Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
  • B01J20/041—Oxides or hydroxides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
  • B01J20/046—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
  • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
  • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/3007—Moulding, shaping or extruding
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/30—Processes for preparing, regenerating, or reactivating
  • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
  • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
  • B01J39/10—Oxides or hydroxides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
  • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
  • B01J41/10—Inorganic material
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
  • C01D15/00—Lithium compounds
  • C01D15/04—Halides
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
  • C01F7/00—Compounds of aluminium
  • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
  • C01F7/021—After-treatment of oxides or hydroxides
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
  • C01F7/00—Compounds of aluminium
  • C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
  • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/12—Surface area

Definitions

• the present invention relates to the field of solid materials for the adsorption of lithium.
• the present invention relates to a new process for the preparation of a crystallized and shaped solid material, for example in the form of extrudates, of formula LiCI.2Al (OH) 3 , nH 2 O with n being included between 0.01 and 10, comprising at least one shaping step, for example by extrusion carried out in the absence of a binder and a final hydrothermal treatment step making it possible to increase the strength and the mechanical strength of the material when this it is brought into contact with a brine solution or a dilute solution and preferably in water.
• the present invention also relates to a process for extracting lithium from saline solutions using said crystallized solid material of formula LiCl 2 Al (OH) 3 , nH 2 O with n being between 0.01 and 10 prepared according to new preparation process according to the invention.
• 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.
• Lithium in the structure and thus the extraction of lithium Lithium in the structure and thus the extraction of lithium.
• a solid aluminum trihydroxide AI (OH) 3 prepared or commercial, is contacted with a lithium precursor.
• OH solid aluminum trihydroxide AI
• 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.
• 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 brine impregnated with concentrated NaX solution, c) elution of LiX salt captured by the solid by passage of an unsaturated solution of LiX,
• 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 LiCI.2Al (OH) 3 , nH 2 O powder to obtain a paste which is then shaped by granulation followed by drying in air.
• 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 LiCI.2Al (OH) 3 , nH 2 O powder to obtain a paste which is then shaped by granulation followed by drying in air.
• 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 defects and having good cohesion and good mechanical strength when it is put in 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.
• Another object of the present invention is to provide a solid material for the implementation of a lithium extraction process of 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 promotes 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 within a column.
• Applicants have discovered a novel process for preparing a crystalline solid material of the formula LiCI.2AI (OH) 3 , nH 2 0 with n ranging from 0.01 to 10, including a specific step combination and in particular that performing at the same time the step of forming a paste, in the absence of binder, directly after a drying step operating under specific conditions, the shaping step being then followed by another drying step also operating under specific conditions, then performing a final hydrothermal treatment step of the shaped materials provides a crystalline solid material of formula LiCI.2AI (OH) 3 , nH 2 0 of good quality , having good cohesion, without apparent defects and also having a good mechanical strength of the material when it is brought into contact with a brine solution or a dilute solution and preferably in water.
• the term "material of formula LiCl 2 Al (OH) 3 .nH 2 O” is preferably understood to mean a material comprising essentially or consisting of a crystalline phase of formula LiCl 2 Al (OH) 3 , nH 2 O.
• the subject of the present invention is a method for preparing a crystalline solid material of formula LiCl 2 Al (OH) 3 , nH 2 0 with n being between 0.01 and 10, said process comprising at least the following stages:
• step b) a filtration step of the suspension obtained in step a) to obtain a paste
• step b) a step of drying the paste obtained at the end of step b) at a temperature of between 20 and 80 ° C., preferably for a period of between 1 h and 12 h,
• step e) a step of drying the shaped material obtained at the end of step d) at a temperature of between 20 and 200 ° C., preferably for a duration of between 1 and 20 hours,
• step f) a step of hydrothermal treatment of the dried shaped material obtained at the end of step e), preferably at a temperature of between 50 and 200 ° C. and preferably for a duration of between 30 minutes and 12 hours; .
• binder means any organic or inorganic compound that may be added in the d) shaping stage, or any precursors of organic or inorganic compounds capable of forming an organic or inorganic binder. situ, under the conditions of step d) shaping
• An advantage of the preparation process according to the invention is that it makes it possible to obtain a shaped crystalline solid material of formula LiCl 2 Al (OH) 3 , nH 2 O with n being between 0.01 and 10, of good quality, without apparent defects, and in particular 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.
• shape 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, i.e. 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, for example by extrusion, prepared according to the invention are tested by means of a Aging protocol accelerated stirring table, either in brine or in water.
• 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.
• the solid mixture shaped-brine or water is sieved using a grid of 315 ⁇ . Then the shaped solids remaining on the sieve are washed with the medium used during the stirring.
• the liquid fraction thus obtained containing fine solid particles (diameter less than 315 ⁇ ) in suspension, is filtered using a Buchner equipped with a filter paper whose pores have a dimension of 0.45 ⁇ . 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 other dilute solutions and particular of water.
• the materials prepared according to the invention also have an improved mechanical strength compared to the materials of the prior art.
• 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 solutions and in particular water, less than 40% and preferably less than 30%.
• Another advantage of the preparation method according to the invention is that it makes it possible to obtain a crystallized solid material shaped, for example in the form of extrudates, of the formula LiCl 2 Al (OH) 3 , nH 2 O with n being between 0.01 and 10, having no or few cracks that could cause harmful swelling 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 crystalline solid material of formula LiCl 2 Al (OH) 3 , nH 2 0 with n being between 0.01 and 10, prepared according to the new preparation method according to the invention.
• An advantage of the extraction method according to the invention is to allow the selective extraction of lithium from a saline solution and thus obtain a high purification factor compared to the initial saline solution, calculated as the X / Li ratio which is equal to the molar ratio of X / Li concentrations in the initial saline solution divided by the molar ratio of X / Li concentrations in the final solution, X being selected from sodium (Na), potassium (K) , magnesium (Mg), calcium (Ca), boron (B), sulfur (S) and strontium (Sr).
• the subject of the present invention is also a crystallized solid material of formula LiCl 2 Al (OH) 3 , nH 2 0 with n being between 0.01 and 10, for example in the form of extrudates, obtainable according to a method of the invention.
• 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.
• At least one source of alumina and at least one source of lithium are mixed in an aqueous medium to obtain a suspension in step a).
• the source of alumina is Al (OH) 3 aluminum trihydroxide.
• Al (OH) 3 aluminum trihydroxide may advantageously be commercial.
• the aluminum trihydroxide Al (OH) 3 is prepared by precipitation of aluminum trichloride (AlCl 3 ) and sodium hydroxide (NaOH).
• AI (OH) 3 is prepared prior to mixing with at least one lithium source.
• Aluminum trichloride AlCl 3 and sodium hydroxide NaOH are advantageously mixed in the presence of water to form a precipitate which is advantageously filtered and washed at least once.
• the precipitate obtained is then mixed according to step a) with at least one lithium source to obtain a suspension.
• the lithium source (s) may be any compound comprising the lithium element and capable of releasing this element in aqueous solution in reactive form.
• 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 ), taken alone or as a mixture.
• the lithium source is lithium chloride (LiCl).
• At least one source of alumina and at least one source of lithium are mixed in the presence of water to obtain a suspension in step a).
• said mixing step a) operates with vigorous stirring.
• said mixing step a) is carried out at a temperature of between 40 and 120 ° C. and preferably between 60 and 100 ° C., preferably for a period of between 1 hour and 10 hours, preferably between 1 and 8 hours, preferably between 1 and 6 hours and more preferably between 1 and 3 hours.
• the suspension obtained at the end of step a) undergoes a step b) of filtration to obtain a paste.
• the filtration is carried out on a Buchner filter, by displacement of water.
• the paste obtained at the end of step b) is dried in a drying step c) at a temperature of between 20 and 80 ° C., for a duration for example of between 1 hour and 12 hours. h.
• said drying step operates, preferably in an oven, at a temperature between 20 and 60 ° C and very preferably between 30 and 50 ° C, for a period of time for example between 1 h and 10 h.
• the operating conditions of said drying step c) make it possible to obtain a dried pulp with a loss on ignition (PAF) of between 45 and 75% and preferably between 50 and 70%.
• PAF loss on ignition
• the loss on ignition obtained allows shaping, for example by extrusion of the dried paste in good conditions and obtaining resistant extrudates without defects, ie without cracks.
• 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.
• said dried paste obtained at the end of the drying step c) undergoes, directly after the drying step c), a step d) of shaping, said forming step being performed in the absence of binder.
• said shaping step d) is carried out in the absence of binders chosen from inorganic binders, such as, for example, hydraulic binders or inorganic binders that can be generated under the conditions of said step d) by addition of precursors of inorganic binders, and organic binders, such as for example paraffins or polymers.
• binders chosen from inorganic binders, such as, for example, hydraulic binders or inorganic binders that can be generated under the conditions of said step d) by addition of precursors of inorganic binders, and organic binders, such as for example paraffins or polymers.
• the solid material according to the invention does not comprise a binder, especially chosen from inorganic binders and organic binders.
• said shaping step d) is carried out according to the methods known to those skilled in the art, such as for example by extrusion, by pelletization, by the method of coagulation in drop (oil-drop), by granulation turntable.
• said shaping step d) is carried out by extrusion.
• said dried paste does not undergo intermediate steps between said drying step c) and said extrusion shaping step d), preferably no kneading and mixing step. more preferably, no acid / basic mixing step.
• said extrusion forming step d) is carried out without the addition of acid or base to the dried pulp introduced in said step d).
• step d) extrusion shaping is advantageously carried out in a manner known to those skilled in the art.
• 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 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, and perhaps for example of circular, annular, trilobed, quadrilobed or multilobed section.
• the shaped solid material according to the invention can thus have such characteristics.
• the shaped solid material has a section or diameter 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 shaped material according to the present invention may be wire length for example between 1 and 10 cm, for example between 2 and 6 cm.
• the shape can be hollow (tubular) or full.
• the shaped material and for example the extrudates obtained at the end of step d) undergoes (ssen) a step e) of drying at a temperature of between 20 and 200 ° C. during a preferably between 1 hour and 20 hours, to obtain the crystalline solid material of formula LiCI.2AI (OH) 3 , nH 2 0 shaped, for example in the form of extrudates.
• said drying step e) is carried out at a temperature of between 20 and 100.degree. C., preferably between 20.degree. And 80.degree. preferred between 20 and 60 ° C, for a period of between 1 and 18 hours, preferably between 5 and 14 hours and preferably between 8 and 14 hours.
• Said drying step e) is advantageously carried out according to the techniques known to those skilled in the art and preferably in an oven.
• the dried shaped material and, for example, the extrudates obtained after step e) is (are) subjected to a hydrothermal treatment step, preferably at a temperature of between 50.degree. and 200 ° C and preferably for a period between 30 min and 12 hours.
• said step f) 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 for a period of time between 30 minutes and 120 hours.
• Said hydrothermal treatment step f) is advantageously carried out according to a technique known to those skilled in the art.
• said step f) is carried out in an autoclave, under autogenous pressure and under a saturated water atmosphere.
• said step f) 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.
• the shaped and dried material, for example extruded, obtained (s) at the end of step e) are not in contact with the liquid at the bottom of the autoclave.
• the acid is advantageously chosen from nitric acid, hydrochloric acid, sulfuric acid and carboxylic acid.
• the base is preferably selected from lithium hydroxide, sodium hydroxide, potassium hydroxide and ammonia.
• the lithium salt is advantageously chosen from lithium chloride and lithium carbonate.
• said step f) is carried out in the presence of a humid 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. weight.
• said step f) can be carried out in a climate drying oven, in the presence of a moist air stream containing between 20 and 100% by weight of water, preferably between 50 and 100% by weight, and preferably between 80 and 100% by weight of water, or in an oven operating under 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% by weight of water. according to the methods known to those skilled in the art.
• the hydrothermal treatment step f) in a controlled atmosphere makes it possible to obtain a crystalline solid material of formula LiCl 2 Al (OH) 3 , nH 2 O with n being between 0.01 and 10 shaded, for example in the form of extrudates, having good strength and good mechanical strength when it is placed in contact with a brine or a dilute solution and preferably water.
• the formed material for example in the form of extrudates obtained, is then advantageously recovered and may optionally be washed.
• Said shaped material, for example extrudates, obtained (s) at the end of step f) may then be optionally subjected to a drying step g), said drying step preferably operating at a temperature of between 15 and 50 ° C for a period of time for example between 1 h and 12 hours to obtain the crystalline solid material of formula LiCI.2AI (OH) 3 , nH 2 0 shaped.
• Said drying step g) is advantageously carried out according to the techniques known to those skilled in the art, and preferably in an oven.
• the process according to the present invention thus makes it possible to obtain a crystalline solid material of formula LiCl 2 Al (OH) 3 , nH 2 O with n being between 0.01 and 10, preferably between 0.1 and 5, and preferably between 0.1 and 1, for example in the form of extrudates with a 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.
• the X-ray diffraction pattern of the crystallized solid material of formula LiCl 2 Al (OH) 3 , nH 2 O with n being between 0.01 and 1, preferably between 0.1 and 0.5, and preferably between 0.1 and 0.4, obtained according to the invention, shaped, advantageously in the form of extrudates, is characteristic of a non-amorphous material and has at least the following lines:
• the preparation method according to the present invention therefore makes it possible to obtain a crystalline solid material of formula LiCI.2AI (OH) 3 , nH 2 O shaped, for example in the form of extrudates, having both a surface BET low specific, good cohesion, and having no apparent defect and having good strength and good mechanical strength when it is placed in contact with a brine or a dilute solution and preferably in the water.
• the good properties of the material obtained result from the combined effect of shaping, for example by extrusion of a paste, in the absence of binder, directly, after a drying step operating under specific conditions, the setting of 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.
• the subject of the present invention is also a process for extracting lithium from a saline solution using said crystalline solid material of formula LiCl 2 Al (OH) 3 , nH 2 O with n being between 0.01 and 10, 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. .
• 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.
• 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.
• alkali metals preferably sodium (Na), and potassium (K)
• alkaline earth metals preferably magnesium (Mg), calcium (Ca) and strontium ( Sr)
• Mg magnesium
• Ca calcium
• 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 LiCl 2 Al (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.
• said lithium extraction method according to the invention is implemented in a unit comprising between one and six columns, and preferably between two and three columns, comprising at least one bed of crystallized solid material of formula LiCl .2AI (OH) 3 , nH 2 0 with n being between 0.01 and 1.
• 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.
• said step of activating the crystallized solid material of formula LiCI.2AI (OH) 3 , nH 2 0 with n being between 0.01 and 10, for example in the form of extrudates, is carried out only once during of setting the synthesized material in a column 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.
• said activation step is advantageously carried out by ascending or descending, and preferably descending, passage of water or a lithium salt solution having a concentration of between 0.001 mol / L and 0.1 mol / L, preferably between 0.001 mol / L and 0.05 mol / L and preferably between 0.01 and 0.04 mol / L.
• the lithium salt used in solution in said activation step is chosen from lithium chloride (LiCl), lithium nitrate and lithium bromide.
• the lithium salt used in solution in said activation step is lithium chloride (LiCl).
• said activated crystallized solid material undergoes at the end of the activation step a washing step with a solution of lithium chloride (LiCl).
• Said activation step is advantageously carried out at a temperature between 0 ° C. and 90 ° C., and preferably between 10 ° C. and 60 ° C., and preferably between 10 ° C. and 30 ° C. at a flow rate between 0.1 BV / h and 30 BV / h, and preferably between 1 BV / h and 15 BV / h.
• the amount of solution required for activation is advantageously between 1 BV and 30 BV, preferably between 2 BV and 20 BV.
• BV means the volume occupied by the bed of the solid in the column.
• Said step of loading said adsorption-activated material is advantageously carried out by ascending or descending, and preferably ascending, saline solution treated in the extraction process according to the invention, on said activated material.
• Said loading step is advantageously carried out at a temperature of between 0 ° C. and 90 ° C., and preferably between 10 ° C. and 70 ° C. at a flow rate of between 0.1 BV / h and 30 BV / h, and preferably between 1 BV / h and 15 BV / h.
• the amount of solution necessary to saturate said material depends on the adsorption capacity of said material and the lithium concentration of the saline solution.
• the adsorption capacity of said material is between 1 and 50, preferably between 1 and 30 and preferably between 1 and 10 mg of Li / g of dry solid material.
• 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.
• 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 corresponds to the elimination of the impregnant resulting from the step of activating the solid material.
• This fraction can be considered as an effluent or recycled, and preferably recycled as an input stream of the desorption step.
• 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.
• 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.
• 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.
• NaCl sodium chloride
• LiCl lithium chloride
• 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.
• NaCl sodium chloride
• LiCl lithium chloride
• 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.
• 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.
• 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 .
• LiCl lithium chloride
• 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.
• LiCl lithium chloride
• 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.
• 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 purification factor with respect to the initial saline solution, calculated as being the ratio X / Li who 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 LiCl 2 Al (OH) 3 , nH 2 0 with n being between 0.01 and 10, preferably between 0.1 and 0.5 and preferably between 0.1 and 0.4, formed, as defined in the present invention.
• the invention covers a device implementing the lithium extraction method according to the invention.
• the device of the present invention comprises units or means implementing the various steps of the lithium extraction process according to the invention.
• FIG. 1 represents the X-ray diffraction pattern of the solid material of formula LiCI.2AI (OH) 3 , nH 2 O obtained in the form of extrudates according to Example 5 according to the invention.
• a solid material of formula LiCl 2 Al (OH) 3 , nH 2 0 is prepared with n being between 0.01 and 1, according to a synthesis method not in accordance with the invention in that the step of setting up The shape of the paste obtained is produced according to the conventional technique of acid / basic extrusion kneading, a technique implemented according to the knowledge of those skilled in the art and in that the process does not include a final hydrothermal treatment step.
• 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.
• the dried paste obtained is then shaped according to the conventional technique of mixing acid / basic extrusion.
• the dried pulp is introduced into a Brabender type mixer.
• the water acidified with nitric acid is added in 4 minutes, with mixing at 20 rpm.
• the acid mixing is continued for 10 minutes.
• a neutralization step is then carried out by adding an ammoniacal solution in the kneader and kneading is continued for 3 minutes.
• the mixing is carried out with a total acid content, expressed relative to the dried pulp of 2%, and a degree of neutralization of 20%.
• the wet solid obtained is shaped using a piston extruder (MTS) equipped with a cylindrical die 1 mm in diameter.
• MTS piston extruder
• a solid material of formula LiCl 2 Al (OH) 3 , nH 2 0 is prepared with n being between 0.01 and 1, according to a synthesis method not in accordance with the invention in that the step of setting up The shape of the paste obtained is produced by extrusion kneading in the presence of an inorganic binder of the family of hydraulic binders added during the kneading phase and in that the process does not include a final hydrothermal treatment step.
• Example 1 37.7 g of the solid material of formula LiCl 2 Al (OH) 3 , nH 2 0 with n being between 0.01 and 1 is obtained according to the process described in Example 1, with the difference that the shaping step is carried out by kneading - extrusion in the presence of an inorganic binder.
• the dried paste obtained after the first drying of Example 1 is introduced into a Brabender type mixer in the presence of 21.8 g of water and in the presence of 4.6 g of Dyckerhoff cement as a hydraulic binder. and is simply kneaded.
• the paste obtained is shaped using a piston extruder (MTS) equipped with a cylindrical die 1 mm in diameter.
• MTS piston extruder
• the extrudates obtained at the end of the shaping step are then dried in an oven at 40 ° C. for 12 hours.
• the extrudates obtained at the end of the shaping step were also dried in a climate oven at 25 ° C. for 48 hours in saturated air with 98% water.
• a solid material of formula LiCl 2 Al (OH) 3 , nH 2 O is prepared with n being between 0.01 and 1, according to a synthetic process not in accordance with the invention, in that the step of calcining extruded is carried out according to the knowledge of those skilled in the art at a temperature above 500 ° C and in that the process does not include a final hydrothermal treatment step.
• 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.
• the paste obtained is shaped directly using a piston extruder
• 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.
• the paste obtained is shaped directly using a piston extruder (MTS) without any intermediate kneading step of said paste.
• the extruder piston is equipped with a cylindrical die 0.8 mm in diameter. These extrudates are then dried at 40 ° C. for 12 hours in an oven.
• the extrudates obtained do not undergo a hydrothermal treatment step in an autoclave according to the invention.
• the extrudates obtained are also characterized by the following measurements: Elemental analysis shows a good Li / Al / Cl stoichiometry corresponding to the composition of a LiCI.2Al (OH) 3 , nH 2 O structure
• the extrudates are prepared as in Example 4 until the drying step in an oven at 40 ° C for 12h.
• 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.
• the hydrothermal treatment is carried out at a temperature of 100 ° C. for 6 h under a saturated water atmosphere.
• the elemental analysis shows a good Li / Al / Cl stoichiometry corresponding to the composition of a LiCI.2Al (OH) 3 , nH 2 O structure.
• the extrudates are prepared as in Example 4 except that the extrudates obtained are then subjected to a hydrothermal treatment step in an autoclave comprising in its bottom a mixture of water and nitric acid in order to obtain an equal pH at 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 acidified 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 hours under an atmosphere saturated with water.
• the elemental analysis shows a good Li / Al / Cl stoichiometry corresponding to the composition of a LiCI.2Al (OH) 3 , nH 2 O structure.
• the extrudates are prepared as in Example 4 except that the extrudates obtained are then subjected to a hydrothermal treatment step in an autoclave comprising in its bottom a mixture of water and sodium hydroxide to reach a pH equal to 1 1. 10 g of extrudates are placed in a basket placed in a 500 ml autoclave. In the bottom the autoclave is put 20 g of basic 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.
• Extracts of the solid material of formula LiCl 2 Al (OH) 3 , nH 2 O with n 0.25 having a good cohesion and a good appearance are obtained.
• the extrudates obtained are also characterized by the following measurements: Elemental analysis shows a good Li / Al / Cl stoichiometry corresponding to the composition of a LiCI.2Al (OH) 3 , nH 2 O structure
• Example 8 Cohesion and mechanical strength test by accelerated aging on stirring table.
• the mechanical strength of the extrudates can be tested via an accelerated stirring table aging protocol in two different environments:
• Table 1 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.
• the brine-shaped solid mixture is sieved using a grid of 315 ⁇ . Then the shaped solids remaining on the sieve are washed with the medium used during stirring (brine whose composition is shown in Table 1 or water).
• the liquid fraction thus obtained, containing fine solid particles (diameter less than 315 ⁇ ) in suspension, is filtered using a Buchner equipped with a filter paper whose pores have a dimension of 0.45 ⁇ . 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 as well as their mechanical strength. Good cohesion is obtained in particular for solids whose percentage of destruction is less than 60%, and preferably less than 50%.
• An improved strength and mechanical strength is obtained in particular for solids whose percentage of destruction is less than 40%, and preferably less than 30%.
• the mechanical strength of the extrudates obtained according to Examples 1 to 6 is tested in contact with a solution of natural brine and water.
• Example 9 (according to the invention): test of the materials produced according to Comparative Example 4 and Conformal Examples 5, 6 and 7 in the lithium extraction process according to the invention.
• Example 5 The material according to the invention prepared in Example 5 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 total volume of LiCl solution used is 14 BV.
• the loading is carried out using a natural brine whose composition is given in Table 3.
• 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.
• the adsorption capacity of the material is 4.7 mg Li / g dry solid material for a recovery efficiency of lithium of 93%.
• 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.
• 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.
• LiCl lithium chloride
• 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 purification factor which is equal to the X / Li molar ratio in the original 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 extrudates obtained according to Comparative Example 4 and Conformal Examples 5, 6 and 7 have sufficient cohesion for use in a column. Moreover, the materials prepared according to the invention generate less fines during their use. This property is an improvement because it makes it possible to limit the pressure drop, to limit the creation of preferential paths and to reduce the rate of renewal of the material.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Analytical Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Life Sciences & Earth Sciences (AREA)
• Geology (AREA)
• Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Solid-Sorbent Or Filter-Aiding Compositions (AREA)
• Manufacture And Refinement Of Metals (AREA)
• Inorganic Compounds Of Heavy Metals (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=51063671

Family Applications (1)

Country Status (7)

Families Citing this family (14)

Family Cites Families (8)

• 2014
  • 2014-04-25 FR FR1453779A patent/FR3020284A1/fr active Pending
• 2015
  • 2015-04-24 US US15/306,026 patent/US20170043317A1/en not_active Abandoned
  • 2015-04-24 WO PCT/EP2015/058973 patent/WO2015162272A1/fr active Application Filing
  • 2015-04-24 AR ARP150101237A patent/AR100178A1/es unknown
  • 2015-04-24 EP EP15720043.7A patent/EP3134202A1/de not_active Withdrawn
  • 2015-04-24 CN CN201580021946.9A patent/CN106457203A/zh active Pending
• 2016
  • 2016-10-20 CL CL2016002663A patent/CL2016002663A1/es unknown

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events