PROCESS FOR THE PREPARATION OF AN ADSORBENT MATERIAL COMPRISING A BOEHMITE PRECIPITATION STEP OPERAT

专利摘要:
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 and shaped solid material, preferably in extruded form, of formula LiXx.2Al (OH) 3, nH2O with n being between 0 , 01 and 10, where x is 1 when X is an anion selected from chloride, hydroxide and nitrate anions, and x is 0.5 when X is an anion selected from sulfate and carbonate anions, comprising a step a ) precipitation of boehmite under specific temperature and pH conditions, at least one shaping step, preferably by extrusion, said method also comprising a final hydrothermal treatment step, all to increase the capacity of lithium adsorption as well as the adsorption kinetics of the materials obtained with respect to the materials of the prior art when it is used in a lithium extraction process of saline solutions.
公开号:FR3036978A1
申请号:FR1555157
申请日:2015-06-05
公开日:2016-12-09
发明作者:Malika Boualleg；Fabien Burdet；Morgan Gohin
申请人:IFP Energies Nouvelles IFPEN；Eramet SA；
IPC主号:

专利说明:

[0001] PROCESS FOR PREPARING ADSORBENT MATERIAL COMPRISING A BOEHMITE PRECIPITATION STEP OPERATING IN SPECIFIC CONDITIONS AND METHOD OF EXTRACTING LITHIUM FROM SALINE SOLUTIONS USING THE SAME TECHNICAL FIELD The present invention relates to the field of solid adsorption of lithium. In particular, the present invention relates to a new process for the preparation of a crystallized and shaped solid material, preferably in extruded form, of formula LiXx.2A1 (OH) 3, nH20 with n being between 0 , 01 and 10, where x is 1 when X is an anion selected from chloride, hydroxide and nitrate anions, and x is 0.5 when X is an anion selected from sulfate and carbonate anions, comprising a step a ) precipitation of boehmite under specific temperature and pH conditions, at least one shaping step, preferably by extrusion, said method also comprising a final hydrothermal treatment step, all of the features of the method for to increase the adsorption capacity of lithium as well as the adsorption kinetics of the obtained materials compared to the materials of the prior art when it is used in a process for extracting lithium from the soil saline.
[0002] The present invention also relates to a method for extracting lithium from saline solutions using said crystallized solid material of formula LiXx.2A1 (OH) 3, nH20 with n, x and X having the above definition prepared according to the new process preparation according to the invention.
[0003] 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 3036978 2 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 prepared or commercially available Al (OH) 3 aluminum trihydroxide solid 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 LiOH solution to a polycrystalline hydrated alumina to form LiOH / Al (OH) 3, and thus create active lithium sites 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 thus prepared alumina pellets are then used in a process for extracting lithium from high temperature brines. 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 NaX solution, 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 LiC1.2A1 (OH) 3, nH20 comprising a step of mixing aluminum trichloride (AIC13) and lithium carbonate (Li2CO3) in the presence water at 40 ° C. The residue obtained is filtered and washed and then dried for 4 hours at 60 ° C. The balance thus obtained is not formatted. The solid obtained is used for the extraction of lithium contained in salt solutions by contact with water in order to remove a portion 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 preparing 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 contacting said microcrystals with a 6% solution of lithium chloride LiCl at 80 ° C for 2 hours followed by filtration, rinsing and drying for obtain a powder of LiC1.2A1 (OH) 3, nH20 with an unordered and amorphous structure. A solution of a macromolecular polymer selected from fluorinated resins, polyvinyl chloride (PVC), chlorinated polyvinyl chloride (CPVC), ethylene perchlorate and cellulose acetate butyrate (CAB) serving as the The 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 lithium salt extraction process of saline brines makes it possible to obtain a low Mg / Li ratio and a mother liquor rich in lithium and in accordance with the standards for the production of carbonates or chlorides. of 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, with no apparent defect and having good cohesion and good mechanical strength when the latter is brought into contact with a brine solution or in water. 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 of extracting lithium from saline solutions using said solid material.
[0004] Another object of the present invention is to provide a solid material for carrying out a process for extracting lithium from saline solutions, in which the solid material makes it possible to limit the generation of fine particles, in particular because the fine particles increase the pressure drop, promote the creation of preferential paths and increase the rate of renewal of the material during the passage of the brine through a bed of a material in a column. Applicants have discovered a new process for preparing a crystallized solid material of the formula LiXx.2A1 (OH) 3, nH20 with n being between 0.01 and 10, x being 1 when X is an anion selected from chloride, hydroxide and nitrate anions, and x being 0.5 when X is an anion selected from sulfate and carbonate anions, including a specific step combination and in particular that performing both the step a) precipitation of boehmite under specific temperature and pH conditions, the step of forming a paste, preferably by extrusion, after a drying step operating under specific conditions, the step of setting The form is then followed by another drying step also operating under specific conditions, and then carrying out a final hydrothermal treatment step of the shaped materials makes it possible to obtain a crystallized solid material. formula LiXx.2A1 (OH) 3, nH20 without apparent defects having both a good cohesion, a good mechanical strength of the material when it is brought into contact with a brine solution or in water and having a capacity lithium adsorption as well as improved adsorption kinetics over prior art materials when used in a saline lithium extraction process. Without being bound to any theory, the applicants have demonstrated that the implementation of step a) of precipitation under the operating conditions of temperatures and pH as defined according to the invention makes it possible to obtain a Boehmite precipitate composed of small crystallites. In particular, the precipitate of boehmite obtained has a size, obtained by the Scherrer formula in X-ray diffraction according to the crystallographic directions [020] and [120], respectively between 0.5 and 10 nm and between 0.5 and 15 nm and preferably respectively between 0.5 to 2 nm and between 0.5 to 3 nm and very preferably respectively between 0.5 and 1.5 nm and between 0.5 and 2.5 nm. Scherrer's formula is a formula used in X-ray diffraction on powders or polycrystalline samples which connects the width at half height of the diffraction peaks to the size of the crystallites. It is described in detail in the reference: Appl. Cryst. (1978). 11, 102-113 Scherrer after sixty years: A survey and some new results in the determination of crystallinity size, J. I. Langford and A. J. C. Wilson. The method according to the invention comprising a precipitation step a) as claimed thus makes it possible to obtain a crystallized solid final material of formula LiXx.2A1 (OH) 3, nH20, with n being between 0.01 and 10 X, having the above definition, also poorly crystalline but having a lithium adsorption capacity as well as improved adsorption kinetics compared to prior art materials when used in an extraction process. Lithium salt solutions. SUMMARY AND INTERESTS OF THE INVENTION The term "material of formula LiXx.2A1 (OH) 3, nH20" is preferably understood to mean a material comprising essentially or consisting of a crystallized phase of formula LiXx.2A1 (OH) 3, nH20, n, x and X having the above definition. The present invention relates to a process for preparing a crystallized solid material of formula LiXx.2A1 (OH) 3, nH20 with n being between 0.01 and 10, x being equal to 1 when X is an anion chosen from the anions chloride, hydroxide and nitrate, and x 3036978 being equal to 0.5 when X is an anion chosen from sulfate and carbonate anions, said process comprising at least the following stages: a) a step of precipitation of boehmite, in an aqueous medium, comprising contacting at least one basic precursor preferably selected from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide; and at least one acidic precursor preferably selected from aluminum sulphate, aluminum chloride, aluminum nitrate, sulfuric acid, hydrochloric acid, and nitric acid, wherein at least one one of the basic or acidic precursors comprises aluminum, to obtain a suspension of boehmite, said step a) being carried out at a temperature of between 5 and 35 ° C., and the quanti of the basic precursor being chosen from in order to obtain a pH of the end of precipitation in the reaction medium of between 7.5 and 9.5, b) a step of washing and filtration of the boehmite precipitate obtained in step a), c) a step of contacting the precipitate obtained in step b) with at least one lithium source, d) a filtration step of the suspension obtained in step c) to obtain a paste, e) a drying step of the paste obtained at the end of stage d) at a temperature of between 20 and 80.degree. a cure preferably between 1 h and 12 h, f) a step of forming said dried paste, g) a step of drying the shaped material obtained at the end of step f) at a temperature between 20 and 200 ° C, for a duration of preferably between 1 and 20 hours, h) a hydrothermal treatment step of the dried shaped material obtained at the end of step g), at a temperature between 50 and 200 ° C and for a period of preferably between 30 min and 12 hours. An advantage of the preparation process according to the invention is that it makes it possible to obtain a shaped crystallized solid material, preferably in the form of extrudates, of formula LiXx.2A1 (OH) 3, nH20 with n, x and X having the above definition, of good quality, without apparent defects, and having good cohesion and improved mechanical strength when it is brought into contact with a brine solution or a dilute solution and preferably in water. Another advantage of the present invention is to provide a process for preparing a shaped crystallized solid material, preferably in extruded form, of the formula LiXx.2A1 (OH) 3, nH20 with n, x and X having the above definition, having a lithium adsorption capacity and adsorption kinetics improved over prior art materials when it is used in a lithium salt extraction process.
[0005] The adsorption capacity of the aforementioned material is defined by the amount of lithium adsorbed for a given solution. It is calculated by those skilled in the art by integrating the amount of lithium fixed from a drilling curve also called leakage curve or saturation curve. The integration is carried out on the volume by the difference in lithium concentration between a solution after its loading on the aforementioned material 15 and the theoretical concentration without loading. This amount of material can be related to the amount of material used to obtain a capacity in milligrams of lithium per gram of solid. The kinetics of adsorption of the aforementioned material is measured by those skilled in the art by studying the shape of a drilling curve also called leakage curve or saturation curve. This curve is obtained by means of a column filled with the adsorbent material to form a homogeneous bed, percolating a saline solution containing lithium and by measuring the lithium concentration at the outlet of the adsorbent bed as a function of the volume of the solution used for a given flow. By adsorption capacity improved over the materials of the prior art is meant an adsorption capacity greater than 4.5 mg Li / g dry solid material. By dry solid material is meant a solid material dried at 200 ° C. for 12 hours. By "shaping" 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 substantially does not lose its physical integrity, that is, to say that it retains substantially its formatting. More specifically, a solid formed in the sense of the invention covers a solid maintaining its cohesion in the lithium extraction conditions defined in the examples. The cohesion as well as the mechanical strength of the shaped material, preferably by extrusion, prepared according to the invention are tested during the production of the drilling curves also called leakage curves or saturation curves. A solid exhibiting good mechanical strength does not produce fine particles and makes it possible to operate the column without observation of clogging. A solid having poor mechanical strength produces fine particles which induce clogging of the column. The cohesion as well as the mechanical strength of the shaped material, preferably by extrusion, prepared according to the invention are also tested by means of an accelerated aging protocol on a stirring table, either in a brine or in the water.
[0006] The stirring table is animated with 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 168 hours, the brine or water-shaped solid mixture is sieved through a mesh grid. The shaped solids remaining on the sieve are then washed with the medium used during filtration. agitation. The liquid fraction thus obtained, containing fine solid particles (diameter less than 315 μm) in suspension, is filtered using a Buchner equipped with a filter paper whose pores have a dimension of 0.45 μm. 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 materials prepared according to the invention makes it possible to assess the cohesion of said materials. Good cohesion is obtained in particular for materials whose percentage of destruction is less than 60%, and preferably less than 50%, when they are brought into contact with a solution of brine or any other dilute aqueous solution and especially water.
[0007] The materials prepared according to the invention also have an improved mechanical strength compared to the materials of the prior art. By "improved mechanical strength" is meant that the materials prepared according to the invention have a percentage of destruction, when they are brought into contact with a solution of brine or any other dilute aqueous solution and in particular water Less than 30% and preferably less than 20%.
[0008] Another advantage of the preparation process according to the invention is that it makes it possible to obtain a crystallized solid material shaped, preferably in the form of extrudates, of formula LiXx.2A1 (OH) 3, nH20 with n X and X having the above definition having no or few cracks which could cause swelling detrimental to the cohesion and mechanical strength of the material when it is brought into contact with a brine solution or a dilute solution and preferably in water. The subject of the present invention is also a method for extracting lithium from saline solutions using said shaped crystallized solid material of formula LiXx.2A1 (OH) 3, nH20 with n being between 0.01 and 10, where x is equal to at 1 when X is an anion selected from chloride, hydroxide and nitrate anions, and x being 0.5 when X is an anion selected from sulfate and carbonate anions, prepared according to the novel preparation method according to the invention . An advantage of the extraction process according to the invention is to allow the selective extraction of lithium from saline and thus obtain a high purification factor compared to the initial saline solution, calculated as 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).
[0009] The present invention also relates to a crystallized solid material of formula LiXx.2A1 (OH) 3, nH20 with n being between 0.01 and 10, x being equal to 1 when X is an anion chosen from chloride anions, hydroxide and nitrate, and x being equal to 0.5 when X is an anion chosen from sulphate and carbonate anions, preferably in the form of extrudates, obtainable according to a method of the invention.
[0010] 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 In accordance with the invention, the process comprises a step a) of precipitating boehmite in an aqueous reaction medium, said step comprising contacting at least one basic precursor preferably chosen from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide; and at least one acidic precursor preferably selected from aluminum sulfate, aluminum trichloride, aluminum nitrate, sulfuric acid, hydrochloric acid, and nitric acid, wherein at least one of the basic or acidic precursors comprises aluminum, to obtain a boehmite suspension, said step a) being carried out at a temperature between 5 and 35 ° C, and the amount of the basic precursor being chosen so as to obtain a pH of precipitation end in the reaction medium of between 7.5 and 9.5. The mixture in the aqueous reaction medium of at least one basic precursor and at least one acidic precursor requires either that at least the basic precursor or the acidic precursor comprises aluminum, or that the two precursors basic and acidic include aluminum.
[0011] Preferably, the basic precursor is sodium hydroxide (NaOH). Preferably, the acidic precursor is aluminum trichloride (AIC13). Preferably, the basic precursor (s) and acid (s) are added in said first precipitation step a) in aqueous solutions. Preferably, the aqueous reaction medium is water.
[0012] Preferably, said step a) is carried out with stirring. Preferably, said boehmite precipitation step a) is carried out at a temperature between 5 and 30 ° C, and preferably between 10 and 30 ° C and very preferably between 10 and 25 ° C, and the quantity of the basic precursor being chosen so as to obtain a pH of the end of precipitation in the reaction medium of between 7.5 and 9 and preferably between 7.7 and 8.8. Preferably, the precipitation step a) is carried out for a period of between 10 minutes and 5 hours, preferably between 15 minutes and 2 hours. Said step a) of precipitation makes it possible to obtain a suspension of precipitated boehmite or aluminum oxyhydroxide (AIOOH).
[0013] The implementation of step a) of precipitation under the operating conditions of temperatures and pH as defined makes it possible to obtain a boehmite precipitate having small crystallites. The term "small crystallites" means a precipitate of boehmite composed of crystallites whose size, obtained by the Scherrer formula in X-ray diffraction according to the crystallographic directions [020] and [120], is respectively between 0.5 and 10 nm and between 0.5 and 15 nm and preferably respectively between 0.5 to 2 nm and between 0.5 to 3 nm and very preferably respectively between 0.5 and 1.5 nm and between 0, 5 and 2.5 nm. According to the invention, the process comprises a step b) of washing and filtration of the boehmite precipitate obtained at the end of step a).
[0014] Preferably, said washing step is a water washing step.
[0015] According to the invention, the process comprises a step c) of bringing the boehmite precipitate obtained in step b) into contact with at least one lithium source. 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 lithium salts and preferably from lithium chloride (LiCl), lithium hydroxide (LiOH), nitrate Lithium (LiNO3), lithium sulphate (Li2SO4) and lithium carbonate (Li2CO3), alone or as a mixture. Very preferably, the lithium source is lithium chloride (LiCl).
[0016] In this case, X is the chloride anion and x = 1. Preferably, the boehmite precipitate obtained in step b) and at least one lithium source are mixed in the presence of water to obtain a suspension in step c). Preferably, said mixing step c) is carried out with vigorous stirring.
[0017] Preferably, said contacting step c) is carried out at a temperature between 20 and 95 ° C and preferably between 50 and 95 ° C, and preferably between 70 and 95 ° C for a period of time between 15 minutes and 12 hours and preferably between 30 minutes and 5 hours. According to the invention, the suspension obtained at the end of step c) undergoes a d) filtration step to obtain a paste. According to the invention, the paste obtained at the end of step d) is dried in a drying step e), preferably at a temperature of between 20 and 80 ° C., for a period of preferably between 1 hour and 1 hour. 12 pm Preferably, said drying step is carried out, 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 e) 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 shaping, preferably by extrusion, of the dried dough under good conditions and the production of shaped materials, preferably in the form of extrudates, which are resistant and without apparent defects. is without crack. In order to determine the PAF before the shaping step, a portion of the paste obtained is removed and placed in an oven for 6 hours at 200 ° C. The PAF is obtained by difference between the mass of the sample before and after passage in the oven.
[0018] According to the invention, said dried paste obtained at the end of the drying step e) undergoes a f) shaping step. Preferably, said shaping step f) is carried out according to the methods known to those skilled in the art, such as, for example, extrusion, pelletizing, by the method of drop coagulation (oil-drop), by granulation at the turntable. Preferably, said shaping step f) is carried out by extrusion. Very preferably, said step f) is carried out by direct extrusion or by extrusion-mixing.
[0019] Direct shaping of the dried dough resulting from step e) is understood to mean a step in which said dried dough does not undergo intermediate steps between the drying step e) and its introduction into the extruder and in particular no mixing step. The term "kneading-extrusion step" is understood to mean a step in which the dried pulp obtained at the end of the drying step e) undergoes, in a first kneading step, in the presence or absence of at least one binder or compound. binder precursor, then the paste is then subjected to an extrusion step. Said e) shaping-extrusion shaping step is advantageously carried out in a manner known to those skilled in the art.
[0020] Preferably, said dried paste obtained at the end of drying step e), and optionally at least said binder or binder precursor, in the case where they are present, are mixed, preferably in a single 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 kneading conditions are adjusted in a manner known to those skilled in the art and aim to obtain a homogeneous and extrudable paste. In the extrusion kneading processes known to those skilled in the art, the extrudability of the dough may advantageously be adjusted with the addition of water and / or acid in solution, in order to obtain a paste suitable for performing step 30 e) 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.
[0021] According to a first embodiment of step f), said shaping step f) may advantageously be implemented directly after the drying step e). Preferably, step f) of direct shaping of the dried paste is carried out in the absence of a binder chosen from inorganic binders, such as, for example, hydraulic binders or inorganic binders that can be generated. under the conditions of said step e) by adding precursors of inorganic binders, and organic binders, such as for example paraffins or polymers. In this case, said dried paste is preferably not subjected to an intermediate step between said drying step e) and said extrusion forming step f), and preferably no mixing step and more preferably preferred no acid / basic mixing step. Thus, more preferably, said forming step f) according to the first embodiment is carried out without addition of acid or base to the dried pulp introduced in said step f).
[0022] Said step f) of shaping by direct extrusion is advantageously carried out in a manner known to those skilled in the art. In particular, the dried paste resulting from the drying step e) advantageously passes through a die, using, for example, a piston or a continuous twin-screw or single-screw extruder. The diameter 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 cross-section, trilobal, quadrilobed or multilobed.
[0023] According to a second embodiment of step f), said shaping step f) can advantageously be carried out by kneading-extrusion in the presence of at least one binder chosen from organic or inorganic binders and preferably without adding acid or base to the dried pulp introduced in said step f). In said second embodiment of step f), the kneading step is preferably carried out without the addition of acid or base. Thus, no step of acidification or neutralization of the dried pulp is carried out in step e) of shaping-extrusion forming 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 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 with a trilobal, quadrilobed or multilobed circular cross section.
[0024] Said organic binder (s) which may be used in said shaping step (d) are advantageously chosen from paraffins and polymers, alone or as a mixture. Preferably, said at least one organic binder (s) is chosen from polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), an aqueous dispersion of a mixture of paraffin waxes and polyethylene, for example for example Cerfobol R75, polysaccharides, methylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose and carboxymethylcellulose and taken alone or as a mixture, preferably from polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA) and an aqueous dispersion of a mixture of paraffin waxes and polyethylene such as for example Cerfobol R75, and preferably polyvinylpyrrolidone (PVP) and polyvinyl alcohol (PVA). A very preferred organic binder is polyvinylpyrrolidone (PVP). Cerfobol R75 comprises 28.4% dry paraffinic organic mass diluted in an aqueous phase.
[0025] The proportion of said one or more organic binder (s) added in said shaping step e) is advantageously between 0.5 and 20% by weight, preferably between 0.5 and 15% by weight. mass, preferably between 1 and 13% 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 e) of the process according to the invention. The addition of at least one organic binder in said step e) also makes it possible to obtain a crystallized solid material in the form of extrudates with improved stirring resistance in contact with the brine. Preferably, said inorganic binder (s) used in said shaping step (e) are advantageously chosen from silicic binders, clay-type binders and inorganic binders which can be generated. under the conditions of said step e) by addition of inorganic binder precursors. Preferably, said inorganic binder (s) used in said shaping step e) are advantageously chosen from silicic binders.
[0026] Preferably, the silicic binders are advantageously chosen from precipitated silica and silica derived from by-products such as fly ash such as, for example, silico-aluminous or silico-calcic particles, silicic acid, metasilicate of sodium and silica fumes. Colloidal silica, for example in the form of a stabilized suspension, such as, for example, commercial products such as Ludox® or Klebosol® may also be used. Preferably, the silicic binder is in amorphous or crystalline form. Very preferably, the silica is used in powder form or in colloidal form. The proportion of said one or more inorganic binder (s) added in said shaping step (d) is advantageously between 0.5 and 20 by weight, preferably between 0.5 and 15% by weight. preferably between 1 and 13% by weight, relative to the total mass of dry pulp to be shaped. The addition of at least one inorganic binder in said step e) facilitates its extrusion shaping.
[0027] The addition of at least one inorganic binder in said step e) also makes it possible to obtain a shaped crystallized solid material, preferably in the form of extrudates having an improved stirring resistance in contact with the brine. In the case where said step e) 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 e), said step e) of setting in the 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 / AI is between 0.01 and 1.2.
[0028] The introduction into shaping step f) of a solid precursor of alumina and an acid in solution allows the in situ generation of a mineral binder resulting from the reaction of the alumina precursor and introduced acid, during said shaping step. On the other hand, the solid precursor of alumina and the acid in solution must be introduced in said step f) 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.
[0029] The solid precursor of alumina is advantageously chosen from aluminum oxides, aluminum hydroxides and aluminum oxyhydroxides which are soluble or dispersible in the phosphoric acid solution, preferably from aluminum hydroxides and aluminum oxyhydroxides. Very preferably, said solid alumina precursor is 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 (Mastersizer granulometer Malvern), between 9 10 and 80 preferably between 10 and 60 lm and preferably between 15 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 f) is between 0.5 and 50% by weight relative to the mass of dry paste to be shaped, preferably between 2 and 30%. in bulk, 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. Most 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 alumina solid precursor become with the action of the acid and mechanical energy provided during the shaping step f), an amorphous phase of inorganic binder. Preferably, the acid (s) 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. .
[0030] 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 5 is derived from the solid precursor of alumina. 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 and preferably.
[0031] The use of an acid / Al molar ratio of between 0.01 and 1.2, which is 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 extrusion shaping and to increase the cohesion and mechanical strength of the extrudates obtained according to this embodiment. According to the invention, the shaped material and preferably the extrudates obtained at the end of step d) undergoes (ssen) a step g) drying at a temperature between 20 and 200 ° C for oneureure preferably between 1 hour and 20 hours, to obtain the crystalline solid material of formula 20 LiXx.2A1 (OH) 3, nH20 shaped, preferably in the form of extrudates. Preferably, said drying step g) is carried out at a temperature of between 20 and 100 ° C., preferably between 20 and 80 ° C. and very preferably between 20 and 60 ° C., preferably for a period of time. preferably between 1 and 18 hours, preferably between 5 and 14 hours and preferably between 8 and 14 hours. The specific conditions of said drying step e) make it possible to obtain a crystallized solid material having the desired LiXx.2A1 (OH) 3, nH20 phase. Said drying step g) is advantageously carried out according to the techniques known to those skilled in the art and preferably in an oven.
[0032] In accordance with the invention, the dried shaped material and preferably the extrudates obtained at the end of step g) are (are) subjected to a hydrothermal treatment step at a temperature of between 50.degree. 200 ° C and for a period of preferably between 30 min and 12 hours. Preferably, said step h) is carried out at a temperature between 70 and 200 ° C, preferably between 70 and 180 ° C, and very preferably between 80 and 150 ° C, for example during a duration between 30 minutes and 120 hours. Said hydrothermal treatment step h) is advantageously carried out according to a technique known to those skilled in the art.
[0033] According to a preferred embodiment, said step h) is carried out in an autoclave, under autogenous pressure and under a saturated water atmosphere. Preferably, said step h) is carried out by introducing a liquid at the bottom of the autoclave, said liquid being chosen from water, alone or as a mixture with at least one acid, a base or a lithium salt. Preferably, the shaped and dried material, and preferably the extrudates obtained at the end of step g) are not in contact with the liquid at the bottom of the autoclave. In the case where water is introduced into the autoclave in admixture with an acid, the acid is advantageously chosen from nitric acid, hydrochloric acid, sulfuric acid and carboxylic acid.
[0034] In the case where water is introduced into the autoclave in admixture with a base, the base is preferably selected from lithium hydroxide, sodium hydroxide, potassium hydroxide and ammonia. In the case where water is introduced into the autoclave mixed with a lithium salt, the lithium salt is advantageously chosen from lithium chloride and lithium carbonate. Preferably, said step h) is carried out in the presence of a moist atmosphere comprising a water content of between 20 and 100% by weight, and preferably between 50 and 100% by weight, and preferably between 80 and 100% by weight. % by mass relative to the total mass of the atmosphere in the autoclave.
[0035] According to one embodiment, said step h) can be carried out in a climate drying oven, in the presence of a humid air stream containing between 20 and 100% by weight of water, preferably between 50 and 100% by weight, and preferably between 80 and 100% water mass, or in an oven operating under a moist air flow containing between 20 and 100% by weight of water, preferably between 50 and 100% by weight and preferably between 80 and 100% by weight. water mass according to the methods known to those skilled in the art. The hydrothermal treatment step h) in a controlled atmosphere makes it possible to obtain a crystalline solid material of formula LiXx.2A1 (OH) 3, nH20 with n being between 0.01 and 10, x being equal to 1 when X is an anion selected from chloride, hydroxide and nitrate anions, and x being 0.5 when X is an anion selected from sulphate and carbonate anions, preferably shaped as extrudates, having a good held and good mechanical strength when it is placed in contact with a brine or a dilute solution and preferably water. At the end of said step h), the material, preferably shaped in the form of extrudates, obtained is then advantageously recovered and may optionally be washed. Said shaped material and preferably the extrudates obtained at the end of step h) can then optionally be subjected to a drying step i), said drying step preferably operating at a temperature of a temperature of between 15 and 50 ° C for a duration of preferably between 1 hour and 12 hours to obtain the crystallized solid material of formula LiXx.2A1 (OH) 3, nH20 with n being between 0.01 and 10, x being 1 when X is an anion selected from chloride, hydroxide and nitrate anions, and x being 0.5 when X is an anion selected from sulfate and carbonate shaped anions. Said drying step i) is advantageously carried out according to the techniques known to those skilled in the art, and preferably in an oven. The method according to the present invention thus makes it possible to obtain a crystallized solid material of formula LiXx.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, x being 1 when X is an anion selected from chloride, hydroxide and nitrate anions, and x being 0.5 when X is an anion selected from sulfate and carbonate anions, preferably in the form of section extrusions (larger dimension of the cross section) or diameter of 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.
[0036] 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 section extrusions (larger dimension of the cross section) or diameter between 0. , 2 and 5 mm and preferably between 0.3 and 1.8 mm, said extrudates having been obtained by the combination of a specific shaping step as described above and a step of i) final drying carried out at a temperature between 20 and 200 ° C, preferably between 20 and 60 ° C and in particular at 40 ° C, for a period of preferably between 1 and 20 hours, preferably between 5 and and 14 hours, preferably between 8 and 14 hours and in particular for 8 hours.
[0037] The crystalline solid material of formula LiXx.2A1 (OH) 3, nH20 shaped, preferably in the form of extrudates, prepared according to the sequence of steps a) to i) of the preparation process according to the invention may be to 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 field of diffraction angle θ = 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 LiXx.2A1 (OH) 3, nH20 shaped, preferably in the form of extrudates, advantageously has a specific surface area measured according to the BET method of between 1 and 30 m 2 / g and preferably between 1 and 20 m2 / g. The X-ray diffraction pattern of the material in the form of extrudates corresponds to a crystallized solid of formula LiXx.2A1 (OH) 3, nH20 according to JCPDS sheet No. 0031-07-00, with n being between 0.01 and 10, preferably between 0.1 and 0.5, preferably between 0.1 and 5 and most preferably between 0.1 and 1, obtained according to the invention, shaped, advantageously in the form of extruded. The preparation method according to the present invention thus makes it possible to obtain a crystallized solid material of formula LiXx.2A1 (OH) 3, nH20, n, x and X having the above definition shaped preferably in the form of extrudates having both a low BET specific surface area, a good cohesion, and having no apparent defect and exhibiting good strength and mechanical strength when placed in contact with a brine or diluted solution and preferably in water. The good properties of the material obtained result from the combined effect of shaping, preferably by extrusion of a paste, in the absence of a binder, directly, after a drying step operating under specific conditions, of the setting in. implementation of a drying step according to the shaping, also operating under specific conditions and also the implementation of a final hydrothermal treatment step operating preferably in an autoclave. Furthermore, the crystallized solid material formed, preferably in the form of extrudates, thus obtained of formula LiXx.2A1 (OH) 3, nH20 with n, x and X having the above definition, has an adsorption capacity lithium and adsorption kinetics improved over prior art materials when it is used in a lithium extraction process of saline solutions. The materials obtained according to the invention have an improved adsorption capacity compared to the materials of the prior art greater than 4.5 mg Li / g dry solid material, i.e. solid dried at 200 ° C, preferably between 4.5 and 10 mg Li / g, preferably between 4.5 and 8 and very preferably between 4.5 and 7 mg Li / g solid material dry. The present invention also relates to a process for extracting lithium from a saline solution using said crystallized solid material of formula LiXx.2A1 (OH) 3, nH20 with n being between 0.01 and 10, x being equal to 1 when X is an anion chosen from chloride, hydroxide and nitrate anions, and x being equal to 0.5 when X is an anion chosen from sulfate and carbonate anions, prepared 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. 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 concentrated brines made of lithium, water seawater, 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 lithium extraction process. 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 method 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 LiXx.2A1 (OH) 3, nH20, with n, x and X having the above definition, shaped and prepared according to the preparation method according to the invention.
[0038] Preferably, said lithium extraction process according to the invention is carried out in a unit comprising at least two columns, and preferably between two and three columns, comprising at least one bed of crystallized solid material of formula LiXx.2A1 (OH) 3, nH20, with n, x and X having the above definition.
[0039] Said lithium extraction method advantageously comprises at least the following steps: a step of activating said crystallized solid material of formula LiXx.2A1 (OH) 3, nH20, with n, x and X having the above definition, a step loading 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 desorption step of lithium made by passing water or an aqueous solution of lithium salt on said material to obtain an eluate comprising at least lithium. Preferably, the lithium extraction method according to the invention comprises a prior step of setting said material in a column. Preferably, said step of activating the crystallized solid material of formula LiXx.2A1 (OH) 3, nH20, with n, x and X having the above definition, preferably shaped, and preferably in the form of extrudates , is carried out only once during the columnization of the synthesized material 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.
[0040] Preferably, said activation step is advantageously carried out by the ascending or descending passage, and preferably descending, of an activation solution chosen from water and a lithium salt solution having a concentration of between 0.001 mol. 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.
[0041] 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).
[0042] Said activation step is advantageously carried out 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. with a residence time of 30 ° C. this activation solution is preferably stored in the column between 0.03 and 10 h, and preferably between 0.06 and 1 h.
[0043] The amount of solution required for activation is advantageously between 1 and 30 column volumes, preferably between 2 and 20 column volumes. The column volume or "Bed Volume" according to the English terminology is also called the volume occupied by the bed of the solid in the column or BV according to the terminology specific to the technical field known to those skilled in the art.
[0044] Said activated crystallized solid material may optionally undergo at the end of the activation step a washing step with a washing solution and preferably a solution of lithium chloride (LiCl). 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. Advantageously, said loading step is advantageously carried out at a temperature between 0 ° C. and 90 ° C., and deference between 10 ° C. and 70 ° C. with a residence time of said solution, preferably of said treated saline solution. in the column preferably between 0.03 and 10 h, and preferably between 0.06 and 1 h. Preferably, 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 the materials according to the invention is greater than 4.5 mg Li / g dry solid material, preferably between 4.5 and 10 mg Li / g, preferably 4.5 and 8 and most preferably between 4.5 and 7 mg Li / g 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.
[0045] 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. below, while loading the other two columns.
[0046] The first fraction of the output stream of said adsorption loading step, advantageously between 0 and 1 column volumes, corresponds to the removal of the impregnant 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, above 1 column volume, the entire output stream of said adsorption loading step, hereinafter referred to as raffinate, which has undergone no chemical treatment, is preferably and preferably returned to the original salt solution deposit. At the end of the step of loading by passing the treated saline solution 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) 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 descending. 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 of sodium chloride (NaCl), greater than 0.5 mol / l, preferably of between 2 mol / l and saturation and a concentration of lithium salt and of preferably lithium chloride (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 between 0 ° C. and 90 ° C., and preferably between 10 ° C. and 10 ° C., and with a residence time of said solution, preferably of said wash solution in the column between 0.03 and 10 h, and preferably between 0.06 and 1 h. The amount of solution required for washing is between 0.1 and 10 column volumes, and preferably in the range 0.5 to 5 column volumes. The exit stream of said washing step is considered an effluent or is advantageously recycled, and preferably recycled at the inlet of the loading step or directly at the inlet of the second column in the case where said process extraction of lithium according to the invention is carried out in a unit comprising at least two columns. 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 concentrated 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 to desorb elements such as boron, sulphates, alkalis other than lithium and sodium 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 .
[0047] Preferably, said desorption step is carried out by ascending or descending, and preferably descending, passage of a desorption solution selected from water and 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 70 ° C. and 70 ° C., with a residence time of said desorption solution in the column preferably between 0.degree. , 03 and 10 h, and preferably between 0.06 and 1 h. The amount of lithium chloride solution (LiCl) required for the desorption is advantageously between 0.01 and 10 column volumes, and preferably between 0.05 and 5 column volumes. 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 and 4 column volumes, and preferably between 0.2 and 3 column volumes.
[0048] The whole of the other fractions of the output stream of this step not constituting the final product called the eluate, is considered as an effluent or is advantageously recycled, and preferably recycled at the inlet of the washing step or the loading step.
[0049] 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.
[0050] 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 purification factor relative to the initial saline solution, calculated as the X / Li ratio 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 selected 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 LiXx.2A1 (OH) 3, nH20 with n being between 0.01 and 10, x being 1 when X is an anion selected from chloride, hydroxide and nitrate anions, and x being equal to 0.5 when X is an anion selected from sulfate anions and carbonate, 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 FIGS. 1, 3, 5 and 7 show the X-ray diffraction patterns of the precipitated boehmites obtained respectively in Examples 1 and 2 according to the invention and 3 and 4 not in accordance with the invention.
[0051] Figures 2, 4, 6 and 8 show the X-ray diffraction patterns of solid materials of formula LiXx.2A1 (OH) 3, nH20 with X = Cl, x = 1 and n being between 0.01 and 10 obtained in the form of extrusions respectively in Examples 1 and 2 according to the invention and 3 and 4 not in accordance with the invention.
[0052] FIG. 9 represents the saturation curve according to example 5, made from the extrudates obtained in examples 1 to 4. The invention is illustrated by the following examples, which in no way present a limiting character.
[0053] Examples: Example 1: (according to the invention): A solid material of formula LiC1.2A1 (OH) 3, nH20 is prepared with n being between 0.01 and 1, according to a synthesis method according to the invention in which the shaping step is carried out by direct extrusion, without binder. AoOH boehmite precipitation 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) was prepared. Then, with magnetic stirring, 67.5 g of sodium hydroxide (NaOH) are added for 30 minutes to adjust the pH. The pH reached at the end of the synthesis is 8. The temperature is maintained at 20 ° C. throughout the cure of the precipitation stage. This cake is suspended in a 3 L beaker with 320 mL of water. A sample of the precipitate obtained is taken from the reaction medium. The DRX (FIG. 1) of the precipitate shows that the precipitate obtained in example 1 is indeed a boehmite precipitate. The boehmite precipitate obtained in Example 1 is poorly crystallized. The crystallite size of the boehmite obtained is measured according to the Sherrer method: Size according to [020] = 0.6 ± 0.1 (nm); Size according to [120] = 1.4 ± 0.1 (nm) 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., which loses 8 hours, follow the first 2 steps.
[0054] The solid material thus prepared is characterized by the formula LiC1.2A1 (OH) 3, nH20 with n = 0.25 according to a synthesis method according to the invention. The shaping step of the paste obtained is carried out directly after the drying step, without prior mixing step and in the absence of binder. The paste obtained is shaped using a piston extruder (MTS) equipped with a cylindrical die 1 mm in diameter. The extrudates are prepared as in Example 4 until the drying step in an oven at 40 ° C for 12 hours. The resulting extrudates are then subjected to an autoclave hydrothermal treatment step comprising water. 10 g of extrudates are placed in a basket placed in a 500 ml autoclave. In the bottom of the autoclave are put 20 g of distilled water. The extrudates are not in contact with the liquid at the bottom of the autoclave. The hydrothermal treatment is carried out at a temperature of 100 ° C. for 6 h under a saturated water atmosphere.
[0055] Extrudates of the solid material of formula LiC1.2A1 (OH) 3, nH20 with n = 0.25 having good cohesion and appearance are obtained. A phase LiC1.2A1 (OH) 3, nH20 is detected on the X-ray diffraction pattern of the extruded solid material of formula LiC1.2A1 (OH) 3, nH20 with n = 0.25 obtained in Example 1 ( Figure 2).
[0056] The extrudates obtained are also characterized by the following measurements: The elemental analysis shows a good Li / Al / Cl stoichiometry corresponding to the composition of a LiC1.2A1 (OH) 3 structure, nH20 Al = 21.2% by mass; Li = 4.2% mass; Cl, = 19% mass. The extrudates obtained have a specific surface area: SBET = 3 m 2 / g.
[0057] The extrudates obtained according to Example 1 have a good visual cohesion, have no or very few cracks, and have both a very good cohesion and a very good mechanical strength when they are in contact with a brine ( percentage of destruction less than 15% during the cohesion test) or water (percentage of destruction less than 20% during the cohesion test).
[0058] EXAMPLE 2 (According to the Invention): A solid material of formula LiC1.2A1 (OH) 3, nH20, with n being between 0.01 and 1, according to a synthesis method according to the invention, is prepared in which the shaping step is carried out by direct extrusion, without binder. 1 / precipitation of boehmite AIOOH 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) is added for 30 minutes to adjust the pH. The pH reached at the end of the synthesis is 8.5. The temperature is maintained at 20 ° C throughout the duration of the step. This cake is suspended in a 3 L beaker with 320 mL of water. A sample of the precipitate obtained is taken from the reaction medium. The DRX (Figure 3) of the precipitate shows that the precipitate obtained in Example 2 is indeed a boehmite precipitate. The boehmite precipitate obtained in Example 2 is poorly crystallized. The crystallite size of the boehmite obtained is measured according to the Sherrer method: Size according to [020] = 0.9 ± 0.1 (nm); Size according to [120] = 1.6 ± 0.2 (nm) 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., which loses 8 hours, follow the first 2 steps. The solid material thus prepared thus prepared is characterized by the formula LiC1.2A1 (OH) 3, nH20 with n = 0.25 according to a synthesis method according to the invention. The shaping step of the paste obtained is carried out directly after the drying step, without prior mixing step and in the absence of binder. 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.
[0059] The resulting extrudates are then subjected to an autoclave hydrothermal treatment step comprising water. 10 g of extrudates are placed in a basket placed in a 500 ml autoclave. In the bottom of the autoclave are put 20 g of distilled water. The extrudates are not in contact with the liquid at the bottom of the autoclave. The hydrothermal treatment is carried out at a temperature of 100 ° C for 6 h under a saturated atmosphere of water.
[0060] Extruded solid material of formula LiC1.2A1 (OH) 3, nH20 with n = 0.25 having good cohesion and a good appearance are obtained. A LiC1.2A1 (OH) 3, nH20 phase is detected on the X-ray diffraction pattern of the extrudates of the solid material of formula LiC1.2A1 (OH) 3, nH20 with n = 0.25 of FIG.
[0061] The extrudates obtained are also characterized by the following measurements: The elemental analysis shows a good Li / Al / CI stoichiometry corresponding to the composition of a LiC1.2A1 (OH) 3 structure, nH20 Al = 20.00% by weight; Li = 4.03% mass; Cl = 20.5% mass, C = 5.87% mass. The extrudates obtained have a specific surface area: SBET = 3 m 2 / g.
[0062] The extrudates obtained according to Example 2 visually exhibit good cohesion, have no or only few cracks and exhibit both very good cohesion and very good mechanical strength when they are brought into contact with a brine ( percentage of destruction less than 15% during the cohesion test) or water (percentage of destruction less than 20% during the cohesion test).
[0063] EXAMPLE 3 (Comparative): A solid material of formula LiC1.2A1 (OH) 3, nH20 is prepared with n being between 0.01 and 1, according to a synthesis method not according to the invention, in that the precipitation end pH of the boehmite synthesis step is carried out at a pH greater than 9.5. 1 / precipitation of boehmite AIOOH 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) is added for 30 minutes to adjust the pH. The pH reached at the end of the synthesis is 10. The temperature is maintained at 20 ° C. for the duration of the stage. This cake is suspended in a 3 L beaker with 320 mL of water. A sample of the precipitate obtained is taken from the reaction medium. The DRX (FIG. 5) of the precipitate shows that the precipitate obtained in Example 3 is indeed a boehmite precipitate. The crystallite size of the boehmite obtained is measured according to the Sherrer method: Size according to [020] = 2.1 ± 2 (nm); Size according to [120] = 2.8 ± 3 (nm) 2 / Addition of lithium chloride LiCl.
[0064] 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., which loses 8 hours, follow the first 25 steps. The shaping step of the paste obtained is carried out directly after the drying step, without prior mixing step and in the absence of binder. The paste obtained is shaped using a piston extruder (MTS) equipped with a cylindrical die 1 mm in diameter.
[0065] Extrudates of the solid material of formula LiC1.2A1 (OH) 3, nH20 with n = 0.25 having good cohesion and appearance are obtained. A phase LiC1.2A1 (OH) 3, nH20 is detected on the X-ray diffraction pattern of the extruded solid material of formula LiC1.2A1 (OH) 3, nH20 with n = 0.25 of FIG. The elemental analysis shows a good Li / Al / Cl stoichiometry corresponding to the composition of a structure LiC1.2A1 (OH) 3, nH20 Al = 20.00% by weight; Li = 4.03% mass; Cl = 20.5% mass, C = 5.87% mass. The extrudates obtained have a specific surface area: SBET = 3 m 2 / g. The extrudates obtained according to Example 3 visually exhibit good cohesion, have no or very few cracks and exhibit both very good cohesion and very good mechanical strength when they are brought into contact with a brine ( percentage of destruction less than 15% during the cohesion test) or water (percentage of destruction less than 20% during the cohesion test).
[0066] EXAMPLE 4 (Comparative): A solid material of formula LiC1.2A1 (OH) 3, nH20 is prepared with n being between 0.01 and 1, according to a synthesis method not according to the invention, in that the temperature of the precipitation step of boehmite is carried out at a temperature of 40 ° C. AoOH boehmite precipitation 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) was prepared. Then, with magnetic stirring, 67.5 g of sodium hydroxide (NaOH) are added for 30 minutes to adjust the pH. The pH reached at the end of the synthesis is 8.
[0067] The temperature is maintained at 40 ° C throughout the duration of the step. This cake is suspended in a 3 L beaker with 320 mL of water. A sample of the precipitate obtained is taken from the reaction medium. The DRX (Figure 7) of the precipitate shows that the precipitate obtained in Example 4 is indeed a boehmite precipitate. The crystallite size of the boehmite obtained is measured according to the Sherrer method: Size according to [020] = 1.9 ± 3 (nm); Size according to [120] = 2.6 ± 2 (nm) 2 / Addition of lithium chloride LiCl.
[0068] 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., which loses 8 hours, follow the first 2 steps.
[0069] The shaping step of the paste obtained is carried out directly after the drying step, without prior mixing step and in the absence of binder. 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 are then subjected to a hydrothermal treatment step in an autoclave comprising water. 10 g of extrudates are placed in a basket placed in a 500 ml autoclave. In the bottom of the autoclave are put 20 g of distilled water. The extrudates are not in contact with the liquid at the bottom of the autoclave.
[0070] The hydrothermal treatment is carried out at a temperature of 100 ° C. for 6 hours under a saturated water atmosphere. Extruded solid material of formula LiC1.2A1 (OH) 3, nH20 with n = 0.25 having good cohesion and appearance are obtained. A LiC1.2A1 (OH) 3, nH20 phase is detected on the X-ray diffraction pattern of the extrudates of the solid material of formula LiC1.2A1 (OH) 3, nH20 with n = 0.25 of FIG. The extrudates obtained are also characterized by the following measurements: The elemental analysis shows a good Li / Al / CI stoichiometry corresponding to the composition of a structure LiC1.2A1 (OH) 3, nH20 Al = 20.00% by weight; Li = 4.03% mass; Cl = 20.51% mass.
[0071] The extrudates obtained have a specific surface area: SBET = 2 m 2 / g.
[0072] The extrudates obtained according to Example 4 have a good visual cohesion, have no or few cracks and have both a very good cohesion and a very good mechanical strength when they are in contact with a brine (percentage of destruction less than 15% in the cohesion test) or water (percentage of destruction less than 20% in the cohesion test). Example 5: adsorption capacity and adsorption kinetics test. The kinetics of lithium adsorption by the extrudates and their adsorption capacity is tested by the production of a drilling curve also known as a leakage curve or column saturation curve. A saturation curve is carried out for each of the extrudates obtained in Examples 1 to 4: 15 g of solid are placed in a column of 10 column volumes of a 0.02 mol / L lithium chloride (LiCl) saline solution. crosses the closed circuit column until a stable lithium concentration is reached in solution. A natural solution containing about 0.06 mol / L of lithium crosses the column by upward passage, at a rate of 6 BV / h, this is that is, six times the volume occupied by the extruded bed in one hour. The lithium concentration is measured at the outlet of the column as a function of the volume of solution passed. FIG. 9 illustrates the saturation curves obtained for each of the extrudates obtained in the examples according to the invention 1 and 2 and not in accordance with the invention 3 and 4. The extrudates obtained according to examples 1 and 2 according to the invention are compared to those obtained in Examples 3 and 4 obtained according to preparation methods not in accordance with the invention. The extrusions of Examples 1 and 2 obtained according to the invention show a leakage of lithium arriving at larger past brine volumes. Their lithium adsorption capacities are respectively 5.8 and 6.2 mg (Li) / g (dry solid), compared to 1.7 and 4.3 mg (Li) / g (dry solid) for solids. obtained according to Examples 3 and 4, according to methods of preparation not in accordance with the invention. 35

权利要求:
Claims (20)
[0001]
REVENDICATIONS1. Process for the preparation of a crystallized solid material of formula LiXx.2A1 (OH) 3, nH20 with n being between 0.01 and 10, x being equal to 1 when X is an anion chosen from chloride, hydroxide and nitrate anions , and x being equal to 0.5 when X is an anion chosen from sulphate and carbonate anions, said process comprising at least the following steps: a) a step of boehmite precipitation, in an aqueous medium, comprising bringing into contact at least one basic precursor preferably selected from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide; and at least one acidic precursor preferably selected from aluminum sulphate, aluminum chloride, aluminum nitrate, sulfuric acid, hydrochloric acid, and nitric acid, wherein at least one one of the basic or acid precursors comprises aluminum, to obtain a boehmite suspension, said step a) carried out at a temperature of between 5 and 35 ° C., and the amount of the basic precursor being chosen so as to obtain a pH of end of precipitation in the reaction medium of between 7.5 and 9.5, b) a step of washing and filtration of the boehmite precipitate obtained in step a), c) a step of contacting of the precipitate obtained in step b) with at least one lithium source, d) a filtration step of the suspension obtained in step c) to obtain a paste, e) a step of drying the paste obtained at from step d) at a temperature between 20 and 80 ° C for a period of preferably between 1h and 12h, f) a step of forming said dried paste, g) a step of drying the shaped material obtained at the end of step f) at a temperature between 20 and 200 ° C, for a period preferably between 1 and 20 hours, h) a hydrothermal treatment step of the dried shaped material obtained at the end of step g) at a temperature between 50 and 3036978 34 200 ° C and for a period of preferably between 30 min and 12 hours.
[0002]
2. The process according to claim 1, wherein the basic precursor is sodium hydroxide (NaOH).
[0003]
3. Method according to one of claims 1 or 2, wherein the acidic precursor is aluminum trichloride (AIC13). 10
[0004]
4. Method according to one of claims 1 to 3, wherein said step a) of precipitation of the boehmite is carried out at a temperature between 10 and 25 ° C.
[0005]
5. Method according to one of claims 1 to 3, wherein the amount of the basic precursor is chosen so as to obtain a pH of the end of precipitation of said step a) in the reaction medium of between 7.7 and 8, 8.
[0006]
6. Method according to one of claims 1 to 5, wherein the source (s) of lithium is (are) selected from lithium chloride (LiCl), lithium hydroxide (LiOH) Lithium nitrate (LiNO3), lithium sulphate (Li2SO4) and lithium carbonate (Li2CO3), alone or as a mixture.
[0007]
The method of claim 6, wherein the lithium source is lithium chloride (LiCl). 25
[0008]
8. Method according to one of claims 1 to 5, wherein said f) shaping step is performed by extrusion.
[0009]
The method of claim 8, wherein said shaping step (f) is carried out directly after the drying step e).
[0010]
10. Crystalline solid material of formula LiXx.2A1 (OH) 3, nH20 with n being between 0.01 and 10, x being equal to 1 when X is an anion chosen from chloride, hydroxide and nitrate anions, and x being equal to 0.5 when X is an anion chosen from sulphate and carbonate anions, shaped, preferably in extruded form, obtainable by a process as defined in any one of claims 1 to 9.
[0011]
11. A process for extracting lithium from saline solutions, said process using said solid material of formula LiXx.2A1 (OH) 3, nH20 with n being between 0.01 and 10, x being equal to 1 when X is an anion chosen from chloride, hydroxide and nitrate anions, and x being equal to 0.5 when X is an anion chosen from sulfate and carbonate anions, prepared according to the process as defined according to one of claims 1 to 9; or as defined in claim 10 for the extraction of lithium from saline solutions.
[0012]
12. Extraction process according to claim 11, wherein said lithium extraction process comprises at least the following steps: an activation step of said crystallized solid material of formula LiXx.2A1 (OH) 3, nH20, a step of loading said activated adsorption material made 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 step lithium desorption method performed by passing water or an aqueous solution of lithium salt on said material to obtain an eluate comprising at least lithium.
[0013]
13. Extraction process according to claim 12, 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. L and 0.1 mol / L.
[0014]
14. Extraction process according to claim 13, wherein said activating step is carried out at a temperature between 0 ° C and 90 ° C, and with a residence time of said lithium chloride solution or water in the column between 0.03 and 10 h.
[0015]
15. Extraction method according to one of claims 12 to 14, wherein said charging step is carried out at a temperature between 0 ° C and 90 ° C, and 3036978 36 with a residence time of said salt solution in the column between 0.03 and 10 h.
[0016]
16. Extraction method according to one of claims 12 to 15, wherein said washing solution used in the washing step is water or an aqueous solution of sodium chloride (NaCl), optionally comprising chloride of lithium (LiCl).
[0017]
17. Extraction method according to one of claims 12 to 16, wherein said washing step is carried out at a temperature between 0 ° C and 90 ° C, and with a residence time of said washing solution in the column between 0.03 and 10 h.
[0018]
18. Extraction process according to one of claims 12 to 17, wherein said desorption step is carried out by upward or downward passage of a desorption solution selected from water and a solution of lithium chloride (LiCl ) containing from 0.001 mol / L to 2 mol / L of LiCl.
[0019]
19. Extraction method according to one of claims 12 to 18, wherein said desorption step is carried out at a temperature between 0 ° C and 90 ° C, and with a residence time of said desorption solution in the column between 0.03 and 10 h.
[0020]
20. 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 prepared according to the process as defined according to one of claims 1 at 9, or as defined in claim 10.

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优先权:

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申请号 | 申请日 | 专利标题

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FR1555157|2015-06-05|

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FR1555157A|FR3036978B1|2015-06-05|2015-06-05|PROCESS FOR THE PREPARATION OF AN ADSORBENT MATERIAL COMPRISING A PRECIPITATION STEP OF BOEHMITE OPERATING UNDER SPECIFIC CONDITIONS AND METHOD FOR EXTRACTING LITHIUM FROM SALINE SOLUTIONS USING THE SAME|FR1555157A| FR3036978B1|2015-06-05|2015-06-05|PROCESS FOR THE PREPARATION OF AN ADSORBENT MATERIAL COMPRISING A PRECIPITATION STEP OF BOEHMITE OPERATING UNDER SPECIFIC CONDITIONS AND METHOD FOR EXTRACTING LITHIUM FROM SALINE SOLUTIONS USING THE SAME|

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ARP160101658A| AR104902A1|2015-06-05|2016-06-03|PREPARATION PROCEDURE FOR AN ABSORBENT MATERIAL THAT INCLUDES A BOEHMITA PRECIPITATION STAGE|

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US15/579,811| US10786802B2|2015-06-05|2016-06-03|Process for preparing an adsorbing material comprising a precipitating step of boehmite according to specific conditions and process for extracting lithium from saline solutions using this material|

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CN201680032816.XA| CN107787248B|2015-06-05|2016-06-03|Method for preparing adsorbent material comprising step of precipitating boehmite under specific conditions and method for extracting lithium from salt solution using the same|

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EP16730287.6A| EP3302787A1|2015-06-05|2016-06-03|Method for preparing an adsorbent material comprising a step of precipitating boehmite taking place under specific conditions and method for extracting lithium from saline solutions using said material|

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PCT/EP2016/062667| WO2016193439A1|2015-06-05|2016-06-03|Method for preparing an adsorbent material comprising a step of precipitating boehmite taking place under specific conditions and method for extracting lithium from saline solutions using said material|

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CL2017003061A| CL2017003061A1|2015-06-05|2017-12-01|Process for preparing and adsorbing material comprising a step of precipitation of boehmite under specific conditions and lithium extraction process from saline solutions using this material|