FR3015458A1 - PROCESS FOR THE PREPARATION OF A SHAPED ADSORBENT MATERIAL COMPRISING A SHAPING STEP IN THE PRESENCE OF A MINERAL BINDER AND METHOD OF EXTRACTING LITHIUM FROM SALINE SOLUTIONS USING THE MATERIAL - Google Patents

Abstract

There is described a process for preparing a crystalline solid material of formula LiCl.2Al (OH) 3, nH2O with n being between 0.01 and 10, comprising a) a step of mixing, in an aqueous medium, at least one source of alumina and at least one source of lithium, to obtain a suspension, b) a filtration step of the suspension obtained in step a) to obtain a paste, c) a step of drying the paste obtained at the end of step b), at a temperature of between 20 and 80 ° C. for a period of between 1 h and 12 h, d) a step of shaping by extrusion - extrusion of said dried paste, in the presence of at least one solid precursor of alumina and at least one acid in solution in proportions such that the acid / Al molar ratio is between 0.01 and 1.2, to obtain extrudates, and e) drying extrudates obtained at the end of step d) at a temperature of between 20 and 200 ° C. for a duration of between 1 and 20 hours, to obtain the crystalline solid material of formula LiCl.2Al (OH) 3, nH2O in the form of extrudates. The invention also relates to a method for extracting lithium from saline solutions using the material thus prepared. The invention relates to a crystalline solid material of formula LiCl.2Al (OH) 3, nH2O with n being between 0.01 and 10 formed. The invention also relates to a device implementing the lithium extraction process.

Description

PROCESS FOR THE PREPARATION OF A SHAPED ADSORBENT MATERIAL COMPRISING A SHAPING STEP IN THE PRESENCE OF A MINERAL BINDER AND METHOD FOR EXTRACTING LITHIUM FROM SALINE SOLUTIONS USING THE MATERIAL Technical Field The present invention relates to the field of solid materials for the adsorption of lithium. In particular, the present invention relates to a new process for the preparation of a crystallized solid material shaped in the form of extrusion-extrusion extrudates in the presence of a precursor of a specific inorganic binder, of formula LiC1.2A1 (OH ) 3, nH20 with n being between 0.01 and 10 and with a process for extracting lithium from saline solutions using said crystalline solid material of formula LiC1.2A1 (OH) 3, nH20 with n being between 0 , 01 and 10 prepared according to the new preparation method according to the invention. The invention relates to a crystalline solid material of formula LiC1.2A1 (OH) 3, nH20 with n being between 0.01 and 10 shaped. The invention also relates to a device implementing the lithium extraction process. PRIOR ART Lithium ions coexist with massive amounts of metals such as, for example, alkalis, alkaline earths, boron and sulphates, in particular in saline solutions such as brines. Thus, they must be extracted economically and selectively from these salt solutions. Indeed, the chemical properties of lithium and alkali metals, preferably sodium (Na), and potassium (K) and alkaline earth metals, preferably magnesium (Mg), calcium (Ca) and strontium ( Sr), make it difficult to separate these elements. The solid materials of formula LiC1.2A1 (OH) 3, nH20 with n being between 0.01 and 10 are known for their use in the phenomena of adsorption / desorption of lithium ions and in particular in the processes of extraction of lithium ions. lithium from saline solutions. These unstable structures would allow the intercalation of lithium atoms in the structure and thus the extraction of lithium. Several operating protocols leading to solids capable of selectively adsorbing lithium have been demonstrated in the prior art. In all cases, a solid aluminum trihydroxide Al (OH) 3, prepared or commercial, is contacted with a lithium precursor. Three main precursors are used: the most used is lithium chloride (LiCl). An aluminum hydroxide (LiOH) or a lithium carbonate (Li2CO3) can also be used.

US Pat. No. 6,280,693 describes a process for preparing a LiCl / Al (OH) 3 solid by adding an aqueous solution of LiOH to a polycrystalline hydrated alumina to form LiOH / Al (OH) 3, and thus create lithium sites active in the crystalline layers of alumina without altering its structure. The conversion of LiOH / Al (OH) 3 to LiCl / Al (OH) 3 is then carried out by adding dilute hydrochloric acid. The alumina pellets thus prepared are then used in a process for extracting lithium from brine at high temperature. The lithium extraction method described in US Pat. No. 6,280,693 uses the solid detailed above and comprises the following steps: a) Saturation of a bed of solid by a brine containing a lithium salt LiX, X being chosen from halides, nitrates, sulphates and bicarbonates, b) displacement of the brine impregnated with a concentrated solution NaX, c) elution of LiX salt captured by the solid by passage of an unsaturated solution of LiX, d ) Moving the impregnant with a concentrated solution of NaX, steps a) to d) are then repeated at least once. The patent RU 2,234,367 describes a process for preparing a solid of formula LiC1.2A1 (OH) 3, nH20 comprising a step of mixing aluminum trichloride (AIC13) and lithium carbonate (Li2CO3) in the presence of water at 40 ° C. The residue obtained is filtered and washed and then dried for 4 hours at 60 ° C. The solid thus obtained is not shaped. The solid obtained is used for the extraction of lithium contained in saline solutions by contact with water in order to remove part of the lithium and then placed in contact with a saline solution containing lithium. The static capacity thus obtained is between 6.0 and 8.0 mg of lithium per g of solid.

CN1243112 discloses a process for the preparation of a solid of formula LiC1.2A1 (OH) 3, nH20 comprising a step of precipitating al (OH) 3 aluminum hydroxide microcrystals by contacting AICI3 and sodium hydroxide NaOH, and then bringing said microcrystals into contact with a 6% solution of lithium chloride LiCl at 80 ° C. for 2 hours followed by filtration, rinsing and drying to obtain a powder of LiC1.2A1 (OH) 3, nH20 with an unordered and amorphous structure. A solution of a macromolecular polymer chosen from fluorinated resins, polyvinyl chloride (PVC), chlorinated polyvinyl chloride (CPVC), ethylene perchlorate and cellulose acetate butyrate (CAB) acting as binder is then mixed with the LiC1.2A1 (OH) 3, nH20 powder to obtain a paste which is then shaped by granulation followed by drying in air. The use of such a solid in a process for extracting lithium from salt lake brines makes it possible to obtain a low Mg / Li ratio and a lithium-rich mother liquor that complies with the standards for the production of carbonates or chlorides. lithium.

An object of the present invention is to provide a solid material for the selective extraction of lithium from brine, said solid material being of good quality, and having a good cohesion, without apparent defects.

An object of the present invention is to provide a new process for preparing such a solid material. Another object of the present invention is to provide a method for extracting lithium from saline solutions using said crystalline solid material of formula LiC1.2A1 (OH) 3, nH20 shaped, advantageously prepared according to the new preparation process according to the invention. 'invention. SUMMARY AND INTEREST OF THE INVENTION Applicants have discovered a new process for the preparation of a crystalline solid material of the formula LiC1.2A1 (OH) 3, nH20 with n being between 0.01 and 10, and in particular that the fact to carry out the step of shaping - extrusion of a paste in the presence of at least one solid precursor of alumina and at least one acid in solution in proportions such that the acid / Al molar ratio is between 0.01 and 1.2, after a drying step operating under specific conditions, the shaping step being then followed by a final drying step also operating under specific conditions, made it possible to obtain a crystalline solid material of formula LiC1.2A1 (OH) 3, nH20 in the form of extrudates of good quality, having a good cohesion, without apparent defects. Said shaped solid material is of good quality, and has a good cohesion, without apparent defect.

The term "material of formula LiC1.2A1 (OH) 3.nH20" preferably means a material comprising essentially or consisting of a crystalline phase of formula LiC1.2A1 (OH) 3, nH20, optionally in the presence of binder (s) . The subject of the present invention is a process for preparing a crystalline solid material of formula LiC1.2A1 (OH) 3, nH20 with n being between 0.01 and 10, said process comprising at least the following stages: a) a step of mixing, in an aqueous medium, at least one source of alumina and at least one source of lithium, to obtain a suspension, b) a filtration step of the suspension obtained in step a) for to obtain a paste, c) a step of drying the paste obtained at the end of step b), at a temperature between 20 and 80 ° C for a period of between 1h and 12h, d) a step of setting in the form of kneading - extrusion of a paste in the presence of at least one solid precursor of alumina and at least one acid in solution in proportions such that the acid / Al molar ratio is between 0.01 and 1 , 2, to obtain extrusions, e) a step of drying the extrudates obtained at the end of step d) at a temperature between 20 and 200 ° C for a period of between 1 and 20 hours, to obtain the crystalline solid material of formula LiC1.2A1 (OH) 3, nH20 in the form of extrudates. An advantage of the preparation process according to the invention is that it makes it possible to obtain a crystallized solid material shaped, advantageously in the form of extrudates, of formula LiC1.2A1 (OH) 3, nH20 with n being between 0 , 01 and 10, of good quality and without apparent defects, having a good cohesion. Another advantage of the preparation process according to the invention is that it makes it possible to obtain a crystallized solid material shaped, advantageously in the form of extrudates, of formula LiC1.2A1 (OH) 3, nH20 with n being between 0.01 and 10, having no or few cracks that could cause harmful swelling to the cohesion and strength of the material when it is brought into contact with a brine solution.

The present invention therefore also relates to a crystallized solid material of formula LiC1.2A1 (OH) 3, nH20 with n being between 0.01 and 10, shaped. This shaped solid material is obtainable according to the method of the invention. By "shaped" is meant that the material is solid and has sufficient cohesion when the solid is brought into contact with a brine solution so that it does not lose substantially its physical integrity, that is to say to say that it retains substantially its formatting. More specifically, a solid shaped in the sense of the invention preferably covers a solid substantially retaining its shaping under the conditions defined in the examples. In particular, the terms "shaped" cover a material preferably extruded (called extruded).

An essential criterion of the preparation process according to the invention is the introduction into step d) of shaping-extrusion shaping, of a solid precursor of alumina and of at least one acid in solution allowing the generation in situ of a binder during the shaping step. The in situ generation of the binder makes it possible to obtain a material having increased mechanical strength properties, in particular in terms of mechanical strength, especially in contact with the brine under stirring. The use of the material prepared according to the invention in a lithium extraction process limits the production of fine particles resulting from the aging of the extrudates.

The subject of the present invention is also a method for extracting lithium from saline solutions using said crystallized solid material in the form of extrudates of formula LiC1.2A1 (OH) 3, nH20 with n being between 0.01 and 10, prepared according to the new preparation method according to the invention. An advantage of the extraction method according to the invention is to allow the selective extraction of lithium from a saline solution and thus to obtain a high decontamination factor relative to the initial saline solution, calculated as being the ratio X / Li which is equal to the molar ratio of concentrations X / Li in the initial saline solution divided by the molar ratio of concentrations X / Li in the final solution, X being chosen from sodium (Na), potassium (K), magnesium (Mg), calcium (Ca), boron (B), sulfur (S) and strontium (Sr).

The present invention also relates to a lithium extraction device of saline solution (s). The device according to the invention thus implements the extraction method according to the invention.

According to the invention, at least one source of alumina and at least one source of lithium are mixed in an aqueous medium to obtain a suspension in step a).

Preferably, the source of alumina is Al (OH) 3 aluminum trihydroxide. Al (OH) 3 aluminum trihydroxide may advantageously be commercial. Preferably, aluminum trihydroxide Al (OH) 3 is prepared by precipitation of aluminum trichloride (AIC13) and sodium hydroxide (NaOH). In this case, said source of alumina and preferably aluminum trihydroxide Al (OH) 3 is prepared before mixing with at least one lithium source. Aluminum trichloride AlCl 3 and sodium hydroxide NaOH are advantageously mixed in the presence of water to form a precipitate which is advantageously filtered and washed at least once. The precipitate obtained is then mixed according to step a) with at least one lithium source to obtain a suspension.

The lithium source (s) may be any compound comprising the lithium element and capable of releasing this element in aqueous solution in reactive form. Preferably, the source (s) of lithium is (are) chosen from among the lithium salts and preferably from lithium chloride (LiCl), lithium hydroxide (LiOH), nitrate of lithium Lithium, (LiNO3), lithium sulphate (Li2SO4) and lithium carbonate (Li2CO3), alone or as a mixture. Very preferably, the lithium source is lithium chloride (LiCl). Preferably, at least one source of alumina and at least one source of lithium are mixed in the presence of water to obtain a suspension in step a). Preferably, said mixing step a) operates with vigorous stirring. Preferably, said mixing step a) operates at a temperature between 40 and 120 ° C and preferably between 60 and 100 ° C for a period of between 1 hour and 10 hours, preferably between 1 and 8 hours, preferably between 1 and 6 hours and more preferably between 1 and 3 hours.

According to the invention, the suspension obtained at the end of step a) undergoes a step b) of filtration to obtain a paste. Preferably, the filtration is carried out on a Buchner filter, by displacement of water.

According to the invention, the paste obtained at the end of step b) is dried in a c) drying step at a temperature between 20 and 80 ° C, for a period of between 1h and 12 h. Preferably, said drying step operates, preferably in an oven, at a temperature between 20 and 60 ° C and very preferably between 30 and 50 ° C for a period of between 1 h and 10 h. The operating conditions of said drying step c) make it possible to obtain a dried pulp with a loss on ignition (PAF) of between 45 and 75% and preferably between 50 and 70%. The loss on ignition obtained allows the extrusion of the dried paste in good conditions and obtaining extruded without defects, ie without cracks. In order to determine the PAF before the forming step, a portion of the paste obtained is removed and put in an oven for 6 hours at 120 ° C. The PAF is obtained by difference between the mass of the sample before and after passage in the oven.

According to the invention, said dried paste obtained at the end of the drying step c) undergoes a step d) of shaping-extrusion shaping in the presence of a binder formulation comprising and preferably consisting of at least one solid precursor of alumina and at least one acid in solution in proportions such that the acid / Al molar ratio is between 0.01 and 1.2, to obtain extrudates.

The term "kneading-extrusion step" is understood to mean a step in which the dried pulp obtained at the end of drying step c) initially undergoes a kneading step, generally in the presence of at least one binder or compound. binder precursor, then the paste is then subjected to an extrusion step. Said step d) of kneading / extrusion shaping is advantageously carried out in a manner known to those skilled in the art. Preferably, said dried paste obtained at the end of drying step c), and at least said solid precursor of alumina and at least said acid in solution in proportions described are mixed, preferably at one time, in a mixer. The kneader is advantageously chosen from batch kneaders, preferably with a cam or Z-arm, or with the aid of a twin-screw mixer-mixer. The mixing conditions are adjusted in a manner known to those skilled in the art and aim to obtain a homogeneous and extrudable paste. The paste then advantageously passes through a die, using, for example, a piston or a continuous twin-screw or single-screw extruder. The diameter or section of the die of the extruder is advantageously variable and is between 0.1 and 5 mm, preferably between 0.2 and 3 mm and preferably between 0.3 and 2 mm. The shape of the die, and therefore the shape of the material obtained in extruded form, is advantageously cylindrical, for example of circular, annular, trilobed, quadrilobed or multilobed section. The shaped solid material according to the invention can thus have such characteristics. In particular, the shaped solid material has a diameter or section substantially equivalent to that of the die of the extruder, and advantageously between 0.1 and 5 mm, preferably between 0.2 and 3 mm and preferably between 0 and , 3 and 2 mm. The diameter or section may vary due to a possible retraction of the solid. Thus, the shaped material according to the present invention may be wire length for example between 1 and 10 mm, for example between 2 and 6 mm. The cylindrical shape can be hollow (tubular) or solid. Advantageously, the solid material according to the invention may comprise at least one binder preferably chosen from organic binders and inorganic binders. Advantageously, the solid material according to the invention may comprise at least one inorganic binder and optionally at least one organic binder. The introduction into step d) of shaping, of a solid precursor of alumina and of an acid in solution allows the in situ generation of a mineral binder resulting from the reaction of the precursor of alumina and of the acid introduced during said shaping step. Moreover, the solid precursor of alumina and the acid in solution must be introduced in said step d) in the proportions as claimed. The generation of said inorganic binder resulting from the reaction of the solid precursor of alumina and of the introduced acid requires the use of a solid precursor of alumina capable of dispersing predominantly or of dissolving predominantly in the acid solution employed. The solid precursor of alumina is advantageously chosen from aluminum oxides, aluminum hydroxides and aluminum oxyhydroxides that are soluble or dispersible in the phosphoric acid solution, preferably from aluminum hydroxides and oxyhydroxides. 'aluminum. Very preferably, said solid alumina precursor is an aluminum oxyhydroxide and more preferably said solid alumina precursor is boehmite or pseudo-boehmite.

Said solid precursor of alumina is advantageously in the form of a powder consisting of solid particles having a median diameter, determined by laser diffraction particle size, between 9 and 80 μm, preferably between 10 and 60 μm and preferably between 10 and 60 μm. and 45 lm. The particles of the solid precursor of alumina are advantageously constituted by agglomerates of elementary units, called crystallites, whose dimensions are advantageously between 2 and 150 nm, preferably between 4 and 150 nm and preferably between 4 and 100 nm. determined by transmission electron microscopy (TEM). The morphology of the crystallites, the size and the manner in which the crystallites are organized depend mainly on the synthesis route of the alumina precursor used to prepare said micrometric particles.

Preferably, the proportion of the solid precursor of alumina added in step d) of the preparation process according to the invention is between 0.5 and 50% by weight relative to the mass of dry paste to be shaped, preferably between 2 and 30% by weight, and preferably between 3 and 25% by weight.

According to step d) of the preparation process according to the invention, at least one acid in solution is introduced into the mixture. Preferably, the acid is chosen from phosphoric acid, hydrochloric acid, nitric acid, acetic acid and citric acid, alone or as a mixture. Very preferably, the acid is phosphoric acid.

Phosphoric acid is also called orthophosphoric acid. The role of the acid solution is to promote the formation of an amorphous phase of inorganic binder resulting from the reaction with the solid precursor of alumina. In this way, the particles of the solid precursor of alumina become, with the action of the acid and the mechanical energy provided during the step d) of shaping the process for the preparation of the material according to the invention, a amorphous phase of inorganic binder According to step d) of the preparation process according to the invention, the acid (s) in solution is (are) introduced in such proportions that the acid / Al molar ratio is included between 0.01 and 1.2, and preferably between 0.05 and 1.

In the case where the introduced acid is phosphoric acid, it is introduced in solution in proportions such that the molar ratio P / Al is between 0.01 and 1.2, preferably between 0.3 and 1, 0. In the P / Al molar ratio, P is derived from the introduced phosphoric acid and Al is derived from the solid alumina precursor. The specific P / Al molar ratio as claimed corresponds to a proportion of phosphoric acid such that the ratio of the mass of acid introduced onto the mass of introduced alumina solid precursor is between 30 and 225% by weight, of preferably between 59 and 170% by weight.

The use of an acid / Al molar ratio of between 0.01 and 1.2, characteristic of a high acid ratio dissolution, in the d) shaping stage of the preparation process according to the invention. The invention makes it possible both to form the amorphous phase of the inorganic binder resulting from the reaction with the solid precursor of alumina, but also to facilitate the extrusion shaping and to increase the cohesion and the mechanical strength of the extrudates obtained by the preparation process according to the invention. According to the invention, the extrudates obtained at the end of step d) undergo a drying step e) at a temperature of between 20 and 200 ° C. for a duration of between 1 hour and 20 hours, in order to obtain the crystalline solid material of formula LiC1.2A1 (OH) 3, nH20 in the form of extrudates. Preferably, said drying step e) operates at a temperature between 20 and 100 ° C, preferably between 20 and 80 ° C and very preferably between 20 and 60 ° C, for a period of between 1 and 18 hours, preferably between 5 and 14 hours and preferably between 8 and 14 hours. Said drying step e) is advantageously carried out according to the techniques known to those skilled in the art and preferably in an oven. The process according to the present invention thus makes it possible to obtain a crystalline solid material of formula LiC1.2A1 (OH) 3, nH20 with n being between 0.01 and 10, preferably between 0.1 and 5, and preferred between 0.1 and 1, in the form of extrudates of diameter or section between 0.2 and 5 mm, preferably between 0.3 and 4 mm, preferably between 0.3 and 3 mm, very preferably preferred between 0.3 and 2 mm and even more preferably between 0.3 and 1.8 mm. The best results in terms of mechanical strength and cohesion of the crystallized solid material obtained according to the preparation method according to the invention are obtained in the case of extrudates of diameter or section between 0.2 and 5 mm and preferably between 0.3 and 1.8 mm, said extrudates having been obtained at the end of a drying step e ) carried out at a temperature between 20 and 60 ° C and in particular at 40 ° C for a period of between 5 and 14 hours, preferably between 8 and 14 hours and in particular for 8 hours. The crystalline solid material of formula LiC1.2A1 (OH) 3, nH20 shaped, advantageously in the form of extrudates, prepared according to the sequence of steps a), b), c) and d) of the preparation process according to the invention. The invention can be characterized by the following techniques: nitrogen adsorption for the determination of the specific surface area according to the BET method; X-ray diffractometry in the diffraction angle range δ = 0.8 to 40 ° ± 0.02 ° in reflection geometry to identify the structure of said material and the elemental analysis. The crystalline solid material of formula LiC1.2A1 (OH) 3, nH20 shaped, advantageously in the form of extrudates, advantageously has a specific surface area measured according to the BET method of between 1 and 250 m 2 / g and preferably between 1 and 100 m2 / g.

The X-ray diffraction pattern of the solid material of formula LiC1.2A1 (OH) 3, nH20 with n being between 0.01 and 1, preferably between 0.1 and 0.5 and preferably between 0.1. and 0.4, obtained according to the invention, shaped, advantageously in the form of extrudates, is characteristic of a non-amorphous material and has at least the following lines: d (A) 11,505 7,69 20,195 4, 39 23.065 3.85 35.937 2.5 39.948 2.26 55.406 1.66 63.243 1.47 64.349 1.45 The characteristic peaks of the precursors of alumina are also present on the diffractogram of the final extrusions in variable proportions, according to that introduced during of the shaping step. The preparation method according to the present invention thus makes it possible to obtain a crystalline solid material of formula LiC1.2A1 (OH) 3, nH20 shaped, advantageously in the form of extrudates, having both a low BET specific surface area. , a good cohesion, and having no apparent defects. The crystalline solid material of formula LiC1.2A1 (OH) 3, nH20 shaped, advantageously, in the form of extrudates thus obtained also has excellent strength properties.

Thus, the subject of the present invention is a crystalline solid material of formula LiC1.2A1 (OH) 3.nH20 with n being between 0.01 and 10, shaped, preferably in the form of extrudates. In particular, the extruded solid material can be obtained according to the preparation method of the invention.

In particular, the crystalline solid material of formula LiC1.2A1 (OH) 3, nH20 shaped, advantageously in the form of extrudates according to the invention has a mechanical strength especially in contact with brine with stirring. Thus, the use of the material prepared according to the invention in a lithium extraction process limits the production of fine particles resulting from the aging of the extrudates.

This is due to the combined effect of the implementation of the kneading-extrusion shaping step in the presence of a specific binder formulation ensuring both the cohesion and the mechanical strength of the extrudates obtained and the setting of implement, before and after said shaping step, two drying stages operating under very specific conditions. The subject of the present invention is also a process for extracting lithium from a saline solution using said crystalline solid material of formula LiC1.2A1 (OH) 3, nH20 with n being between 0.01 and 10 according to invention. Said saline solution used in the extraction process according to the invention advantageously comprises a lithium concentration of between 0.001 mol / L and 0.5 mol / L, preferably between 0.02 mol / L and 0.3 mol / L. .

Said saline solution also contains other species, such as, for example, the species chosen from the following list: Na, K, Rb, Cs, Mg, Ca, Sr, Ba, F, Cl, Br, I, SO4, 003, NO3, and HCO3. Said saline solution may advantageously be saturated with salts or not.

Said saline solution may be any natural saline solution, concentrated or resulting from a lithium extraction or transformation process. For example, said saline solution used in the extraction process according to the invention may advantageously be chosen from brine from salt lakes or from geothermal sources, brines subjected to evaporation to obtain brines concentrated in lithium, water of sea, effluents from cathode production plants, or production of lithium chloride or hydroxide and the effluents of the lithium extraction process from minerals. The lithium extraction process according to the invention is preferably a selective extraction process of lithium. Indeed, it allows the separation of lithium from alkali metals, preferably sodium (Na), and potassium (K) and alkaline earth metals, preferably magnesium (Mg), calcium (Ca) and strontium ( Sr), present in a massive amount in the saline solutions treated in said extraction process. The lithium extraction process according to the invention also allows the selective separation of lithium from other compounds such as boron and sulphates. The lithium extraction process according to the invention is advantageously carried out in a unit comprising at least one column, said column or columns comprising at least one bed of said crystallized solid material of formula LiC1.2A1 (OH) 3, nH20 with n being between 0.01 and 1, shaped and prepared according to the preparation method according to the invention.

Preferably, said lithium extraction method according to the invention is implemented in a unit comprising between one and four columns, and preferably between two and three columns.

The present invention covers a device comprising such units. The device according to the invention may comprise one or more units according to the invention. Said lithium extraction method advantageously comprises at least the following steps: a step of activating said crystallized solid material of formula LiC1.2A1 (OH) 3, nH20 with n being between 0.01 and 10, a loading step said adsorption-activated material made by passing said saline solution over said activated material, at least one step of washing the saline solution impregnating said material by passing a washing solution on said material, a lithium desorption step carried out by said passing water or an aqueous solution of lithium salt on said material to obtain an eluate comprising at least lithium.

Preferably, said step of activating the crystallized solid material of formula LiC1.2A1 (OH) 3, nH20 with n being between 0.01 and 10, in the form of extrudates, is carried out only once during the implementation. column of the material synthesized and shaped according to the preparation method according to the invention. Said activation step makes it possible to activate the sites intended to selectively adsorb lithium. Preferably, said activation step is advantageously carried out by ascending or descending, and preferably descending, passage of water or a lithium salt solution having a concentration of between 0.001 mol / L and 0.1 mol / L, preferably between 0.001 mol / L and 0.05 mol / L and preferably between 0.01 and 0.04 mol / L.

Preferably, the lithium salt used in solution in said activation step is chosen from lithium chloride (LiCl), lithium nitrate and lithium bromide. Very preferably, the lithium salt used in solution in said activation step is lithium chloride (LiCl). According to a preferred embodiment, said activated crystallized solid material undergoes at the end of step d activating a washing step with a solution of lithium chloride (LiCl). Said activation step is advantageously carried out at a temperature between 0 ° C. and 90 ° C., and preferably between 10 ° C. and 60 ° C., and preferably between 10 ° C. and 30 ° C. at a flow rate between 0.1 BV / h and 30 BV / h, and preferably between 1 BV / h and 15 BV / h. The amount of solution required for activation is advantageously between 1 BV and 30 BV, preferably between 2 BV and 20 BV. BV means the volume occupied by the bed of the solid in the column. Said step of loading said adsorption-activated material is advantageously carried out by ascending or descending, and preferably ascending, saline solution treated in the extraction process according to the invention, on said activated material. Said loading step is advantageously carried out at a temperature of between 0 ° C. and 90 ° C., and preferably between 10 ° C. and 70 ° C. at a flow rate of between 0.1 BV / h and 30 BV / h, and preferably between 1 BV / h and 15 BV / h. The amount of solution necessary to saturate said material depends on the adsorption capacity of said material and the lithium concentration of the saline solution. The adsorption capacity of said material is between 1 and 50, preferably between 1 and 30 and preferably between 1 and 10 mg of Li / g of dry solid material. In the case where said lithium extraction method according to the invention is implemented in a unit comprising two columns, the first column is advantageously saturated with lithium during said charging step. The second column, receiving the output stream of the first column, is advantageously charged until a lithium leak not exceeding 10% of the lithium concentration of the inlet stream is obtained, preferably 5%, thus making it possible to maximize the recovery yield of lithium. In the case where said lithium extraction process according to the invention is carried out in a unit comprising three columns, the third column, already saturated with lithium, is devoted to the steps of washing and then desorption of lithium, described above. after, while loading the other two columns.

The first fraction of the output stream of said adsorption loading step, advantageously between 0 BV and 1 BV, corresponds to the removal of the impregnant resulting from the activation step of the solid material. This fraction can be considered as an effluent or recycled, and preferably recycled as an input stream of the desorption step. In the case of the treatment of a natural brine or seawater, beyond 1 BV, the entire output stream of said adsorption loading step, hereinafter referred to as raffinate, which has not undergone any chemical treatment, is preferably and preferably returned to the original salt solution deposit.

At the end of the step of loading by passing the saline solution treated in the process according to the invention on the activated material, the saline solution impregnates said activated material. The saline solution impregnating the activated material is then washed in at least one washing step by passing a washing solution on said material.

Said step (s) of washing the saline solution impregnating said material, is (are) advantageously carried out (s) by upward or downward passage of a washing solution on said material, and preferably downward. Preferably, said washing solution is selected from water and an aqueous solution of sodium salt and preferably sodium chloride (NaCl), optionally comprising a lithium salt and preferably lithium chloride (LiCl), said solution advantageously having a concentration of sodium salt and preferably sodium chloride (NaCl), greater than 2 mol / l, preferably of between 2 mol / l and saturation and a concentration of lithium salt and preferably chloride lithium (LiCl), between 0 mol / L and 2 mol / L. According to a preferred embodiment, said saline solution impregnating the activated material undergoes a final washing step by passing an aqueous washing solution of sodium chloride (NaCl) optionally comprising lithium chloride (LiCl), on said material. Said washing step is advantageously carried out at a temperature of between 0 ° C. and 90 ° C., and preferably between 10 ° C. and 70 ° C., and at a flow rate of between 0.1 BV / h and 30 BV / h, and preferably between 1 BV / h and 15 BV / h. The amount of solution required for washing is between 0.1 BV and 10 BV, typically in the range 0.5 BV to 5 BV.

The outlet stream of said washing step is considered as an effluent or is advantageously recycled, and preferably recycled at the inlet of the loading stage or directly at the inlet of the second column in the case where said process of extraction of the lithium according to the invention is carried out in a unit comprising at least two columns. The device according to the present invention may advantageously comprise a unit for recycling the outlet flow of the washing unit. Said washing step allows the washing of the saline solution impregnated in said material during the step of loading said material by adsorption, while limiting the desorption of lithium. In the case where said washing solution is a saturated aqueous solution of sodium chloride (NaCl), said washing step not only makes it possible to eliminate the saline solution impregnated in said material during the step of loading said material by adsorption but also desorb elements such as boron, sulphates, alkalis other than lithium and alkaline earths. The lithium desorption step is then carried out by passing water or an aqueous solution of lithium chloride (LiCl) on said material at the end of the washing step to obtain an eluate comprising at least lithium . Preferably, said desorption step is carried out by ascending or descending, and preferably descending, passage of water or a solution of lithium chloride (LiCl) containing from 0.001 mol / l to 2 mol / l of LiCl, and preferably from 0.01 mol / l to 1 mol / l. Said desorption step is advantageously carried out at a temperature between 0 ° C. and 90 ° C., and preferably between 10 ° C. and 70 ° C. at a flow rate of between 0.1 BV / h and 30 BV / h, and preferably between 1 BV / h and 15 BV / h. The amount of lithium chloride solution (LiCl) required for the desorption is advantageously between 0.01 and 10 BV, and preferably between 0.05 BV and 5 BV. The output stream of said lithium desorption step generates the final product of the process, called the eluate. The eluate is advantageously recovered between 0 BV and 4 BV, and preferably between 0.2 BV and 3 BV.

All the other fractions of the output stream of this step not constituting the final product called eluate, is considered as an effluent or is advantageously recycled, and preferably recycled at the inlet of the washing step or the loading step.

The eluate obtained at the end of the extraction process according to the invention is a solution containing mainly Li, Na and Cl elements as well as impurities preferably chosen from K, Mg, Ca, Sr, B or SO4. The eluate is then advantageously concentrated and then purified to obtain a lithium salt of high purity. Said lithium extraction method according to the invention allows the selective extraction of lithium from a saline solution and thus makes it possible to obtain a high decontamination factor with respect to the initial saline solution, calculated as the ratio X Li, which is equal to the molar ratio of concentration X / Li in the initial saline solution divided by the molar ratio of concentration X / Li in the eluate, X being chosen from sodium (Na), potassium (K), magnesium (Mg), calcium (Ca), boron (B), sulfur (S) and strontium (Sr).

The present invention also covers a lithium extraction device characterized in that it comprises a unit comprising at least one column, said column comprising at least one lining comprising the crystalline solid material of formula LiC1.2A1 (OH) 3, nH20 with n being between 0.01 and 10, shaped, as defined according to the present invention.

More particularly, the invention covers a device implementing the lithium extraction method according to the invention. Even more specifically, the device of the present invention comprises units or means implementing the various steps of the lithium extraction method according to the invention. By "according to the invention" or equivalent terms, it is meant to cover any embodiment, variant, advantageous or preferred characteristic, taken alone or in any of their combinations, without any limitation.

Description of the Figures: FIG. 1 represents a photo of the crystallized solid material of formula LiC1.2A1 (OH) 3, nH20 obtained in the form of extrudates according to the example according to the invention 1.

FIG. 2 represents the X-ray diffraction pattern of the crystallized solid material of formula LiC1.2A1 (OH) 3, nH20 obtained in the form of extrudates according to the example according to the invention 1 FIG. 3 represents a photo of the solid material of formula LiC1.2A1 (OH) 3, nH20 obtained in the form of extrudates according to Example 2 not according to the invention according to the invention. The invention is illustrated by the following examples, which in no way present a limiting character.

Examples: Example 1 (according to the invention): A solid material of formula LiC1.2A1 (OH) 3, nH20 with n = 0.25 is prepared according to a synthesis method according to the invention in that the step of shaping of the dough is carried out by kneading / extrusion in the presence of at least one solid precursor of alumina and phosphoric acid in solution, to obtain extrudates. 1 / Synthesis Al (OH) 3 In a beaker cooled by an ice bath, a solution containing 326 ml of deionized water and 135.6 g of aluminum chloride hexahydrate (AIC13) is prepared. Then, with magnetic stirring, 67.5 g of sodium hydroxide (NaOH) are added slowly. This cake is suspended in a 3 L beaker with 320 mL of water. 2 / Addition of lithium chloride LiCl. A solution containing 78.5 g of lithium chloride LiCl provided by Prolabo and 1326 ml of water which is added to the plumped cake is prepared. This reaction medium is stirred and heated at 80 ° C for 2 h. Filtration and drying in an oven at 40 ° C for 8 h follow the first 2 steps to obtain a dry paste. 22.16 g of dry pulp to be shaped obtained after drying are then introduced into a tank of a Brabender type mixer. Then 8.275 g of a Pural SB3 boehmite powder representing 25% mass of alumina solid precursor relative to the mass of dry pulp to be extruded and 12.225 g of phosphoric acid at 85% by weight are added. The proportion of phosphoric acid in solution is such that the ratio of the mass of acid introduced on the solid precursor mass of alumina is 168%. The mixture is then kneaded for 30 minutes.

The paste obtained is shaped by passing through a piston extruder (MTS) equipped with a cylindrical die 0.8 mm in diameter. The extrudates obtained are then dried at 40 ° C. for 12 hours.

The extrudates obtained are characterized by the following measurements: A LiC1.2A1 (OH) 3, nH20 phase is detected on the X-ray diffraction pattern of the extruded crystalline solid material of formula LiC1.2A1 (OH) 3, nH20 with n = 0.25 of Figure 2. Said extruded have good cohesion and a good appearance. The extrudates obtained are shown in the photo of FIG. 1. The elemental analysis of the extrudates obtained also shows a good Li / Al / CI stoichiometry corresponding to the composition of a structure LiC1.2A1 (OH) 3, nH20 Al = 21 2% mass; Li = 4.2% mass; Cl, = 19% mass.

The extrudates obtained have a specific surface area: SBET = 25 m 2 / g. Example 2 (Comparative) A solid material of formula LiC1.2A1 (OH) 3, nH20, with n being between 0.01 and 1, is prepared according to a synthesis method not in accordance with the invention in that the Step of shaping of the paste obtained is carried out by extrusion kneading in the presence of an inorganic binder of the family of hydraulic binders added during the kneading phase. 37.7 g of the solid material of formula LiC1.2A1 (OH) 3, nH20 with n being between 0.01 and 1 is obtained according to the process described in Example 1, with the difference that the shaping step is carried out by kneading - extrusion in the presence of an inorganic binder. The dried pulp obtained after the first drying of Example 1 is introduced into a Brabender type mixer in the presence of 21.8 g of water and in the presence of 4.6 g of Dyckerhoff cement as a hydraulic binder. and is simply kneaded. The paste obtained is shaped using a piston extruder (MTS) equipped with a cylindrical die 1 mm in diameter. The extrudates obtained at the end of the shaping step are then dried in an oven at 40 ° C. for 12 hours.

The extrudates obtained at the end of the shaping step were also dried in a climate oven at 25 ° C. for 48 hours in saturated air with 98% water. Both drying methods have led to the same result: the extrudates obtained are shown in Figure 3, they are friable and have many cracks.

EXAMPLE 3 (Comparative) A solid material of formula LiC1.2A1 (OH) 3, nH20, with n being between 0.01 and 1, is prepared according to a synthesis method not in accordance with the invention in that step shaping of the paste obtained is carried out according to the conventional technique of mixing acid / basic extrusion implemented according to the knowledge of the skilled person. 1 / Al (OH) 3 synthesis In an ice-bath beaker, a solution containing 326 ml of deionized water and 135.6 g of aluminum chloride hexahydrate (AIC13) is prepared. Then, with magnetic stirring, 67.5 g of sodium hydroxide (NaOH) are added slowly. This cake is suspended in a 3 L beaker with 320 mL of water. 2 / Addition of lithium chloride LiCl. A solution containing 78.5 g of lithium chloride LiCl provided by Prolabo and 1326 ml of water which is added to the plumped cake is prepared. This reaction medium is stirred and heated at 80 ° C for 2 h. Filtration and drying in an oven at 80 ° C for 8 h follow the first 2 steps.

The dried paste obtained is then shaped according to the conventional technique of mixing acid / basic extrusion. The dried pulp is introduced into a Brabender type mixer. The water acidified with nitric acid is added in 4 minutes, with mixing at 20 rpm. The acid mixing is continued for 10 minutes. A neutralization step is then carried out by adding an ammoniacal solution in the kneader and kneading is continued for 3 minutes.

The mixing is carried out with a total acid content, expressed relative to the dried pulp of 2%, and a degree of neutralization of 20%. At the end of the mixing, no cohesive paste could be obtained. The wet solid obtained is shaped using a piston extruder (MTS) equipped with a cylindrical die 1 mm in diameter. No intact extrudates could be obtained. The rushes obtained are very friable and have no hold in the brine. EXAMPLE 4 Cohesion Test The mechanical strength of the extrudates obtained according to Examples 1, 2 and 3 is tested on contact with a brine solution. The different results are summarized in Table 1. Table 1: MEF protocol implemented and appearance of the corresponding extrusions Examples 1 (compliant) 2 (non-3 (non-compliant) compliant) Mixing step Mixing Mixing acid forming extrusion with extrusion with basic binder according to a binder cement extrusion without the invention binder Die 0.8 mm 1 mm 0.8 mm Final drying 40 ° C, 12 h Climate weather, 25 ° C, 98% water or 40 ° C, 12h 40 ° C, 12 h extruded (e) Aspect of the extruded in contact with the brine 0.8 mm die many "rushes" which quickly disintegrate cracks, extruded which become powder. 40 ° C: extruded without apparent defects Phase in LiC1.2A1 (OH) 3, LiC1.2A1 (OH) 3, - DRX nH2O nH2O The extrudates obtained according to the invention (Example 1) compared to those obtained according to methods of Preparation not in accordance with the invention, have good cohesion, have no or few cracks that could cause harmful swelling to the cohesion and strength of the material when it is brought into contact with a brine solution. Moreover, said extrudates according to the invention remain intact and produce very few fines when placed in a brine solution.

EXAMPLE 5 Test of mechanical resistance by accelerated aging on a stirring table of materials made according to examples 1 (compliant), 2 (non-compliant) and 3 (non-compliant).

The mechanical strength of the extrudates of Examples 1, 2 and 3 is tested by means of an accelerated stirring table aging protocol. For each batch from Examples 1, 2 and 3, 5 g of extrudates and 25 ml of natural brine are placed in a cylindrical container with a capacity of 60 ml. This container is attached to the stirring table for the duration of the test.

The composition of the natural brine used in this test is given in Table 2. Table 2: composition of the natural brine used for the mechanical strength test Na K Li Mg Ca B SO4 Sr Cl Concentration 4.4 0.24 0.068 0.086 0.040 0.031 0.035 0.001 4.89 (mol / L) The stirring table is animated by a horizontal unidirectional movement of amplitude 4 cm at a speed of 190 movements per minute. The extrudates are stirred for a total of 168 hours. At the end of these 168h, the extruded-brine mixture is sieved using a 315 lm grid. Then the extrudates remaining on the sieve are washed with brine whose composition is indicated in Table 2. The liquid fraction thus obtained, containing fine solid particles (diameter less than 315 lm) in suspension, is filtered using a Büchner equipped with a filter paper whose pores have a dimension of 0.45 lm. The cake formed by agglomeration of the fine particles is washed with deionized water.

The solid residue thus obtained is dried in an oven at 50 ° C. until the mass stabilizes. The ratio of the mass of solid residue to the initial extruded mass is then calculated, giving access to a percentage of destruction of the extrudates.

The percentage of destruction of the extrudates of Example 1, produced according to the invention, is 15%. The non-compliant extrudates from Examples 2 and 3 have a destruction percentage of respectively 60% and 100%. This comparison shows an increased mechanical resistance of the extrusions in contact with the brine due to the invention. Example 6: Test of the material according to the invention produced according to Example 1 in the lithium extraction process according to the invention.

The material according to the invention prepared in Example 1 is introduced into a double-walled column to form a cylindrical bed with a diameter of 2.5 cm and a height of 30 cm. The material is then activated at ambient temperature T = 20 ° C. with LiCl solution of lithium chloride of concentration 0.02 mol / L in downflow at a flow rate of 3 BV / h. The total volume of LiCl solution used is 14 BV. Once the activation stage is complete, the loading is carried out using a natural brine whose composition is given in table 2. Table 2: composition of the natural brine used for the loading Na K Li Mg Ca B SO4 Sr Cl Concentration 4.4 0.24 0.068 0.086 0.040 0.031 0.035 0.001 4.89 (mol / L) The adsorption-activated material is charged by passing natural brine over the activated material at a temperature of 60 ° C. ° C., the temperature being maintained by means of a circulating water heated in the double jacket, with a flow rate of 3 BV / h in ascending flow.

Under the conditions of the example, the adsorption capacity of the material is 4.7 mg Li / g dry solid material for a recovery efficiency of lithium of 93%. After loading, the washing step is performed using an aqueous solution of sodium chloride. This solution is prepared at saturation of sodium chloride NaCl at 20 ° C. The solution is then heated to 60 ° C and passed to the same downflow temperature in the column at a rate of 3 BV / h for a total amount of 6 BV. Then the lithium desorption step is carried out by passing a solution of lithium chloride (LiCl) of concentration 0.02 mol / L on said material. This desorption is carried out at a temperature of 20 ° C. with a flow rate of 3 BV / h and in downflow. The eluate containing the lithium is recovered between 0.75 and 2.25 BV. The composition of the eluate and the resulting decontamination factors are summarized in Table 3. TABLE 3 Composition of the eluate and decontamination factors X Na K Li Mg Ca B SO4 Sr Cl Composition 0.52 3.3.10 4 0.11 8.6.10-3 4.3.10-3 1.0.10-3 9.4.10-5 8.0.10-6 0.66 (mol / L) Factor of 1000 - 15 10 40 500 90 10 Decontamination Elemental concentrations in the brine and in the eluate are determined by the optical ICP method known to those skilled in the art.

The Cl concentration in the eluate and brine is determined by the ion chromatography method known to those skilled in the art. The extraction process according to the invention thus allows the selective extraction of lithium from natural brine. The selectivity to lithium is expressed as a decontamination factor which is equal to the X / Li molar ratio in the initial natural brine divided by the X / Li molar ratio in the eluate and which takes into account the external supply of lithium by the washing solution. The results obtained indicate that the solid prepared according to the invention is particularly selective in potassium (K), in strontium (Sr) in boron (B) and in sulphates (SO4). EXAMPLE 7 Test of materials not in accordance with the invention made according to Examples 2 and 3 in a lithium extraction process.

The solid material of formula LiC1.2A1 (OH) 3, nH20 prepared according to Example 2, according to a synthesis method not in accordance with the invention, in that the step of forming the paste obtained is carried out by extrusion mixing in the presence of an inorganic binder of the family of hydraulic binders added during the kneading phase is tested in a lithium extraction process operating under conditions identical to those of Example 6. As indicated in the example 2, the extrudates obtained are friable and have many cracks.

The material prepared in Example 2 is introduced into a double-walled column identical to that used in Example 6. However, as soon as the material activation step, there is the appearance of powder, causing rapid clogging of the column and the impossibility of circulating the brine. In the same way, the solid material of formula LiC1.2A1 (OH) 3, nH20 prepared according to Example 3, according to a synthesis method not in accordance with the invention in that the shaping step of the paste obtained is carried out according to the conventional technique of mixing acid / basic extrusion implemented according to the knowledge of those skilled in the art is tested in a lithium extraction process operating under conditions identical to those of Example 6. As indicated in Example 2, the extrudates obtained are friable and have many cracks.

After its introduction into a double-jacketed column identical to that used in Example 6, and as of the material activation step, there is the appearance of powder, quickly causing clogging of the column and the impossibility of doing circulate the brine.

Materials prepared according to a preparation method not in accordance with the invention do not allow their use in a selective lithium extraction process because of their poor cohesion.

Claims (22)

REVENDICATIONS1. Process for preparing a crystalline solid material of formula LiC1.2A1 (OH) 3, nH20 with n being between 0.01 and 10, said process comprising at least the following steps a) a mixing step, in an aqueous medium , at least one source of alumina and at least one lithium source, to obtain a suspension, b) a filtration step of the suspension obtained in step a) to obtain a paste, c) a step drying the paste obtained at the end of step b), at a temperature between 20 and 80 ° C for a period of between 1h and 12h, d) a step of shaping by mixing - extrusion of a paste in the presence of a binder formulation comprising at least one solid precursor of alumina and at least one acid in solution in proportions such that the acid / Al molar ratio is between 0.01 and 1.2, for obtain extrusions, e) a step of drying the extrudates obtained at the end of step d) at a temperature comprised e between 20 and 200 ° C for a period of between 1 and 20 hours, to obtain the crystalline solid material of formula LiC1.2A1 (OH) 3, n1-120 in the form of extrudates. 2. Method according to claim 1 wherein the source of alumina is aluminum trihydroxide A1 (01-1) 3. 3. Method according to one of claims 1 or 2 wherein the source (s) of lithium is (are) selected from lithium chloride (LiCl), lithium hydroxide (LiOH) nitrate Lithium (LiNO3), lithium sulphate (Li2SO4) and lithium carbonate (Li2CO3), alone or in admixture. 4. The method of claim 3 wherein the lithium source is lithium chloride (LiCl). 5. Method according to one of claims 1 to 4 wherein said alumina precursor used in the shaping step d) is selected from aluminum oxides, aluminum hydroxides and aluminum oxyhydroxides soluble or dispersible in the phosphoric acid solution. 6. The method of claim 5 wherein said alumina precursor is selected from boehmite or pseudo-boehmite. 7. Method according to one of claims 1 to 6 wherein the acid solution introduced in step d) is selected from phosphoric acid, hydrochloric acid, nitric acid, acetic acid and citric acid, alone or in admixture. The process of claim 7 wherein the acid is phosphoric acid. 9. Method according to one of claims 1 to 8 wherein the proportion of the solid precursor of alumina is between 0.5 and 50% by weight relative to the mass of dry paste to be shaped. 10.- crystallized solid material of formula LiC1.2A1 (OH) 3, nH20 with n being between 0.01 and 10, shaped, preferably in the form of extrudates. 11.- crystallized solid material of formula LiC1.2A1 (OH) 3, n1-120 with n being between 0.01 and 10, in the form of extrudates, obtainable by a process as defined according to any of claims 1 to 9. 12. A method of extracting lithium from saline solutions using said solid material as defined in claim 10 or 11. 13. Extraction method according to claim 12 wherein said lithium extraction process comprises at least the following steps: a step of activating said crystallized solid material of formula LiC1.2A1 (OH) 3, nH20 with n being included between 0.01 and 10, a step of loading said activated adsorption material carried out by passing said saline solution on said activated material, a step of washing the saline solution impregnating said material by passing a washing solution on said material, a lithium desorption step performed by passing water or an aqueous solution of lithium salt on said material to obtain an eluate comprising at least lithium. 14. Extraction process according to claim 13, wherein said activation step is carried out by the upward or downward passage of water or a solution of lithium chloride (LiCl) having a concentration of between 0.001 mol / L. and 0.1 mol / L. 15. Extraction method according to rune of claims 13 to 14 wherein said activation step is carried out at a temperature between 0 ° C and 90 ° C, and at a flow rate between 0.1 BV / h and 30 BV / h, BV / h meaning volume occupied by the bed of the solid in one column per hour. 16. Extraction method according to one of claims 13 to 15 wherein said step of loading said adsorption-activated material is carried out by upward or downward passage of the saline solution on said activated material. 17. Extraction method according to one of claims 13 to 16 wherein said charging step is carried out at a temperature between 0 ° C and 90 ° C, and at a flow rate between 0.1 BV / h and 30 BV / h, BV / h meaning volume occupied by the bed of the solid in one column per hour. 18. Extraction process according to one of claims 13 to 17wherein said washing solution used in the washing step is an aqueous solution of sodium chloride (NaCl) optionally comprising lithium chloride (LiCl) or sodium chloride. 'water. 19. Extraction method according to one of claims 13 to 18 wherein said washing step is carried out at a temperature between 0 ° C and 90 ° C, and at a flow rate between 0.1 BV / h and 30 BV / h, BV / h meaning volume occupied by the bed of the solid in one column per hour. 20. Extraction process according to one of claims 13 to 19 wherein said desorption step is carried out by upward or downward passage, water or a solution of lithium chloride (LiCl) containing 0.001 mol / L to 2 mol / L of LiCl. 21. Extraction method according to one of claims 13 to 20 wherein said desorption step is carried out at a temperature between 0 ° C and 90 ° C, and at a flow rate between 0.1 BV / h and 30 BV / h, BV / h meaning volume occupied by the bed of the solid in one column per hour. 22. A lithium extraction device characterized in that it comprises a unit comprising at least one column, said column comprising at least one packing comprising the crystallized solid material of formula LiC1.2A1 (OH) 3, nH20 with n being included between 0.01 and 10, shaped as defined in claim 10 or 11.