WO1999065824A1

WO1999065824A1 - Method for separating trivalent lanthanide cations by selective complexing

Info

Publication number: WO1999065824A1
Application number: PCT/FR1999/001386
Authority: WO
Inventors: Christian Husson; Philippe Vottero
Original assignee: Commissariat A L'energie Atomique
Priority date: 1998-06-12
Filing date: 1999-06-11
Publication date: 1999-12-23
Also published as: FR2779711B1; FR2779711A1

Abstract

The invention concerns a method for separating trivalent lanthanide cations by selective complexing from an aqueous solution containing them. More precisely, the invention concerns a method for separating a trivalent lanthanide cation from an aqueous solution containing besides said lanthanide cation one or several other lanthanide cation(s) by contacting said solution with a specific ligand derived the all-cis-1,3,5-triamino-2,4,6-trihydroxycyclohexane (TATHC). Said solutions can be in particular aqueous solutions derived from plants reprocessing used fuel, such as solutions from fuel or aqueous effluent dissolution. They can also consist of aqueous solutions derived from rare earth, thorium and/or uranium ore treatment.

Description

PROCESS FOR SEPARATING TRIVALENT LANTHANIDE CATIONS BY SELECTIVE COMPLEXATION

DESCRIPTION

The present invention relates to a process for the separation of trivalent lanthanide cations by selective complexation from an aqueous solution containing them. More specifically, the invention relates to a process for the separation of a trivalent lanthanide cation from an aqueous solution containing, in addition to said lanthanide cation, one or more other lanthanide cation (s) by contacting of said solution with a specific ligand.

Such solutions may in particular be aqueous solutions originating from installations for the reprocessing of spent nuclear fuels, such as solutions for dissolving the fuel or aqueous effluents.

They can also be constituted by aqueous solutions originating from the processing of rare earth ores, thorium and / or uranium.

The term "lanthanides" designates the 15 elements having atomic numbers from 57 to 71 inclusive, that is to say: lanthanum, cerium, praseodymium, neodymium, promethium, samarium, 1 europium, gadolinium, terbium, disprosium, holmium, erbium, thullium, ytterbium and lutetium. These elements have multiple applications in all industrial fields. Thus, these elements are used in the field of ceramics, metallurgy, glassware, catalysis in organic chemistry, in the nuclear industry and more recently in the microelectronics and superconductivity sector.

Certain elements of the lanthanide family are also used in medicine as tracers.

There are various methods for the separation of elements of the lanthanide family from other metals present in ores and in particular in monazite.

The separation of the lanthanides between them is also carried out on an industrial level but remains extremely difficult because the differences in properties of the lanthanides between them are extremely small.

In particular, the lanthanides have low separation coefficients from one element to another, except for the cerium which can be oxidized at degree IV. In the prior art, most of the methods for separating the lanthanides from one another are liquid-liquid extraction processes in which the selective extraction of one of the lanthanides, generally found in aqueous solution, is carried out at using an extraction solvent immiscible with said solution, and comprising an extraction agent in solution in an organic diluent.

Among the extractants, mention may be made in particular of amines, and especially organophosphorus compounds such as di (2-ethylhexyl) phosphoric acid, quaternary ammonium salts and tributylphosphate (TBP). Thus, patent EP-A-0 284 503 describes the separation of the lanthanides contained in an aqueous solution, by contacting with an organic phase containing an asymmetric phosphine oxide as extracting agent, and a diluent organic which is preferably an aliphatic hydrocarbon.

Document BR-A-89 06103 relates to the separation of samarium, europium and gadolinium from rare earth concentrates containing yttrium, by liquid-liquid extraction with a dilute solution of di- 2-ethylphosphoric.

All the liquid-liquid extraction methods mentioned have the drawback of introducing, due to the presence of an organic diluent, new organic species which can prove to be extremely troublesome for the rest of the operations.

Furthermore, the presence of phosphorus in most extractants is also likely to affect subsequent treatments, in particular by incineration.

Finally, none of the methods of the prior art cited above provides sufficient separation coefficients to allow efficient separation of the lanthanides contained in an aqueous solution. There is therefore a need for a process for the separation of lanthanides, more specifically trivalent lanthanide cations, from an aqueous solution containing them which is simple to implement, which has a limited number of steps, which ensures high separation coefficients, and which uses compounds which do not generate a treatment problem during the subsequent stages. The object of the invention is therefore inter alia to provide a process for the separation of a trivalent lanthanide cation from an aqueous solution, containing, in addition to said lanthanide cation to be separated, one or more other cation (s) ( s) lanthanides, which meets the needs indicated above, which does not have the drawbacks, defects, limitations and disadvantages of the methods of the prior art and which solves the problems posed by the methods of the prior art.

This object, and others still, are achieved, in accordance with the invention by a process for the separation of a trivalent lanthanide cation, from an aqueous solution, containing, in addition, said lanthanide cation to be separated, which has the highest atomic number among the lanthanides, one or more other lanthanide cation (s), in which the following succession of steps is carried out:

- bringing said aqueous solution into contact with a sufficient quantity of a ligand, which is a derivative of all-cis-1, 3, 5-triamino-2, 4, 6 trihydroxycyclohexane (hereinafter abbreviated as "TATHC ”), In order to complex all of the lanthanide cation to be separated from the solution, and to form on the one hand essentially or mainly a complex of said ligand with said cation of lanthanide to be separated, of highest atomic number, and possibly other part, at least one other complex of said ligand with another lanthanide cation present in said solution;

- Precipitation of said complex (s) formed from said aqueous solution; - Separation of said complex (s) formed from said aqueous solution;

optionally, in the case where several complexes of said ligand have been formed, purification of said majority complex of said ligand by redissolution of said separate formed complexes, then complexation, precipitation and separation, said purification sequence being repeated until the precipitate formed does not contains more essentially than said majority complex of said ligand with said lanthanide cation to be separated;

drying of said complex of said ligand with said lanthanide cation to be separated.

The method according to the invention has in particular the advantage of being very easy to implement, of ensuring high separation coefficients, very much greater in particular than those obtained in the liquid-liquid extraction processes using for example work of organophosphorus compounds.

In addition, the method according to the invention does not require the use of an organic diluent in large amounts which may cause problems during subsequent treatments. Indeed, the ligand used is used in small quantities and consists only of C, H, 0 and N; it therefore does not generate secondary pollution in the event of incineration.

The ligand according to the invention which, surprisingly, allows selective or specific complexation in water of the trivalent lanthanide cations is a derivative of TATHC. The synthesis of these cyclohexane ligands was described for the first time in 1956 in the document by G. QUADBECK and E. RϋHM "Zur synthesis von Aminocycliten" (Chem. Ber. Vol. 89, p. 1645, 1956) which describes the synthesis of 1, 3, 5-triamino-2, 4, 6-trihydroxy-cyclohexane in the form of sulfate monohydrate by catalytic hydrogenation of triaminophloroglucin sulfate (1,3, 5-triamino-2, 4, 6-trihydroxy- benzene) in a sulfuric acid solution. The dehydrated sulfate is then obtained by vacuum evaporation with heating.

The document by FW LICHTENTHALER and H. LEINERT "NR Studien an Zuckern und Cyclanolen, II, cis- Inosatriamin- (1.3.5.) (Chem. Ber. Vol. 99, p. 903, 1966) is based on the work of QUADBECK et al described above and demonstrates that the catalytic hydrogenation of triaminophloroglucin leads with a yield of 65% to a single isometer which is identified by NMR as being in the cis configuration.

The document by K. HEGETSCH EILER "Polyalcohols and polyaminoalcohols as selective receptors for metal ions" Bol. Soc. Chil. Who m. , 42, 257-279 (1997) studies the bonding properties with metals of polyalcohols and polyaminopolyalcohols, and in particular the complexing properties of polyaminopolyalcohols such as 1, 3, 5-triamino-l, 3, 5-trideoxy -cis-inositol (TACI, i.e. TATHC). This ligand forms complexes with the ions of almost all metals from Li to Bi.

The complexes of La, Eu, Gd with the "TACI" are only characterized in the solid state by X-rays. No other characterization by spectroscopic methods (RN, RPE, UV) nor measurement of the stability constant of the complexes formed with "TACI" carried out by potentiometric titration concerns, in this document, the rare earth metals.

Preferably, according to the invention, said TATHC derivative is chosen from the compounds of formula (I) below:

R2 Ri

wherein each of Ri and R ₂ is selected from hydrogen and alkyl groups of 1 to 4 carbon atoms. For convenience, formula (I) has been represented in planar formula, but it is obvious that cyclohexane is essentially in the chair form.

Preferred compounds are those in which the substituents of the cyclohexane ring are all in the cis position.

Preferably, the ligand is the whole cis 1,3,5-triamino-2, 4, 6-trihydroxycyclohexane (TATHC) which gives the best results. It is therefore the compound in which all of the Ri and R ₂ are hydrogen and all of the OH and NH ₂ are in the "cis" position.

This compound is represented by the following formula (II):

The compounds in which in formula (I) the groups:

are identical, and are chosen from dialkylamino and monoalkylamino groups - the alkyl groups preferably being methyl, ethyl, n-propyl and i-propyl groups - such as monomethylamino and dimethylamino, also give good results but with overall durations longer process times.

Among these compounds, there may be mentioned, for example, the whole cis 1, 3, 5-tri (dimethylamino) -2, 4, 6-cyclohexane.

The treated aqueous solution generally contains the lanthanide cations in the form of salts hydrated or not with an anion. Said anion is generally chosen from chloride, nitrate, perchlorate, and trifluoromethanesulfonate (triflate) anions. A preferred anion is the nitrate anion which is found for example in solutions of acid dissolution of spent nuclear fuels. The method according to the invention allows the separation of the lanthanide cations whatever the concentration, generally the aqueous solution has a concentration of lanthanide cation to be separated from 0.1 to 1 mole / liter.

In addition to said lanthanide salts, the aqueous solution may be a "saline" solution, that is to say a solution which comprises one or more other salts such as nitrates, chlorides, etc. for example of alkali or alkaline earth metals.

Likewise, the aqueous solution can be an acid solution, for example a nitric solution. In this case, most of the salts in the solution are nitrates.

In relation to the above, it is possible to keep the ionic strength of the aqueous solution constant during the complexing step (s), for example by adding, if necessary, one or more salt (s) to the solution. treated aqueous; this added salt may for example be potassium nitrate.

Thus, the process of the invention can be used for example to separate the lanthanides from aqueous solutions originating in particular from the reprocessing of spent nuclear fuels, such as generally acid dissolution solutions and aqueous effluents from these installations which are often saline environments. The process of the invention can also be used to separate the lanthanides from the concentrates obtained by leaching from rare earth ores and the like. The contacting of the aqueous solution with said ligand is preferably easily carried out according to the invention by simply adding said ligand in solid form to said aqueous solution without it being necessary as in many methods of the prior art. use any organic or other thinner.

The contacting of the aqueous solution with said ligand can also be carried out by adding a solution of said ligand to the aqueous solution.

This solution of said ligand can for example also be an aqueous solution of said ligand at a concentration for example of 0.5 to 2 mol / l.

In all cases, the amount of ligand added is an amount sufficient to complex all of the lanthanide cation to be separated from the solution.

Preferably, a just sufficient amount of ligand will be used.

The method according to the invention is based on the reaction between said ligand such as TATHC and the lanthanide cations.

This reaction can be carried out according to a first variant without adding any other reagent, the yield to be quantitative with respect to the lanthanide then requires the use of a non-stoichiometric amount of ligand, which also serves as an annex base.

The reaction scheme in the case of a lanthanide nitrate is then as follows:

3Ln ³⁺ 9N0 ₃ ^" +4 (TATHC) → [Ln ₃ (H- ₃ TATHC)] ³⁺ (N0 ₃ ^" ) ₃ +2 (H ₃ TATHC) ³⁺ + 6N0 ₃ ^' (1) The compounds H ₃ TATHC ³⁺ and H- ₃ TATHC ^{3 ~} are represented by the following formulas (III) and (IV):

According to a second variant, the part of the ligand not used to form the complex in the preceding reaction (1) is in fact replaced by an addition of an additional base solution (6 equivalents) preferably chosen from aqueous sodium hydroxide solutions, potash, ... In this way, the entire ligand can be used for complexing and the economic yield of the reaction is improved.

In the following reaction (2), potash is taken as an example of an additional base, and a lanthanide nitrate as an example of a lanthanide salt:

3Ln ³⁺ 9N0 ₃ ^" + 2TATHC + 60H ^" → [(H. ₃ TATHC) ₂ Ln ₃ ] ³⁺ (NO ^" ₃ ) ₃ + 6N0 ₃ ^~ (2)

The inventors have been able to demonstrate that, surprisingly, the value of the formation constant of the trivalent lanthanide complexes with the derivatives of

TATHC is growing continuously from lanthanum to lutetium. These constants had never been measured in the prior art, and a fortiori the growth of these constants throughout the lanthanide series had never been described or suspected. The differences in magnitude of these constants are such that from lanthanum to lutetium any element can specifically or selectively displace an element of lower atomic number in a complex formed with the latter. Based on the numerical values of the ratios of the formation constants of the lanthanide cation complexes (see Tables I and II below), we can consider, as a first approximation, that if the numerical value of this ratio is greater than or equal to 10, then the metal of higher atomic number completely displaces the metal of lower number from its complex.

It should however be noted that, in all cases, the values of these separation coefficients or coefficients are much higher than those of the separation coefficients obtained in the processes of the prior art making use in particular of liquid-liquid extraction.

This is called a "specific" separation process.

In other words, a ligand complex, derived from TATHC, is essentially formed with the lanthanide cation to be separated having the highest atomic number among the lanthanides present in the solution. It is therefore not necessary to have recourse to the optional purification step of the process according to the invention, since essentially only one complex is formed. On the other hand, for values of the ratio of the lower formation constants, on the one hand a majority of a complex of said ligand is formed with the lanthanide cation to be separated, with the highest atomic number, but at least one is also formed. another complex of said ligand with another lanthanide cation present in said solution.

By way of example, and by a value of the ratio of 2 the displacement is of the order of 60 to 70%. In this case, we speak of a separation process "selective" and no longer "specific".

Because several complexes of said derivative have been formed, it is then necessary to carry out the purification of said majority complex of said derivative by the purification step, which then necessarily includes the process according to the invention.

This purification step is described in more detail below.

Following the contacting of the aqueous solution with the ligand and the formation of the complex (s), precipitation is carried out of the said complex (s) formed.

This precipitation is generally carried out by decreasing the solubility of the complex or complexes formed, for example by adding an alcohol to the aqueous solution containing the said complex (s).

Because the complexes are less soluble in water than the salts, the addition of an alcohol to the aqueous solution has the effect of causing the complex (s) to precipitate at the bottom of the water-alcohol solution. Said alcohol is preferably chosen from linear or branched aliphatic alcohols having from 1 to 4 carbon atoms and their mixtures, more preferably this alcohol is isopropanol or ethanol. The complex or complexes formed are then separated from the water-alcohol solution by any suitable liquid-solid separation process, for example by filtration, preferably by vacuum filtration.

In the case where several complexes have been formed, the method according to the invention then comprises a step of purification of said majority complex; by majority complex is meant the complex found in the largest amount.

According to the invention, it is the lanthanide complex with the highest atomic number among the lanthanides which have formed complexes with the ligand.

It was indicated above that this purification step is generally necessary when the numerical value of the ratio of the formation constants is relatively low, it has been empirically determined that for a value of this ratio less than for example 10, a purification step was, most of the time, necessary.

That is, when the numerical value of the ratio of the formation constant of the complex of the lanthanide cation to be separated, of highest atomic number and of any other lanthanide cation complex of lower atomic number found in the solution is greater than or equal to 10, so the process does not include a purification step.

According to the invention, this purification step comprises the dissolution of said separate formed complexes; then the complexation, the precipitation and the separation of said complexes in the manner already described above.

This dissolution is carried out for example in water. The above purification sequence by dissolution, complexation, precipitation and separation is repeated, for example from 2 to 6 times until the precipitate essentially only contains said majority complex of said derivative with said lanthanide cation to be separated.

This is a process quite analogous to fractional crystallization which is well known to those skilled in the art.

Depending on the values of the formation constant ratios as defined above, it can be indicated that generally, when said cation of lanthanide to be separated is chosen from the lanthanide cations of the series going from the lanthanum included up to with gadolinium included, and the other lanthanide cation (s) are chosen from the lanthanide cation (s) of this same series and of lower atomic number, then the purification step can be omitted.

Likewise generally, when said lanthanide cation to be separated is chosen from the lanthanide cations of the series going from the included terbium to the included lutetium and the other lanthanide cation (s) are chosen from the lanthanide cation (s) of the series going from lanthanum included to gadolinium included, then the purification step can be omitted. The process finally comprises a drying step carried out for example at a temperature of 50 to 80 ° C, preferably under vacuum.

The complex obtained after drying can be preserved, or it can undergo other treatments, for example, it can be incinerated, or else said complex can be put back into aqueous solution, and the initial lanthanide salt or a other salt can be regenerated or generated from this solution, by acid treatment with a suitable acid, for example with hydrochloric acid or nitric acid.

The process of the invention has been described below which makes it possible, from an aqueous solution containing several lanthanides, to separate the lanthanide cation having the highest atomic number.

If the starting aqueous solution contains n different lanthanide cations, it will suffice to repeat n-1 times the process according to the invention to successively separate, individually, each of the lanthanide cations contained in the solution and this in decreasing order of atomic numbers.

In the foregoing, it is possible to successively separate all the lanthanides from a solution containing up to 15 lanthanides, that is to say that n has a value of 2 to 15 inclusive.

This is one of the particularly advantageous effects of the method according to the invention to allow the separation, successive, individual, of each of the lanthanide cations with high selectivity. Advantageously and in order to optimize the separation by the successive complexation of the cations, it is possible to determine at the start, that is to say prior to the contacting step, the composition of the solution, for example as a percentage of the lanthanide cations present.

Thus, it will be possible to use the just sufficient quantity of ligand (complexing agent) - determined as a function of the concentration of lanthanide to be separated - and optionally of additional base during each successive stage of lanthanide cation complexation, knowing that the agent ratio complexing agent / metal ion always remains 2/3 in the case of the reaction scheme (2).

The means of this determination fall under conventional assay methods for the analysis of aqueous ionic solutions.

The invention will now be described with reference to the following examples given by way of illustration and not limitation.

EXAMPLE 1

In this example, the values of the formation constants (complexation) relative to equation (3) are determined by potentiometric dosing:

3Ln ³⁺ 9N0 ₃ ^~ +2 (H ₃ TATHC) ³⁺ + 120H ^_ → [n ₃ (H. ₃ TATHC) ₂ ] ³⁺ (N0 ₃ ^_ ) ₃ + 12H ₂ 0 + 12N0 ₃ ^" (3)

The procedure for potentiometric dosing is as follows:

The assays were carried out on an automatic potentiometer 751 GPD Titrino from Metrohm ^® . A series of potentiometric titrations was carried out to determine the stability constants of the trivalent lanthanide complexes in aqueous solution. For each assay, the ionic strength was maintained by adding KN0 ₃ and the temperature was controlled by a bath thermostatically controlled at 25 ° C throughout the duration of the assay. Before and after each assay, the electrode was calibrated with two standardized buffer solutions at pH = 4 and pH = 7.

The assays were carried out by 30 successive additions of 0.05 ml of a standardized 0.1 N KOH solution to a solution of (H ₃ TATHC) ³⁺ in the presence of Ln (N0 ₃ ) ₃ . This solution was degassed beforehand and was maintained under an inert argon atmosphere throughout the assay.

During the assay, an equilibrium time of 1 hour was imposed between each addition of KOH for kinetic reasons. The drift was then less than 1 mV.

For each assay, the following procedure was used.

- 1. Addition of 10 ml of (H ₃ TATHC) ³⁺ at the concentration of 2.10 ^"3 mol / 1;

- 2. Add 6 ml of Ln (N0 ₃ ) ₃ to the concentration of 5.10 ^"3 mmol / 1;

- 3. Addition of 4 ml of water;

- 4. Addition of 200 mg of KN0 ₃ (ionic strength); - 5. Dosage.

The values of the complexing constants K relating to equation (3) for various lanthanide salts are indicated in Table I where they are expressed in -log K. TABLE I

Values of the complexing constants relative to equation (2)

From these complexation (formation) constants, it was possible to calculate the values of the ratios of the complexation (formation) constants between the various metals of the lanthanide series.

These values are grouped in the following table II in the part on the left, and at the bottom

(grey) ; they represent the values of the complexation constant ratios between the metal of the row and that of the column. As already indicated above, the differences in size of the constants are such that from lanthanum to lutetium any element can specifically or selectively move an element with a lower atomic number in a complex formed with it, this is indicated in the Table II in the part on the right, and at the top (white) with sp for "specific complexation" and if for "selective complexation".

TABLE II

EXAMPLE 2

This example illustrates the synthesis of a complex according to the reaction scheme (1). To a solution of TATHC (177 mg, 1 mmol) in water (4 ml) is added europium nitrate hexahydrate (347.6 mg, 0.75 mmol) in solution in water (1 ml). The resulting solution is named Al.

The H NMR spectrum of the solution Al in D ₂ 0 is produced (0.25 mmol of complex +0.50 mmol of (H ₃ TATHC) ³⁺ which is the protonated TATHC.

The spectrum shows the signals of the protonated ligand at δpp = 3.59 and 4.35. They correspond to the protons of the CHOH and CHNH ₃ ^{+ groups} . At 5 ppm are gathered the protons of the exchangeable sites (protons of OH and

NH ₃ ⁺ ) confused with the signal of H ₂ 0.

Finally, when the ligand is complexed, the signals of the protons of the cycle undergo a strong paramagnetic displacement towards the strong fields and are found at δpp _m = -14.35 and -21.80. In solution A1, therefore, two distinct species are present.

EXAMPLE 3

This example illustrates the synthesis of a complex according to the reaction scheme (2).

To a solution of TATHC (177 mg, 1 mmol) in water (5 ml) and added europium nitrate hexahydrate (695.3 mg, 1.50 mmol) in solution in water (2 ml). After a few minutes an IN potash solution (3 ml) is added with stirring. The resulting solution is named A2. The ¹ H NMR spectrum of the solution A2 in D ₂ 0 (0.50 mmol of complex) is produced.

Compared to solution A1, it can be seen that the signals of the protonated ligand (H ₃ TATHC) ³⁺ have practically disappeared at δ _ppm = 3.59 and 4.35, because the ligand has been consumed by the metal ion.

We note the almost only presence of the signals of the ligand complexed at δ _ppm = -14.35 and -21.30. Of course the signal of the exchangeable protons remains confused with the signal of H ₂ 0 at 5 ppm.

EXAMPLE 4

This example illustrates the displacement of neodymium by the europium observed by ¹ H NMR. A) In a manner analogous to example 3, the synthesis of the complex [Nd ₃ (H. ₃ TATHC) ₂ ] ³⁺ , 3N0 _{3 is carried out.} ^", by addition to 1 equivalent of TATHC, 1.5 equivalents of Nd (N0 ₃₎ ₃ .6H ₂ 0 and 3 equivalents of KOH. the NMR spectrum ^X H shows that with the paramagnetic metal ion displacement of signals of the complexed ligand is made towards weak fields at δp _Pm = 19.30 and 21.80. A small part of the uncomplexed ligand is left at δ _ppm = 3.59 and 4.35 as a reference (practically 2.9 equivalents of KOH) b) To the preceding solution obtained in paragraph a), 1.5 equivalents of Eu (NO ₃ ) ₃ , 6H ₂ 0 are added.

The spectrum of RNN ¹ H shows that neodymium is displaced by europium in the complex. Indeed, the europium having taken the place of neodymium in the complex, we observe the disappearance of the signals of the neodymium complex at δ _ppm = 19.30 and 21.80, and the exclusive appearance of the signals of the europium complex at δ _ppm = -14.35 and -21.80, which proves that the neodymium is completely released in the medium in the form of free mineral salt (nitrate form).

EXAMPLE 5

This example illustrates the specific separation of ytterbium, by the method of the invention, from an aqueous solution containing lanthanum, neodymium and ytterbium cations.

To a solution of LaCl ₃ , 6H ₂ 0 (112 mg, 0.33 mmol), NdCl ₃ , 6H ₂ 0 (114 mg, 0.33 mmol) and YbCl ₃ , 6H ₂ 0 (122 mg, 0.33 mmol ) in water (1 ml) is added a solution of TATHC (38 mg, 0.22 mmol) in water (1 ml).

The solution is stirred for 5 minutes. 0.65 ml of an IN sodium hydroxide solution (0.66 mmol) is then added dropwise with stirring. Isopropanol (5 ml) is then added and the suspension is stirred for 5 minutes.

The precipitate is finally filtered and dried under vacuum.

The ytterbium complex is isolated in the form of a white powder (115 mg, 95%).

[Yb ₃ (H- ₃ TATHC) ₂ (6H ₂ 0)] Cl ₃ : ^X H NMR (200 MHz): -46 ppm (3H, s), -42.5 ppm (3H, s).

Claims

1. Process for the separation of a trivalent lanthanide cation, from an aqueous solution, containing, in addition, said lanthanide cation to be separated, which has the highest atomic number among the lanthanides, one or more other (s) ) cation (s) of lanthanides, in which the following sequence of steps is carried out: - bringing said aqueous solution into contact with a sufficient quantity of a ligand, which is a derivative of all-cis-1, 3, 5 -triamino-2, 4, 6-trihydroxycyclohexane (TATHC), to complex all of the lanthanide cation to be separated from the solution, and form on the one hand, essentially or mainly, a complex of said ligand with said lanthanide cation to be separated , of highest atomic number, and optionally on the other hand, at least one other complex of said ligand with another lanthanide cation present in said solution;

- Precipitation of said complex (s) formed from said aqueous solution;

- Separation of said complex (s) formed from said aqueous solution;

optionally, in the case where several complexes of said ligand have been formed, purification of said majority complex of said ligand by redissolution of said separate formed complexes, then complexation, precipitation and separation, said purification sequence being repeated until the precipitate formed does not contains more essentially that said majority complex of said ligand with said lanthanide cation to be separated; drying said complex of said ligand with said lanthanide cation to be separated.

2. Method according to claim 1, in which said derivative of all-cis-1, 3, 5-triamino-2, 4, 6-trihydroxycyclohexane is chosen from the compounds of formula (I)

/ \

R2 Ri

wherein each of Ri and R ₂ is selected from hydrogen and alkyl groups of 1 to 4 carbon atoms.

3. Method according to claim 2 wherein, in formula (I), the groups

are identical and are chosen from dialkylamino and monoalkylamino groups, alkyl groups having from 1 to 4 carbon atoms, such as methyl ethyl, n-propyl, and i-propyl.

4. The method of claim 2, wherein in formula (I) all the substituents of the cyclohexane ring are in the cis position.

5. The method of claim 4, wherein said ligand is the whole cis-1, 3, 5-triamino-2, 4, 6-trihydroxycyclohexane.

6. The method of claim 1, wherein said lanthanide cations are in the form of salts, hydrated or not, with an anion.

7. The method of claim 6, wherein said anion is chosen from chloride, nitrate, perchlorate and trifluoromethane sulfonate anions.

8. The method of claim 6, wherein in addition to said lanthanide salts, the aqueous solution contains one or more other salts.

9. The method of claim 1, wherein the ionic strength of the aqueous solution is kept constant during the step (s) of complexation.

10. The procedure of claim 1, wherein contacting the aqueous solution with said ligand is produced by adding the ligand in solid form to said aqueous solution.

11. The method of claim 1 wherein the contacting of the aqueous solution with said ligand is carried out by adding a solution of said ligand to the aqueous solution.

12. The method of claim 1, wherein a base solution is added additionally to the aqueous solution.

13. The method of claim 1, wherein the precipitation of said complex (s) formed from said aqueous solution is carried out by adding an alcohol to the aqueous solution containing the said complex (s).

14. The method of claim 13, wherein said alcohol is chosen from linear or branched aliphatic alcohols having from 1 to 4 carbon atoms.

15. The method of claim 1, wherein the numerical value of the ratio of the formation constant of the complex of the lanthanide cation to be separated, of highest atomic number, and the formation constant of any other lanthanide cation complex with a lower atomic number in the solution, is equal to or greater than 10, whereby the process does not include a purification step.

16. The method of claim 1, wherein said lanthanide cation to be separated is chosen from the lanthanides of the series ranging from lanthanum included to gadolinium included, and the other lanthanide cation (s) is (are) chosen from the lanthanides of this same series and of lower atomic number whereby the process does not include a purification step.

17. The method of claim 1, wherein said lanthanide cation to be separated is chosen from the lanthanides of the series ranging from the included terbium to the included lutetium and the other lanthanide cation (s) is ( are) chosen from the lanthanides of the series ranging from lanthanum included to gadolinium included, whereby the process does not include a purification step.

18. Method according to any one of claims 1 to 17, in which at the end of the drying, the complex obtained is redissolved in aqueous solution, and the initial lanthanide salt or another salt is regenerated or generated from this. solution by acid treatment.

19. Process according to any one of Claims 1 to 18, in which the starting aqueous solution contains n different lanthanide cations and the process according to any of Claims 1 to 18 is repeated n-1 times to successively separate , individually, each of the lanthanide cations contained in the solution in descending order of the atomic numbers.

20. The method of claim 19, wherein n has a value of 2 to 15 inclusive.

21. The method of claim 19, wherein prior to the contacting step, the composition of the aqueous solution in each of the lanthanide cations present is determined, whereby the sufficient amount is used in each successive step of complexing. of ligand determined as a function of the concentration of the lanthanide to be separated.