclosed in application WO2010/086575 the use of fluorinated compounds in a direct contact exchanger comprising a liquid and hydrophobic fluorinated phase associated with ion exchangers. However, the liquid organic fluori