WO2015097201A1

WO2015097201A1 - Method of preparing an adsorbent material, shaping, by precipitation of aluminium sulphate, and sodium aluminate and method of extracting lithium using said material

Info

Publication number: WO2015097201A1
Application number: PCT/EP2014/079117
Authority: WO
Inventors: Malika Boualleg; Olivier LAFON; Fabien André Pierre BURDET; Romain Charles Joseph René SOULAIROL
Original assignee: Eramet; IFP Energies Nouvelles
Priority date: 2013-12-23
Filing date: 2014-12-23
Publication date: 2015-07-02
Also published as: AR098941A1; FR3015459A1

Abstract

The invention concerns a novel method of preparing a crystallized solid material having the formula Li₂SO₄.4AI(OH)₃,nH₂O, where n is between 0.01 and 10, comprising at least the following steps: (a) precipitating in an aqueous medium aluminium sulphate, sodium aluminate and at least one lithium source in order to obtain a suspension; (b) filtering the suspension obtained in step (a) in order to obtain a paste, the filtering step being followed by at least one step in which the resulting paste is washed; (c) drying the paste obtained at the end of step (b); (d) shaping the dried paste by extrusion in order to obtain extruded products; and (e) drying the resulting extruded products at a temperature of between 20 and 200°C for a period of between 1 and 20 hours, in order to obtain the crystallized solid material in the form of extruded products. The invention also concerns a method of extracting lithium from saline solutions using the material thus obtained. The invention further concerns a crystallized solid material having the formula Li₂SO₄.4AI(OH)₃,nH₂O, where n is between 0.01 and 10 shaped. The invention also concerns a device for performing the lithium-extraction method.

Description

PROCESS FOR PREPARING ADSORBENT MATERIAL, SHAPED BY PRECIPITATION OF ALUMINUM SULPHATE AND SODIUM ALUMINATE, AND LITHIUM EXTRACTION METHOD USING THE SAME

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 of formula Li ₂ S0 _4. 4AI (OH) 3, nH ₂ 0 with n being between 0.01 and 10, comprising a step precipitating at least one lithium source and two specific sources of alumina and in particular aluminum sulphate and sodium aluminate, and to a process for extracting lithium from saline solutions using said material crystalline solid prepared according to the new preparation method according to the invention. The invention relates to a crystallized solid material of formula Li ₂ S0 _4. 4AI (OH) 3, nH ₂ 0 with n being between 0.01 and 10 formed. 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, especially 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 LiCl 2 Al (OH) ₃ , nH ₂ 0 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 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 any case, a Al (OH) ₃ aluminum trihydroxide solid, prepared or commercially available, 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 (Li ₂ CO ₃ ) 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 the 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 the preparation of a solid of formula LiCl 2 Al (OH) ₃ , nH ₂ O comprising a step of mixing aluminum trichloride (AlCl ₃ ) and lithium carbonate (Li ₂ C0 ₃ ) 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.

The CN12431 12 patent describes a process for the preparation of a solid of formula LiCI.2AI (OH) ₃ , nH ₂ O comprising a step of precipitation of aluminum hydroxide microcrystals AI (OH) ₃ by contacting the AICI ₃ 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 LiCI.2AI (OH) ₃ , nH ₂ O powder 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 LiCl 2 Al (OH) ₃ , nH ₂ O 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. The publication VP Isupov (Journal of Structural Chemistry Vol 40 No. 5 1999 - Intercalation compounds of aluminum hydroxide p672-685) describes the materials LiNO ₃ .2AI (OH) 3, nH ₂ 0 and Li ₂ SO 4 _. 4AI (OH) ₃ which are characterized by their X-ray diffraction pattern. Said materials are obtained in powder form and prepared by intercalation, respectively, of lithium nitrate and of lithium sulphate in an aluminum trihydroxide.

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.

Another object of the present invention is to provide a new process for preparing such a solid material.

Another object of the present invention is also to provide a method for extracting lithium from saline solutions using said crystallized solid material shaped, advantageously in the form of extrudates prepared according to the invention.

Summary and interest of the invention

Applicants have discovered that a new process for preparing a crystallized solid material shaped, advantageously in the form of extrudates of formula Li ₂ SO 4 _. 4AI (OH) 3, nH ₂ 0 with n being between 0.01 and 10, comprising a step of precipitation of at least one source of lithium and of two specific sources of alumina and in particular aluminum sulphate and of sodium aluminate, provided said crystallized solid material having good properties for the adsorption of lithium. Said shaped solid material is of good quality, and has a good cohesion, without apparent defect. The expression "material of formula Li ₂ S0 ₄ 4AI (OH) 3, nH ₂ 0" is preferably understood to mean a material comprising essentially or consisting of a crystallized phase of formula Li ₂ SO ₄ .4Al (OH) 3, nH ₂ 0, optionally in the presence of binder (s).

The subject of the present invention is the process for preparing a crystallized solid material in the form of extrudates of formula Li ₂ S0 ₄ 4AI (OH) 3, nH ₂ 0 with n being between 0.01 and 10, said process comprising at least the following steps:

a) a step of precipitating, in an aqueous medium, aluminum sulphate and sodium aluminate and at least one lithium source to obtain a suspension, said precipitation step operating at a temperature of between 20 and 90 ° C and at a pH of between 4 and 10,

b) a step of filtering the suspension obtained in step a) to obtain a paste, said filtration step being followed by at least one washing step of the paste obtained, c) a step of drying the paste obtained at the end of step b),

d) a step of extrusion shaping of said dried pulp to obtain extrusions,

e) 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 said material. An advantage of the preparation process according to the invention is to provide a method of preparation in a single step, therefore a less expensive method of said crystallized solid material in powder form from a precipitation step of at least one lithium source. and two specific sources of alumina and in particular aluminum sulphate and sodium aluminate.

Another advantage of the present invention is also to provide a new process for the preparation of said crystallized solid material making it possible to obtain said shaped solid material, and advantageously in the form of extrudates, of good quality, without apparent defects, and having a good cohesion.

Another advantage of the present invention is also to make it possible to obtain a shaped crystallized solid material, and advantageously in the form of extrudates, having no or few cracks which could cause a swelling detrimental to the cohesion and the holding 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 Li ₂ S0 _4. 4AI (OH) 3, nH ₂ 0 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 formed in the sense of the invention preferably covers a solid substantially retaining its shaping under the lithium extraction conditions defined in the examples. In particular, the terms "shaped" cover a material obtained by granulation (called granule) and preferably by extrusion (called extruded).

The present invention also relates to a method for extracting lithium from saline solutions using said crystallized solid material.

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.

Description of the invention

The subject of the present invention is the process for the preparation of a shaped crystallized solid material, advantageously in the form of extrudates, of formula Li ₂ S0 ₄ 4AI (OH) 3, nH ₂ 0 with n being between 0, 01 and 10, preferably between 0.1 and 5 and preferably between 0.1 and 1.

According to the invention, at least one source of lithium and two specific sources of alumina, aluminum sulphate and sodium aluminate are mixed in an aqueous medium to obtain a suspension in step a). Said step a) is carried out according to a synthesis mode called "one pot" according to the English terminology. It is characterized in the present invention by the co-precipitation of two alumina precursors, with stirring, with a permanent control of the temperature and the pH through a pH meter electrode. The pH of said step a) is maintained in the range claimed by the flow rates of the various added alumina precursors.

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, (LiNO ₃ ), lithium sulphate (Li ₂ SO ₄ ) and lithium carbonate (Li ₂ CO ₃ ), alone or as a mixture.

Very preferably, the lithium source is lithium chloride (LiCl).

Preferably, the aluminum sulfate, sodium aluminate and at least one lithium source are mixed in the presence of water to obtain a suspension in step a). Preferably, said precipitation step a) takes place with vigorous stirring.

Preferably, said precipitation step a) operates at a temperature between 30 and 90 ° C, preferably between 50 and 70 ° C and at a pH between 4 and 9 and preferably between 5 and 9.

Preferably, said precipitation step a) operates for a period of between 5 minutes and 10 hours, preferably between 15 minutes and 5 hours, preferably between 30 minutes and 3 hours, and more preferably between 30 minutes and 2 hours. .

According to the invention, the suspension obtained at the end of step a) undergoes a step b) of filtration to obtain a paste, said filtration step being followed by at least one washing step of the paste obtained.

Preferably, the washing solution is water. Preferably, three washings with water (3 times the volume of the suspension) are 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 drying step c).

In one embodiment, said drying step b) is carried out by atomization. The atomization conditions are known to those skilled in the art. In a second embodiment, said drying step b) is carried out in an oven, at a temperature between 20 and 120 ° C, for a period of between 1 h and 20 h, and preferably at a temperature between 20 and 80 ° C and very preferably between 30 and 60 ° C, and for a period of between 1 hour and 15 hours and preferably between 1 and 12 hours.

The operating conditions of said drying step c) carried out in an oven allow obtaining 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 pulp in good conditions and the production of extrudates without defects, ie without cracking.

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 d) extrusion shaping step to obtain extrusions.

According to a first embodiment, said shaping step d) can advantageously be implemented directly after the c) drying step.

By direct shaping of the dried paste resulting from step c) is meant a step in which said dried paste does not undergo intermediate steps between the drying step c) and its introduction into the extruder and into the extruder. in particular no mixing step.

Preferably, step d) direct shaping of the dried paste is implemented in the case where no binder selected from inorganic binders, such as for example hydraulic binders or inorganic binders may be generated in the conditions of said step d) by addition of inorganic binder precursors, and organic binders, such as for example paraffins or polymers, are added in said step d).

In this case, said dried paste preferably undergoes no intermediate step between said drying step c) and said extrusion shaping step d), and preferably no mixing step and more preferably no acid / basic mixing step. Thus, more preferably, said step d) of setting According to the first embodiment, the form is produced without addition of acid or base to the dried pulp introduced in said step d).

Said step d) direct extrusion shaping is advantageously carried out in a manner known to those skilled in the art.

In particular, the dried paste resulting from the drying step c) 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. 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.

According to a second embodiment, said shaping step d) can advantageously be carried out by kneading-extrusion in the presence of at least one binder chosen from organic binders and inorganic binders which can be generated under the conditions of said step d) by addition of inorganic binder precursors.

The term "kneading-extrusion step" is understood to mean a step in which the dried pulp obtained at the end of drying step c) undergoes, in a first kneading step, generally in the presence of at least one binder or precursor compound of binder, 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 binder or binder precursor are mixed, preferably all at once, in a kneader. The kneader is advantageously chosen from batch kneaders, from preferably with a cam or Z-arm, or with a twin-screw 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.

In the kneading-extrusion processes known to those skilled in the art, the extrudability of the dough can advantageously be adjusted with the addition of water and / or acid in solution, in order to obtain a paste suitable for performing step b) extrusion shaping. In the case where acid is added, a neutralization step is generally carried out. These methods are referred to as acidic / basic extrusion kneading processes.

In the present invention, the kneading step is carried out without the addition of acid or base. Thus, no step of acidification or neutralization of the dried pulp is implemented in the d) shaping step - extrusion according to the invention. 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 0.5 and 5 mm, preferably between 0.5 and 3 mm and preferably between 0.5 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.

Advantageously, the solid material according to the invention may comprise at least one binder preferably chosen from organic binders and inorganic binders.

Said binder (s) organic (s) that can be used in said step d) shaping are advantageously selected (s) from paraffins, and polymers, taken alone or in mixture.

Preferably, said one or more organic binder (s) are chosen from Cerfobol R75, polysaccharides, methylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose, carboxymethylcellulose and polyvinyl alcohol, taken alone or as a mixture .

Very preferably, said organic binder is Cerfobol R75. Cerfobol R75 comprises 28.4% dry paraffinic organic mass diluted in an aqueous phase.

The proportion of said one or more organic binder (s) added in said shaping step (d) is advantageously between 0.1 and 20% by weight, preferably between 0.1 and 15% by weight. , preferably between 0.1 and 12% by weight, very preferably preferred between 0.5 and 10% and even more preferably between 0.5 and 6.5% by weight relative to the total mass of dry pulp to be shaped.

The addition of at least one organic binder in said step d) facilitates the extrusion shaping of step d) of the process according to the invention.

The addition of at least one organic binder in said step d) also makes it possible to obtain a crystallized solid material in the form of extrudates with improved stirring resistance in contact with the brine.

In the case where said step d) is carried out by kneading / extrusion in the presence of at least one binder chosen from inorganic binders that can be generated under the conditions of said step d), said step d) of setting form of the dried paste is advantageously carried out 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 molar ratio acid / Al is between 0.01 and 1, 2.

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 described.

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 granulometry, between 9 and 80 μηι, preferably between 10 and 60 μηι and preferably between 15 and 45 μηι. 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) 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. mass, and preferably between 3 and 25% by weight.

In this embodiment, 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 brought during the shaping step d), an amorphous phase of inorganic binder.

Preferably, the acid or acids in solution is (are) introduced in such proportions that the acid / Al molar ratio is between 0.01 and 1.2, and preferably between 0.03 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 molar ratio P / Al, P is derived from the introduced phosphoric acid and Al is derived from the solid precursor of alumina.

The specific P / Al molar ratio as claimed corresponds to a proportion of phosphoric acid such as the ratio of the mass of acid introduced onto the precursor mass. alumina solid introduced is between 30 and 225% by weight, 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 shaping step (d) makes it possible at the same time to form the amorphous phase of the inorganic binder resulting from the reaction with the solid precursor of alumina, but also to facilitate the shaping by extrusion and to increase the cohesion and mechanical strength of the extrudates obtained according to this embodiment.

According to the invention, the extrudates obtained at the end of step d) undergo a step e) of drying at a temperature of between 20 and 200 ° C. for a period of between 1 hour and 20 hours, to obtain the said solid material 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.

The method according to the present invention thus makes it possible to obtain crystallized solid material 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 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 final drying step e) carried out at a temperature between 20 and 60 ° C and in particular at 40 ° C, for a period of time between 5 and 14 hours, preferably between 8 and 14 hours and in particular for 8 hours.

Said crystallized solid material of formula Li ₂ S0 _4. 4AI (OH) 3, nH ₂ 0 with n being between 0.01 and 10, shaped, advantageously in the form of extrudates, prepared according to the sequence of steps a ), b), c), d) and e) of the preparation process according to the invention can be characterized according to the following techniques: the adsorption of nitrogen for the determination of the specific surface according to the BET method; ray diffractometry X, in the field of diffraction angle 2Θ = 0.8 to 40 ° ± 0.02 ° in reflection geometry to identify the structure of said material and the elemental analysis.

The crystallized solid material formed, advantageously in the form of extrudates, advantageously has a specific surface area measured according to the BET method of between 1 and 150 m ² / g and preferably between 1 and 100 m ² / g.

The X-ray diffraction pattern of the crystallized solid material obtained according to the invention, in extruded form, is characteristic of a non-amorphous material. Said diagram shows that we obtain the solid of formula Li ₂ S0 _4. 4AI (OH) 3, nH ₂ 0 with n being between 0.01 and 10. It has at least the following lines:

According to the preferred embodiment in which said material in powder form is shaped, advantageously by extrusion, said shaping step d) being carried out in the presence of at least one organic binder selected from paraffins, and polymers , taken alone or as a mixture, the X-ray diffraction pattern as defined, of the solid material according to the invention obtained in extruded form is unchanged. According to the preferred embodiment in which said material in powder form is shaped by extrusion, said forming step d) being carried out in the presence of a binder formulation comprising at least one solid precursor of alumina and phosphoric acid in solution in proportions such that the molar ratio P / Al is between 0.01 and 1.2, the X-ray diffraction pattern as defined, of the solid material according to the invention obtained in the form of extruded is unchanged. The characteristic peaks of the alumina precursor of the binder formulation added in the shaping step d) can also be present on the diffractograms of the final extrudates in variable proportions, as a function of that introduced during step d) of FIG. formatting. The preparation method according to the invention thus makes it possible to obtain a crystallized solid material in the form of extrudates of formula Li ₂ S0 ₄ 4AI (OH) 3, nH ₂ 0 with n being included between 0.01 and 10 having both a low BET specific surface area, a good cohesion, and having no apparent defects.

Thus, the subject of the present invention is a crystallized solid material of formula Li ₂ S0 ₄ 4AI (OH) 3, nH ₂ 0 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.

The subject of the present invention is also a process for extracting lithium from a saline solution using said crystallized solid material of formula Li ₂ S0 ₄ 4AI (OH) 3, nH ₂ 0 with n being between 0.01 and according to the 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, SO ₄ , CO _3, N0 _3, and HC0 _3. 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 Li ₂ S0 ₄ 4AI (OH) 3 , nH ₂ 0 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 Li ₂ S0 ₄ 4AI (OH) 3, nH ₂ 0 with n being between 0.01 and 10,

a step of loading said adsorptive activated material carried out by passing said saline solution on 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 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 Li ₂ S0 _4. 4AI (OH) 3, nH ₂ 0 with n being between 0.01 and 10, in the form of extrudates, is carried out once only during the columnization of the synthesized and shaped material 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 comprises a first ascending or descending passage, and preferably a descending one, of a solution chosen from saline solutions and preferably a natural brine solution and sodium and lithium salts, said solution of sodium and lithium salts advantageously having a concentration of sodium salt greater than 2 mol / l, preferably of between 2 mol / l and saturation and a concentration of lithium salt of between 0 mol / l and 2 mol / l and preferably between 0 mol / l and 1 mol / L. Said activation step also advantageously comprises a second 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, of preferably between 0.001 mol / L and 0.05 mol / L and preferably between 0.005 and 0.04 mol / L. Preferably, the sodium and lithium salts used in solution during the first pass in said activation step are chosen from sodium and lithium chlorides, sodium and lithium nitrates, sodium and lithium bromides and iodides. of sodium and lithium and very preferably, the sodium and lithium salts used in solution during the first pass in said activation step are sodium chloride and lithium (NaCl and LiCl).

In the case where the solution used during the first pass of the activation step is a saline solution or a solution of sodium and lithium chloride, the crystalline solid material of formula Li ₂ S0 ₄ 4Al (OH) 3, nH ₂ 0 with n ranging from 0.01 to 10 is converted to crystalline solid material of the formula LiCl 2 Al (OH) ₃ , nH ₂ 0 with n being from 0.01 to 10.

Preferably, the lithium salt used in solution during the second pass in said activation step is chosen from lithium chloride (LiCl), lithium nitrate (LiNO ₃ ), lithium bromide (LiBr), lithium lithium iodide (Lil) and very preferably lithium chloride (LiCl).

Said activation step is advantageously carried out, for the first and second passages, at a temperature of 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 quantity of each solution, corresponding to the first and second passages, necessary 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 lithium washing and then desorbing steps described below. 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 lithium according to the invention is implemented 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 S0 ₄ .

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 crystallized solid material of formula Li ₂ S0 _4. 4AI (OH) 3, nH ₂ 0 with n ranging from 0.01 to 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 process 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 the X-ray diffraction pattern of the solid material of formula υ ₂ 3θ4 _. 4ΑΙ (ΟΗ) 3 ₂ 0 ηΗ obtained as extruded according to Example 1 of 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 crystallized solid material in the form of a powder according to the invention is prepared according to a synthesis method according to the invention comprising a step of precipitation of at least one source of lithium and of aluminum sulphate and of sodium aluminate and a direct extrusion shaping step. Firstly, the lithium chloride m = 76.87 g is dissolved in an initial volume of water of 1167 ml. This solution is placed in a 5 L reactor and is mechanically stirred and heated to 80 ° C. Then, the synthesis involves the simultaneous addition, continuously into the reactor, of aluminum sulphate (acid) (AI ₂ (S0 ₄₎ _3-1 12 g / L of Al ₂ 0 ₃₎ and the sodium aluminate (base) (NaAlO ₂ , 155 g / L Al ₂ O ₃ ) which precipitates to form a white solid. A water flow of 46 ml / min is also added at the same time. Throughout the reaction, the pH is controlled and adjusted to a pH of 9. The synthesis is carried out in 50 minutes with stirring at 350 rpm, with a permanent control of the temperature and the pH by means of a pH meter at a pH of 9. Once complete, the reaction mixture is filtered.

The cake obtained is dried in an oven at 40 ° C for 12 h.

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

Extrusions of the crystallized solid material having good cohesion and appearance are obtained.

The X-ray diffraction pattern of the extrudates of the crystallized solid material thus obtained is shown in FIG. 1 and confirms the presence of the Li ₂ S0 ₄ 4AI (OH) ₃ , nH ₂ 0 phase.

The chemical composition of the solid is Al = 20.9% by mass, S = 5.1% by mass, Li = 2.6% by mass

The extrudates obtained have a specific surface area: S _B ET = 5 m ² / g

Example 2 (according to the invention):

A crystallized solid material in powder form according to the invention is prepared according to a synthesis method according to the invention comprising a step of precipitation of at least one source of lithium and of aluminum sulphate and of sodium aluminate and a kneading - extrusion shaping step in the presence of inorganic binder precursors.

The first stages of precipitation and drying are carried out as in Example 1. 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 have good cohesion and a good appearance.

They are characterized by the following measures:

The X-ray diffraction pattern of the extruded crystallized solid material thus obtained confirms the presence of the Li ₂ S0 _4. 4AI (OH) ₃ , nH ₂ 0 phase and is identical to that shown in FIG.

The extrudates obtained have a specific surface area: S _B ET = 25 m ² / g Example 3 (according to the invention):

A crystallized solid material in powder form according to the invention is prepared according to a synthesis method according to the invention comprising a step of precipitation of at least one source of lithium and of aluminum sulphate and of sodium aluminate and a kneading-extrusion shaping step in the presence of an organic binder.

The first stages of precipitation and drying are carried out as in Example 1. 20.55 g of dried pulp obtained after drying are introduced into a tank of a Brabender type mixer. 2.055 g of Cerfobol R / 75 organic binder, ie 10% of dry organic matter of Cerfobol, or 0.61 g of dry organic mass relative to the mass of solid to form, which represents 3% mass of organic binder Cerfobol relative to the total mass of dry pulp to be shaped.

The mixture is then kneaded for 30 minutes.

The paste obtained is then shaped using a piston extruder (MTS) equipped with a cylindrical die 0.8 mm in diameter. The extrudates obtained are dried at 40 ° C. for 12 hours. The extrudates obtained have good cohesion and a good appearance.

They are characterized by the following measures:

The extrudates obtained have a specific surface area: S _B ET = 5 m ² / g

Example 4: Cohesion test

The mechanical strength of the extrudates obtained according to Examples 1, 2 and 3 according to the invention is tested in contact with a brine solution.

The different results are summarized in Table 1.

Table 1: MEF Protocol Implementation and Aspect of Corresponding Extrusions

1 (according to the invention) 2 (according to the invention) 3 (according to the invention)

Examples

aluminum sulphate aluminum sulphate aluminum sulphate

Step a) + aluminum aluminate + aluminate aluminate

sodium + LiCI sodium + LiCI sodium + LiCI

Mixing with binder

Mixing step with binder

Inorganic mineral direct extrusion

Organic Cerfobol shaping without binder generated in situ +

extrusion extrusion

Die 0.8 mm 0.8 mm 0.8 mm

Final drying

extruded 40 ° C, 12h 40 ° C, 12 h 40 ° C, 12 h

(step e)

Appearance of 0.8 mm die: 0.8 mm die: 0.8 mm die:

extruded at 40 ° C: extruded 40 ° C: extruded 40 ° C: extruded contact without defects without defects apparent brine apparent apparent defects The extrusions of the material according to the invention (examples 1 to 3) obtained according to a preparation process comprising a step of precipitating at least one source of lithium and of aluminum sulphate and of sodium aluminate 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.

Example 5: Mechanical resistance test by accelerated aging on a stirring table.

The mechanical strength of the extrudates can be tested by means of an accelerated aging protocol on a stirring table:

5 g of shaped solid material and 25 mL of natural brine are placed in a cylindrical container of 60 mL capacity. 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

The stirring table is animated by a horizontal unidirectional movement of amplitude 4 cm at a speed of 190 movements per minute. The shaped solids are stirred for a total of 168 hours.

At the end of these 168h, the brine-shaped solid mixture is sieved using a grid of 315 μηι. Then the shaped solids 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 μηι) in suspension, is filtered at room temperature. using a Buchner equipped with a filter paper whose pores have a dimension of 0.45 μηι. 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 solid residue mass to the initial shaped solid mass is then calculated, giving access to a percent destruction of the shaped solids. The percentage of destruction of the shaped solids makes it possible to assess the cohesion of the solids. Good cohesion is obtained in particular for solids whose percentage of destruction is less than 60%, and preferably less than 50%. The extrusions of Examples 1, 2 and 3 satisfy this condition.

Example 6 (according to the invention): 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 room temperature T = 20 ° C. by a first pass of a solution containing 3.4 mol / L of sodium chloride NaCl and 0.2 mol / L of lithium chloride LiCl, in a downflow at a flow rate of 3 BV / h. The volume of solution used is 14 BV.

The activation is then continued at room temperature T = 20 ° C. by a second passage of a solution containing 0.02 mol / L of lithium chloride LiCl, in downflow at a rate of 3 BV / h. The volume of solution used is 14 BV.

At the end of the activation step, the material of formula Li ₂ SO ₄ .Al (OH) 3, nH ₂ O is converted into LiCl ₂ Al (OH) ₃ , nH ₂ 0.

Once the activation step is complete, the loading is carried out using a natural brine whose composition is given in Table 3.

Table 3: Composition of natural brine used for loading

The loading of the activated adsorption material is carried out by passing the natural brine on said activated material at a temperature of 60 ° C., the temperature being maintained by means of a circulation of water heated in the 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 4 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 4.

Table 4: eluate composition and decontamination factors

The element concentrations in the brine and in the eluate are determined by the optical ICP method known to those skilled in the art.

The Cl concentrations in the eluate and brine are 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 (SO ₄ ).

Claims

1. Process for the preparation of a crystallized solid material in the form of extrudates of formula Li ₂ S0 _4. 4AI (OH) 3, nH ₂ 0 with n being between 0.01 and 10, said process comprising at least the following steps:

d) a step of extrusion shaping of said dried pulp to obtain extrusions,

e) 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 said material.

2. The method of claim 1 wherein the lithium source is lithium chloride (LiCl).

3. Method according to one of claims 1 or 2 wherein said step c) of drying is carried out in an oven at a temperature between 20 and 120 ° C for a period of between 1 h and 20 h.

4. Method according to one of claims 1 to 3 wherein said step d) shaping is carried out directly after step c) drying, said dried dough not undergoing intermediate steps between said step c ) and said step d) of extrusion shaping.

5. Method according to one of claims 1 to 3 wherein said step d) shaping is carried out by kneading - by extrusion of the dried pulp, in the presence of at least one organic binder selected from paraffins, and polymers, alone or in combination.

6. Method according to one of claims 1 to 3 wherein said step d) shaping is carried out by kneading - extrusion of the dried pulp in the presence of a binder formulation comprising at least one solid precursor of alumina and alumina. at least one acid in solution in proportions such that the acid / Al molar ratio is between 0.01 and 1.2.

7. - Crystalline solid material of formula Li ₂ S0 _4. 4AI (OH) 3, nH ₂ 0 with n being between 0.01 and 10, shaped, preferably in the form of extrudates.

8.- crystallized solid material of formula Li ₂ S0 _4. 4AI (OH) 3, nH ₂ 0 with n being between 0.01 and 10, in the form of extrudates, obtainable by a method as defined according to any one of claims 1 to 6.

A method of extracting lithium from saline solutions using said solid material as defined in claim 7 or 8.

The extraction method according to claim 9 wherein said lithium extraction process comprises at least the following steps:

1 1. An extraction process according to claim 10 wherein said activating step comprises a first upward or downward passage of a solution selected from salt solutions and sodium and lithium salt solutions, said sodium salt solution and lithium having a sodium salt concentration greater than 2 mol / L, and a lithium salt concentration of between 0 mol / L and 2 mol / L.

12. extraction process according to one of claims 10 to 1 1 wherein said activation step also comprises a second upward or downward passage of water or a solution of lithium salt having a concentration of between 0.001 mol / L and 0.1 mol / L

13. Extraction process according to one of claims 10 to 12 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.

14. Extraction method according to one of claims 10 to 13 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.

15. Extraction process according to one of claims 10 to 14 wherein said washing solution used in the washing step is an aqueous solution of sodium chloride

(NaCl) optionally comprising lithium chloride (LiCl) or water.

16. Extraction method according to one of claims 10 to 15 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.

17. Extraction process according to one of claims 10 to 16 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.

18. Extraction process according to one of claims 10 to 17 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.

19. 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 Li ₂ S0 _4. 4AI (OH) 3, nH ₂ 0 with n being between 0.01 and 10, shaped as defined in claim 7 or 8.