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  • C01F7/00—Compounds of aluminium
  • C01F7/78—Compounds containing aluminium, with or without oxygen or hydrogen, and containing two or more other elements
  • C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
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  • C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
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  • 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
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  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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  • 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
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  • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
  • B01J20/28004—Sorbent size or size distribution, e.g. particle size
  • B01J20/28007—Sorbent size or size distribution, e.g. particle size with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like
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  • 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
  • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
  • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
  • B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
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  • 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
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
  • C01D15/00—Lithium compounds
  • C01D15/02—Oxides; Hydroxides
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  • 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
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  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/62222—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic coatings
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  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
  • C04B35/62605—Treating the starting powders individually or as mixtures
  • C04B35/62625—Wet mixtures
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  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
  • C04B35/62605—Treating the starting powders individually or as mixtures
  • C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
  • C04B35/62675—Thermal treatment of powders or mixtures thereof other than sintering characterised by the treatment temperature
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  • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
  • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
  • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
  • C04B35/632—Organic additives
  • C04B35/636—Polysaccharides or derivatives thereof
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
  • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
  • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
  • C04B2235/3218—Aluminium (oxy)hydroxides, e.g. boehmite, gibbsite, alumina sol
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  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
  • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
  • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
  • C04B2235/3222—Aluminates other than alumino-silicates, e.g. spinel (MgAl2O4)
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  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
  • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
  • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
  • C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
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  • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
  • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
  • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
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  • C04B2235/78—Grain sizes and shapes, product microstructures, e.g. acicular grains, equiaxed grains, platelet-structures
  • C04B2235/781—Nanograined materials, i.e. having grain sizes below 100 nm

Definitions

• TITLE Product comprising lithiated bayerite and process for manufacturing such a product
• the present invention relates to a product comprising lithiated bayerite and to a process for manufacturing a product comprising lithiated bayerite.
• Brines are sources of lithium, for which extraction of said lithium is necessary.
• This extraction, or capture can be carried out using columns filled with an active material, which selectively and reversibly captures lithium when the brine is in contact with it.
• the lithium is then recovered by passing an aqueous solution through these columns.
• the result is a concentrated lithium solution which will be purified before a precipitation step, generally in the form of lithium carbonate.
• Lithium adsorbents in particular lithiated bayerite, are materials advantageously used as active material allowing the obtaining of the concentrated lithium solution within the extraction columns.
• FR3053264 describes a process for preparing a crystallized solid material of formula (LiCI) x .2AI(OH) 3 , nH 2 O with x between 0.4 and 1 and n being between 0.01 and 10.
• US4,348,295 describes a process for manufacturing LiX.2AI(OH) 3 , nH 2 O, X being an anion forming an acid in molecular combination with H or forming a salt in combination with a metal ion, said process comprising a step of reaction of a hydrated alumina with a concentrated solution of LiX at a temperature above 85 °C.
• the material obtained by this process has a limited lithium adsorption capacity.
• this aim is achieved by means of a product comprising, and preferably essentially consisting of:
• the average size of lithiated bayerite crystallites and the cumulative level of aluminum hydroxide and boehmite are measured on said product after exposure to air for 170 hours at 25°C, at atmospheric pressure.
• Said dry product is obtained after drying in air at 200°C for 16 hours, at atmospheric pressure.
• the product has the following chemical analysis, determined on the dry product by inductively coupled plasma spectrometry, in weight percentages:
• the water content is greater than 1%, preferably greater than 5%, preferably greater than 10% and/or preferably less than 95%, preferably less than 80%, preferably less than 70%; the cumulative level of aluminum hydroxide and boehmite is less than or equal to 8%, preferably less than or equal to 5%;
• the crystallized phases of the product comprise lithiated bayerite, boehmite and/or an aluminum hydroxide chosen from gibbsite, bayerite, doyleite, nordstrandite and their mixtures, preferably the crystallized phases of the product comprise lithiated bayerite and an aluminum hydroxide chosen from gibbsite, bayerite, doyleite, nordstrandite and mixtures thereof;
• the only crystallized phase present in the product is lithiated bayerite;
• the product consists of at least 80%, by mass, of water and crystallites of lithiated bayerite, and of aluminum hydroxide and/or boehmite, and of LiCI, and of a binder, preferably the product consists of at least 80%, by mass, of water and crystallites of lithiated bayerite, and of aluminum hydroxide, and of LiCl, and of a binder, preferably the product consists of at least 80% %, by mass, of water and crystallites of lithiated bayerite, and LiCl, and a binder, said binder preferably being a polysaccharide, preferably an alginate.
• the invention also relates to a process for manufacturing a product according to the invention and as previously described, comprising the following steps: a) Aqueous suspension of a source of aluminum, preferably a single source of aluminum aluminum, chosen from a boehmite or an aluminum hydroxide and their mixtures, preferably an aluminum hydroxide, grinding of said aqueous suspension so as to obtain a median size less than or equal to 3 pm if the median size of said source of aluminum is greater than 3 ⁇ m, said suspension being maintained during this step a) at a temperature below 50 ° C, b) Increasing the pH by adding a base, such that the molar ratio between the OH provided by said base and the AI present in the mixture is greater than 0.20, said mixture being kept stirring after introduction of said base, at a temperature below 50°C; c) Addition of a chlorine salt, such that the molar ratio between the Cl provided by said chlorine salt and the AI present in the mixture is greater than 0.25, said mixture being kept stirring after introduction of said chlorine salt at
• Step a) comprises carrying out grinding of the aqueous suspension of a source of aluminum chosen from boehmite or an aluminum hydroxide and their mixtures, so as to obtain a median size ⁇ 1 pm;
• the time t 5 is such that the times ti, t 2 , t 3 and t 4 satisfy the following relationships: [ti/(- 1.2Ti+75)] + [t 2 /(-1.2T 20 +75 )] + [t 3 /(-1.2T 30 +75)] + [t 4 /(-1.2T 40 +75)] ⁇ 1, preferably [ti/(-0.8Ti+50)] + [t 2 /(-0.8T 20 +50)] + [t 3 /(-0.8T 30 +50)] + [t 4 /(-0.8T 40 +50)] ⁇ 1, preferably [ ti/(-0.55Ti+34.5)] + [t 2 /(-0.55T 20 +34.5)] + [t 3 /(-0.55T 30 +34.5)] + [t 4 /(- 0.55T 40 +34.5)] ⁇ 1, and [ti/(-0.225Ti+14.25)] + [t 2 /(-0.225
• the pH of the mixture is reduced to a value less than 7.5 and greater than 6.5;
• the CI/AI molar ratio in the mixture is set to a value less than 3;
• the temperature of the mixture is substantially constant
• the time t 3 is greater than 5 minutes
• step g the time t 4 is less than 15 minutes
• the method comprises, after step g), a step h) of shaping a starting charge comprising the paste obtained at the end of step g), in the form of an object or a coating, preferably in the form of an object, and an optional step i) of reducing the water content of said object or said coating;
• the starting charge comprises a binder, preferably a polysaccharide comprising a group capable of forming an ionic bond with a gelling agent for the formation of a gelled polysaccharide, preferably a polysaccharide chosen from alginates;
• steps h) and i) are carried out, at least partially, simultaneously.
• the invention finally relates to a lithium capture device, in particular an extraction column, comprising a product according to the invention or a product obtained by the process according to the invention as described previously.
• Lithiated bayerite is called the compound of formula LiCI.2AI(OH) 3 .xH 2 O as indicated in the ICDD PDF 00-031 -0700 sheet, but also by extension, compounds presenting a ratio of molar quantities lithium and aluminum, Li/AI different from 0.5. In some modes it may be less than 0.5. In other modes, it may be greater than 0.5.
• the compound of formula AI(OH) 3 is called “aluminum hydroxide”. Gibbsite, bayerite, doyleite and nordstrandite are aluminum hydroxides.
• - AHA is the sum of the areas of the aluminum hydroxide phases, measured on an in copper, without deconvolution treatment, after eliminating the Ka2 line.
• the area of an aluminum hydroxide phase is that of its diffraction peak located in an angular range 29 substantially equal to 18.3°;
• ABO is the area of the diffraction peak of boehmite located in an angular range 29 substantially equal to 14°, measured on the same diagram, without deconvolution treatment, after eliminating the Ka2 line;
• - ABL is the area of the diffraction peak of the (993) plane of lithiated bayerite located in an angular range 29 substantially equal to 11.3°, measured on the same diagram, without deconvolution treatment, after eliminating the line Ka2.
• Polysaccharides are polymers composed of sequences of saccharide units linked by glycosidic bonds.
• Gelable polysaccharide under the action of a gelling agent is a polysaccharide capable of forming a gel under the action of said gelling agent.
• alginate has the formula (CsHyOe ⁇ n.
• Alginate is a polysaccharide chain comprising COO- carboxylate groups.
• Calcium Ca 2+ ions (gelling agent) react with two strands of alginate, that is to say with the COO- carboxylate groups, leading to the polymerization of the alginate chains and the bonding of the molecules together. The reaction thus allows the creation of a gel.
• dry product means a product obtained after drying in air at 299°C for 16 hours (at atmospheric pressure), this drying being for example conventionally carried out in an oven.
• median size of a powder of particles or a suspension of particles, the size dividing said particles of the powder or suspension, into first and second populations equal in mass, these first and second populations not comprising only particles having a size greater than or equal to, or less than, respectively, the median size.
• the median size can, for example, be determined using a laser particle size analyzer.
• the water content is the loss of mass, expressed as a percentage, after drying at 200°C for 16 hours in air, at atmospheric pressure;
• An average size of lithiated bayerite crystallites of less than 23 nm, preferably less than 20 nm;
• a cumulative level of aluminum hydroxide and boehmite less than or equal to 8%, preferably less than or equal to 5%, preferably substantially zero;
• the crystallized phases comprise, preferably consist of lithiated bayerite, boehmite and/or an aluminum hydroxide chosen from gibbsite, bayerite, doyleite, nordstrandite and mixtures thereof, preferably gibbsite.
• the crystallized phases comprise, preferably consist of lithiated bayerite and an aluminum hydroxide chosen from gibbsite, bayerite, doyleite, nordstrandite and their mixtures, preferably gibbsite.
• the only crystallized phase is lithiated bayerite.
• the determination of the crystallized phases, the determination of the cumulative rate of aluminum hydroxide and boehmite and the measurement of the size of the lithiated bayerite crystallites are carried out on the product after exposure to air for 170 hours at 25°C, at atmospheric pressure;
• Li preferably greater than 2.5%, preferably greater than 3%, and/or preferably less than 4.5%, preferably less than 4%, and
• - Cl preferably greater than 11%, preferably greater than 13% and/or preferably less than 24%, preferably less than 22%, and
• Al preferably greater than 17%, preferably greater than 19% and/or preferably less than 28%, preferably less than 26%;
• Li in a content greater than 2%, preferably greater than 2.5%, preferably greater than 3% and less than 5%, preferably less than 4.5%, preferably less than 4%, and
• - Cl in a content greater than 10%, preferably greater than 11%, preferably greater than 13% and less than 26%, preferably less than 24%, preferably less than 22%, and
• the product After drying in air at 200°C for 16 hours, at atmospheric pressure, the product has a Li/Al mass ratio greater than 0.1, preferably greater than 0.15 and/or preferably less than 0.3 , preferably less than 0.25;
• the product After drying in air at 200°C for 16 hours, at atmospheric pressure, the product has a Li/CI mass ratio greater than 0.08, preferably greater than 0.1, preferably greater than 0.13, preferably greater than 0.15 and/or preferably less than 0.4, preferably less than 0.3, preferably less than 0.25;
• the product consists, for at least 80%, preferably for more than 85%, preferably for more than 90%, preferably for more than 95%, preferably for more than 99% by mass, of water and crystallites of lithiated bayerite, and aluminum hydroxide and/or boehmite, and LiCI, and a binder, preferably a polysaccharide, preferably a gelled polysaccharide, preferably an alginate, preferably a gelled alginate.
• the product consists of at least 80%, preferably more than 85%, preferably more than 90%, preferably more than 95%, preferably more than 99% by mass, of water. and said crystallites and aluminum hydroxide and LiCl and a binder, preferably a polysaccharide, preferably a gelled polysaccharide, preferably an alginate, preferably a gelled alginate.
• the product consists of at least 80%, preferably more than 85%, preferably more than 90%, preferably more than 95%, preferably more than 99% by mass, of water. and said crystallites and LiCI and a binder, preferably a polysaccharide, preferably an alginate;
• the product comes in the form of objects in the shape of cylinders, polylobed, rings, or spheres.
• said objects have a larger dimension less than 100 mm, preferably less than 80 mm, preferably less than 50 mm, preferably less than 30 mm, or even less than 10 mm and/or a smaller dimension, measured in a plane perpendicular to the direction of the largest dimension, greater than 1 pm, or even greater than 10 pm ( micrometers);
• the product comes in the form of a coating deposited on a support.
• the thickness of said coating is greater than 10 ⁇ m, preferably greater than 50 ⁇ m, preferably greater than 100 ⁇ m, preferably greater than 200 ⁇ m, and preferably less than 1 mm, preferably less than 500 ⁇ m.
• the support is made of a material chosen from ceramics, metals, organic products, in particular polymers, and their mixtures;
• the product contains a polysaccharide, preferably a gelled polysaccharide, preferably an alginate or a pectin, preferably a gelled alginate or a gelled pectin, preferably an alginate, preferably a gelled alginate
• the mass quantity of the polysaccharide, preferably of the gelled polysaccharide is greater than or equal to 0.1%, preferably greater than or equal to 0.2%, preferably greater than or equal to 0.3% and less than or equal to 5%, preferably less than or equal to 4% , preferably less than or equal to 3%, preferably less than or equal to 2%, preferably less than or equal to 1%.
• the polysaccharide, alginate, contained in the binder can for example be detected by steric exclusion chromatography.
• a product according to the invention can be manufactured according to a process according to the invention comprising steps a) to g), in particular and preferably steps a) to i) mentioned above.
• a source of aluminum chosen from a boehmite or an aluminum hydroxide and their mixtures, preferably an aluminum hydroxide, is placed in aqueous suspension, and if the median size of said source of aluminum is greater than 3 pm, said aqueous suspension is crushed so as to obtain a median size less than or equal to 3 pm, preferably less than or equal to 2 pm, preferably less than or equal to 1 pm, preferably less than or equal to 0, 7 pm, preferably less than or equal to 0.5 pm, said suspension being maintained during this step a) at a temperature below 50°C.
• the aqueous suspension of the aluminum source and the grinding of said aqueous suspension can be carried out simultaneously.
• the grinding of the aqueous suspension is carried out if the median size of the aluminum source is greater than 2 pm, greater than 1 pm.
• an aqueous suspension of an aluminum source chosen from boehmite or aluminum hydroxide and mixtures thereof, preferably aluminum hydroxide is ground so as to obtain a median size ⁇ 1 pm, said suspension being maintained during this step at a temperature below 50°C.
• the aluminum hydroxide is gibbsite.
• aluminum hydroxide, boehmite and their mixtures are the only sources of aluminum used in all the steps of the process according to the invention.
• aluminum hydroxide is the only source of aluminum used in all the steps of the process according to the invention.
• the median size obtained after grinding is less than or equal to 0.7 pm, preferably less than or equal to 0.5 pm.
• the suspension is maintained during step a) at a temperature greater than 15°C, preferably greater than or equal to 20°C.
• the grinding can be carried out using any technique known to those skilled in the art, such as for example by wet grinding.
• step b) the pH of the mixture obtained at the end of step a) is increased by the addition of a base, such that the molar ratio between the OH provided by said base and the AI present in the mixture is greater than 0.20, said mixture being kept stirring after introduction of said base, at a temperature below 50°C.
• the molar ratio between the OH provided by said base and the AI present in the mixture is greater than 0.25, preferably greater than 0.4, preferably greater than or equal to 0.5, and/or preferably less than 10, preferably less than 9, preferably less than 8, preferably less than 7, preferably less than 6, preferably less than 5, preferably less than 4, preferably less than 3, preferably less to 2, preferably less than 1.5.
• the pH of the mixture after addition of the base is greater than 9, preferably greater than 10, and preferably less than 13, preferably less than 12.
• the base does not contain the aluminum element.
• the base used is chosen from NaOH, LiOH, NH 4 OH, KOH, Ca(OH) 2 , RbOH, CsOH, Sr(OH) 2 , Ba(OH) 2 , Mg(OH) 2 , and their mixtures.
• the base is chosen from NaOH, LiOH, NH 4 OH, and mixtures thereof.
• the base is LiOH.
• the stirring time is greater than 5 minutes, preferably greater than 10 minutes, preferably greater than 15 minutes, and preferably less than 5 hours.
• the mixture is kept stirring at a temperature greater than 15°C, preferably greater than or equal to 20°C, preferably greater than or equal to 25°C.
• steps a) and b) are carried out simultaneously.
• step c) a chlorine salt is added to the mixture, such that the molar ratio between the Cl provided by said chlorine salt and the AI present in the mixture is greater than 0.25, said mixture being kept stirring after introduction of said chlorine salt at a temperature below 50°C, said molar ratio between the Cl provided by said chlorine salt and the AI present in the mixture being greater than or equal to 0.5, preferably greater than or equal to 1, preferably greater than 1, if the process does not include step f).
• the method comprises step f).
• the molar ratio between the Cl provided by said chlorine salt and the AI present in the mixture is greater than 0.25, preferably greater than 0.4, preferably greater than 0.5, and preferably less to 10, preferably less than 9, preferably less than 8, preferably less than 7, preferably less than 6, preferably less than 5, preferably less than 4, preferably less than 3, preferably less than 2 , preferably less than 1.5.
• Chlorine salt preferably does not contain the element aluminum.
• the chlorine salt is chosen from LiCI, NaCI, KCI, CaCI 2 , NH 4 CI, MgCI 2 and their mixtures, preferably chosen from LiCI, NaCI, KCI, CaCI 2 and their mixtures.
• the chlorine salt is LiCl.
• the stirring time is greater than 5 minutes, preferably greater than 10 minutes, preferably greater than 15 minutes, and preferably less than 48 hours.
• the mixture is kept stirring at a temperature greater than 15°C, preferably greater than or equal to 20°C, preferably greater than or equal to 25°C.
• the base in step b), the chlorine salt in step c), and their respective quantities are chosen so as to provide a quantity of lithium in the mixture such that the Li/Al molar ratio is greater than or equal to 1.
• said molar ratio is greater than 1.1, preferably greater than 1.2, and preferably less than 4, preferably less than 2.
• steps a), b) and c) are carried out simultaneously.
• step d) the temperature of the mixture is increased to a temperature Ti greater than or equal to 50°C and less than or equal to 60°C, the time ti being the time during which said mixture is at a higher temperature or equal to 50°C.
• the mixture is kept stirring during step d).
• the time ti is greater than 5 minutes, preferably greater than 10 minutes, and preferably less than 15 hours, preferably less than 10 hours.
• step e the mixture is maintained at a temperature greater than or equal to 50 °C and less than or equal to 60 °C for a time t 2 .
• the mixture is kept stirring during step e).
• T 20 be the average temperature during step e
• the temperature of the mixture is substantially constant and equal to T 2 I.
• the time t 2 is greater than 40 minutes, preferably greater than 45 minutes, preferably greater than 60 minutes, and preferably less than 10 hours, preferably less than 7 hours.
• an acid is added to the mixture with stirring so as to reduce the pH of said mixture to a value less than or equal to 8, preferably less than or equal to 7.5, and preferably greater than or equal to 7.5.
• the chlorine salt in step c), said acid, and their respective quantities being chosen so that the CI/AI molar ratio in the mixture is greater or equal to 1, preferably greater than 1, the mixture being maintained at a temperature less than or equal to 60 °C, the time t 3 being the time during which the mixture is at a temperature greater than or equal to 50 °C.
• At least part of the quantity of Cl necessary to obtain a CI/AI molar ratio greater than or equal to 1, preferably greater than 1, is provided by said acid.
• one of the acids may contain Cl, preferably comprises Cl.
• the acid is chosen from HCl, H2SO4, HNO3, HI, HBr, HCIO4, HCIO3, HMnO4, H 2 MnO4 and their mixtures, preferably from HCl, HNO3, HBr, HCIO4, HCIO3 and their mixtures.
• the acid is HCl.
• the CI/AI molar ratio in the mixture is set to a value less than 3, preferably less than 2.
• T 30 be the average temperature during step f).
• the temperature of the mixture is substantially constant and equal to T31.
• the time t 3 is greater than 5 minutes, preferably greater than 10 minutes, and preferably less than 60 minutes, preferably less than 40 minutes.
• step f) depends in particular on the nature of the lithium source for which lithium extraction is envisaged, in particular its pH. For example, if said lithium source has a pH less than 7, the process according to the invention preferably comprises step f).
• the mixture carried out in steps b), c), d), e) and optionally f) can be carried out using any known technique, such as for example using a mixer or a grinder, preferably wet. with control and adjustment of the mixture temperature.
• step g) optional and preferred, the mixture is filtered so as to obtain a paste, said mixture being maintained at a temperature less than or equal to 60 ° C, the time t 4 being the time during which the mixture is at a temperature greater than or equal to 50°C.
• T 4 o the average temperature of the mixture during the time t 4 .
• the temperature of the mixture during time t 4 is substantially constant and equal to T41.
• the temperature of the mixture is lowered below 50°C before filtration begins.
• the time t 4 is less than 15 minutes, preferably less than 10 minutes, preferably less than 5 minutes.
• Any known filtration technique can be implemented during this step, in particular a filter press, a centrifuge, a belt filter, a drum filter.
• step g) the cumulative time ti+t 2 +t 3+ t 4 , or t 5 , time during which the mixture was exposed to a temperature greater than or equal to 50 ° C and less than or equal to 60°C is greater than or equal to 45 minutes and less than 15 hours.
• the time t 5 is greater than 50 minutes, preferably greater than 55 minutes, preferably greater than 1 hour.
• the time t 5 is such that the times ti, t 2 , t 3 and t 4 satisfy the following relationships: [ti/(-1,2Ti+75)] + [t 2 /(-1,2T 20 + 75)] + [t 3 /(-1.2T 30 +75)] + [t 4 /(-1.2T 40 +75)] ⁇ 1 and [ti/(- 0.225Ti+14.25)] + [t 2 /(-0.225T 20 +14.25)] + [t 3 /(-0.225T 30 +14.25)] + [t 4 /(-0.225T 40 +14.25)] > 1. More preferably, the time t 5 is such that the times ti, t 2 , t 3 and t 4 satisfy the following relationships:
• the temperatures in steps d), e) and optionally f) are substantially constant and equal to Ti, T21 and T 3 I, respectively, and the time t 5 is such that the times ti, t 2 , t 3 and t 4 satisfy the following relationships:
• the time t 5 is such that the times ti, t 2 , t 3 and t 4 satisfy the following relationships:
• the method according to the invention comprises, after step g), a step h) of shaping a starting charge comprising the dough obtained at the end of step g) in the form of an object or coating, and an optional step i) of reducing the water content of said object.
• step h) a starting charge comprising the paste obtained at the end of step g) is shaped in the form of an object or a coating deposited on a support.
• the shaping can be carried out using any technique known to those skilled in the art, for example extrusion, granulation, pressing, casting, atomization, serigraphy (or “screen printing” in English), tape casting, or drip casting, particularly when an object is obtained, or by stamping, lamination, coating, granulation, especially when A coating deposited on a support is obtained.
• the starting charge does not include a binder.
• the starting charge also comprises a binder, preferably a polysaccharide comprising a group capable of forming an ionic bond with a gelling agent for the formation of a gelled polysaccharide, in particular in a quantity such that the ratio mass of the quantity of said polysaccharide over the total quantity of said polysaccharide and of the paste obtained at the end of step g) considered dry, is greater than or equal to 0.1% and less than or equal to 5%.
• said mass ratio is greater than or equal to 0.2%, preferably greater than or equal to 0.3%, and preferably less than or equal to 4%, preferably less than or equal to 3%, preferably less than or equal to equal to 2%, preferably less than or equal to 1%.
• the polysaccharide group capable of forming an ionic bond with a gelling agent is a COO- carboxylate group.
• the polysaccharide comprises a group capable of forming an ionic bond with a gelling agent chosen from divalent cations, trivalent cations (for example a Fe or Al cation) and their mixtures, preferably chosen from cations alkaline earth, preferably chosen from the cations of Ca, Sr, Ba, Mg and their mixtures.
• a gelling agent chosen from divalent cations, trivalent cations (for example a Fe or Al cation) and their mixtures, preferably chosen from cations alkaline earth, preferably chosen from the cations of Ca, Sr, Ba, Mg and their mixtures.
• the polysaccharide comprises a group capable of forming an ionic bond with a Ca cation.
• the polysaccharide comprising a group capable of forming an ionic bond with a gelling agent is chosen from alginates and pectins.
• the polysaccharide comprising a group capable of forming an ionic bond with a gelling agent is chosen from alginates, preferably from sodium alginates, potassium alginates, ammonium alginates, calcium alginates, and their mixtures, preferably from sodium alginates, potassium alginates, ammonium alginates, and mixtures thereof.
• the alginate is an ammonium alginate.
• the polysaccharide comprising a group capable of forming an ionic bond with a gelling agent preferably the alginate
• the polysaccharide comprising a group capable of forming an ionic bond with a gelling agent, preferably the alginate
• the alginate can be provided in the form of a solution.
• the starting charge can comprise, in addition to the paste obtained at the end of step g) and the polysaccharide comprising a group capable of forming an ionic bond with a gelling agent, preferably an alginate, a solvent and/or a plasticizer and/or a lubricant, the natures and quantities of which are adapted to the shaping method of step h).
• a gelling agent preferably an alginate, a solvent and/or a plasticizer and/or a lubricant, the natures and quantities of which are adapted to the shaping method of step h).
• the solvent is water.
• the quantity of solvent is adapted to the shaping process implemented in step h) as well as to the presence of polysaccharide comprising a group capable of forming an ionic bond with a gelling agent in the starting charge.
• step f) makes it possible to obtain a paste having a solvent content, preferably water, adapted to the shaping process envisaged in step h).
• the starting charge optionally contains a plasticizer.
• the plasticizer content is between 0.1% and 10%, preferably between 0.5% and 5%, preferably between 0.5% and 2%, by mass based on the mass of the paste obtained at the end of step g) of the starting charge.
• plasticizers conventionally used for the manufacture of porous ceramic products can be used, for example polyethylene glycol, polyolefin oxides, hydrogenated oils, alcohols, in particular glycerol and glycol, esters, and mixtures thereof.
• the starting charge does not contain plasticizers.
• the starting charge optionally contains a lubricant.
• the lubricant content is between 0.1% and 10%, preferably between 0.5% and 5%, preferably between 0.5% and 2%, by mass based on the mass of the paste obtained at the end of step g) of the starting charge.
• All lubricants conventionally used for the manufacture of porous ceramic products can be used, for example petroleum jelly and/or glycerin and/or waxes.
• lubricant and/or plasticizer depend in particular on the shaping technique used in step h).
• the starting charge does not contain lubricants.
• the starting charge does not contain any constituents other than the paste obtained at the end of step g), the binder, preferably a polysaccharide, and a solvent.
• the mixing of the different constituents of the starting charge can be carried out using any technique known to those skilled in the art, for example in a mixer, preferably in a high-intensity mixer or in a Z-arm mixer, in a turbulat, in a crusher. jar with balls, preferably alumina balls.
• mixing is carried out in a high intensity mixer or in a Z-arm mixer.
• the total mixing time is preferably greater than 5 minutes, and preferably less than 30 minutes, preferably less than 20 minutes.
• Step h) can be preceded by a step of eliminating at least part of the solvent, so as to adapt the quantity of solvent, preferably water, to the shaping technique envisaged in the step h).
• All known techniques for eliminating at least part of a solvent, preferably water, can be used, preferably drying, preferably under air, at atmospheric pressure.
• the maximum temperature reached during said drying is greater than 20°C, and preferably less than 100°C.
• the objects obtained after shaping can be in the form of cylinders, polylobed shapes, rings, or spheres.
• said objects have a larger dimension less than 100 mm, preferably less than 80 mm, preferably less than 50 mm, preferably less than 30 mm, or even less than 10 mm and preferably greater than 1 mm and/or or a smaller dimension, measured in a plane perpendicular to the direction of the largest dimension, greater than 1 pm, or even greater than 10 pm (micrometers).
• the coating obtained after shaping may have a thickness greater than 10 ⁇ m, preferably greater than 50 ⁇ m, preferably greater than 100 ⁇ m, preferably greater than 200 ⁇ m, and preferably less than 1 mm, preferably less than 500 ⁇ m. p.m.
• the support is made of a material chosen from ceramics, metals, organic products, in particular polymers, and their mixtures.
• the starting charge contains a polysaccharide, preferably an alginate, and is shaped so as to obtain a preform, said shaping being carried out using any known technique of skilled in the art, for example extrusion, granulation, pressing, casting, atomization, screen printing, tape casting , or drop-by-drop gelation (or “drip casting” in English).
• the shaping is carried out by screen printing.
• the preform is brought into contact with a solution comprising a gelling agent, capable of causing the polysaccharide to gel, preferably alginate.
• the solution comprising a gelling agent capable of causing the polysaccharide to gel, preferably alginate, is well known to those skilled in the art.
• the gelling agent is preferably chosen from divalent cations, trivalent cations and their mixtures, preferably chosen from alkaline earth cations, preferably chosen from the cations of Ca, Sr, Ba, Mg and their mixtures.
• the gelling agent is a Ca cation.
• the solution containing the gelling agent is preferably chosen from a solution comprising a divalent cation salt, a solution comprising a trivalent cation salt, or the source of lithium from which the lithium is extracted, preferably brine, particularly when it contains such a cation.
• the solution comprising a divalent cation salt or a trivalent cation salt is chosen from an iodide solution of said cation and/or a chloride solution of said cation.
• the gelling solution is a solution comprising an alkaline earth cation iodide and/or an alkaline earth cation chloride. More preferably, the gelling solution is a solution comprising an alkaline earth cation chloride, preferably a solution comprising calcium chloride.
• the gelling solution is the lithium source from which the lithium is extracted, preferably the brine from which the lithium must be captured, particularly when this comprises a divalent and/or trivalent cation.
• the gelling solution is a calcium chloride solution, the calcium chloride concentration of which is preferably greater than 1 mol/l, preferably greater than 2 mol/l of solution.
• Bringing the preform into contact with the gelling solution can for example be carried out by immersing the preform in a bath of gelling solution or by sprinkling the preform with the gelling solution.
• the shaping and bringing the preform into contact with the gelling solution are combined, particularly when the preform is implemented by dropwise gelation.
• step i) optional and preferred, the water content of the object or coating obtained at the end of step h) is reduced.
• This reduction in water content can be achieved using drying.
• the maximum temperature reached during said drying is greater than 20°C, and preferably less than 100°C, preferably less than 80°C, preferably less than 60°C.
• the drying cycle has a plateau at said maximum temperature reached.
• the hold time at the level is preferably greater than 5 seconds and preferably less than 20 hours. Drying is preferably carried out in air, at atmospheric pressure.
• the water content of the product at the end of step i) is greater than 1%, preferably greater than 5%, preferably greater than 10% and preferably less than 60%, on the basis of the mass of the product.
• steps h) and i) can be carried out, at least partially simultaneously.
• the invention also relates to a product according to the invention obtained by the process according to the invention. Examples
• the products in the examples are first exposed to air for 170 hours at 25°C, at atmospheric pressure.
• the acquisitions are carried out using an X'Pert type device from the company Panalytical, equipped with a copper anode, over an angular range 20 between 5° and 80°, with a step of 0.017°, and a counting time of 300 s/step.
• the front optic features a fixed 0.25° divergence slit, 0.02 rad Soller slit, 10mm mask, and fixed 0.5° anti-scatter slit.
• the sample is rotating on itself.
• the rear optic features a fixed 0.25° anti-scatter slit, a 0.02 rad Soller slit and a nickel filter.
• the diffraction patterns are then qualitatively analyzed using EVA software and the ICDD2016 database.
• the PDF data sheet 00-031 -0700 from the ICDD2016 database allows the identification of the phase (LiCI).2AI(OH) 3 , xH 2 O.
• the crystallized phase of lithiated bayerite highlighted may present a slight angular shift of the peaks in relation to said data sheet, a consequence in particular of the quantity of Li inserted in the structure of the lithiated bayerite.
• the average size of the crystallites of lithiated bayerite, D, of the products of the examples is conventionally determined by X-ray diffraction on a powder of said product, previously exposed to air for 170 hours at 25°C, at atmospheric pressure, by means of an X'Pert type device from the company Panalytical, using the following Debye-Scherrer equation:
• V(B 2 - & 2 ) cos 0 10 TM
• A being the wavelength of the 031 -0700 from the ICCD database), in degrees
• b being the width at half height of the peak of the monocrystalline silicon standard used, here measured equal to 0.05°
• the acquisition of the diffraction patterns of the monocrystalline silicon standard and of the example is carried out, over an angular range 29 between 5° and 80°, with a step of 0.017°, and a counting time of 300 s /step for the example and 100 s/step for the monocrystalline silicon standard.
• the front optic features a fixed 0.25° divergence slit, 0.02 rad Soller slit, 10mm mask, and fixed 0.5° anti-scatter slit. The sample is rotating on itself.
• the rear optic features a fixed 0.25° anti-scatter slit, a 0.02 rad Soller slit and a nickel filter.
• the width at half maximum of the peaks is determined using the EVA software, and the average size of the lithiated bayerite crystallites is determined using the FWHM function.
• the determination of the cumulative rate of aluminum hydroxide and boehmite was carried out using the same X-ray diffraction diagrams used to demonstrate the crystallized phases present. After eliminating the Ka2 line and using the EVA software, it is possible to measure the AHA area of the aluminum hydroxide diffraction peak present in an angular range 29 substantially equal to 18.3°, the area ABO of the diffraction peak of boehmite being in an angular range 29 substantially equal to 14°, and the area ABL of the diffraction peak of lithiated bayerite being in an angular range 29 substantially equal to 1 1.3° .
• the cumulative rate of aluminum hydroxide and boehmite is then calculated according to formula (1) given previously:
• the cumulative rate of aluminum hydroxide and boehmite is equal to 9.
• the contents of the different elements present in the example products are determined, on products dried in air at 29°C for 16 hours, at atmospheric pressure, by inductively coupled plasma spectrometry. (or “ICP” in English).
• the water content is determined as the mass loss, expressed as a percentage, after drying in air at 299°C for 16 hours, at atmospheric pressure. After such drying, the product is said to be “dry”.
• the content of elements other than H and O, partly Li, Cl and Al, is determined on the dry product by inductively coupled plasma spectrometry, using a 5899 ICP-OES device from the Agilent brand.
• the median size of a powder or suspension is measured using a laser particle size analyzer model LA959V2 marketed by the company Horiba.
• a gibbsite AI(OH) 3 powder having a median size equal to 1.6 pm, of purity greater than 99.5% by mass and a specific surface area equal to 5 m 2 /g, for examples 1 to 5,
• Lithium hydroxide monohydrate LiOH, H 2 O
• LiOH, H 2 O Lithium hydroxide monohydrate
• Lithium chloride LiCI of purity greater than 99.5%% by mass, for examples 1 to 5,
• Hydrochloric acid HCl of purity greater than 99% by mass, in aqueous solution at 16M, for examples 2 to 5,
• ammonium alginate with a purity greater than 99% by mass, for examples 2 to 5.
• the mixture obtained is filtered through a Büchner, at room temperature (below 50° C.), with filter papers with a permeability equal to 2 ⁇ m so as to obtain a paste.
• step a for each example, 500 g of aluminum hydroxide are added to 2000 g of water, at a temperature equal to 25° C., in a LabStar mill sold by the company Netzsch and ground for 75 minutes.
• the aluminum hydroxide suspended in water has a median size equal to 0.55 pm.
• step b for each example, (LiOH, H 2 O) is added to the mixture obtained at the end of step a), so that the molar ratio between the OH provided by (LiOH, H 2 O) and the AI initially present in the mixture is as described in Table 1.
• the temperature at which this step took place, the mixing time as well as the pH of the mixture measured at the end of this step are also described in Table 1.
• step c) for each example, LiCI is added to the mixture obtained at the end of step b), so that the molar ratio between the Cl provided by LiCI and the AI initially present in the mixture is as described in Table 1.
• the temperature at which this step took place and the mixing time are described in Table 1.
• step d) the quantity of lithium in the mixture, expressed by the Li/Al molar ratio, is as described in Table 1.
• step d) the mixture is heated using a heating plate, to a temperature Ti, the time ti being the time during which said mixture is at a temperature greater than or equal to 50°C. Table 1 describes for each example the temperature Ti and the time ti.
• step e) for each example, the mixture is maintained at a constant temperature T21 for a time t 2 .
• Table 1 describes the temperature T 2 I and the time t 2 for each example.
• step f for each example, HCl is added to the mixture obtained at the end of step e), so that the pH of the mixture is lowered to the value indicated in table 1, the value of the molar ratio CI /AI in the mixture after addition of HCl being as described in table 1, the introduction of the acid taking place at a temperature equal to T 3 I kept constant during step f), the time t 3 being the time during which the mixture is at a temperature greater than or equal to 50 °C. T31 and t 3 are described in Table 1.
• step g for each example, the mixture is filtered through a Büchner, at room temperature (below 50° C.), with filter papers of permeability equal to 2 ⁇ m so as to obtain a paste.
• the time t 4 during which the mixture is at a temperature greater than or equal to 50 ° C is described in table 1.
• the time t 5 equal to the sum of the times ti+t 2 +t 3 +t 4 , is also described, for each example, in table 1.
• the products of Examples 2 and 3 consist of more than 99% by mass of water, lithiated bayerite, and LiCl.
• the products of Examples 4 and 5 consist of more than 99% by mass of water, lithiated bayerite, gibbsite and LiCl.
• the dough obtained was then shaped in the following way.
• the paste obtained after filtration was spread on a metal grid of thickness equal to 1 mm and perforated with circular holes of diameter equal to 1.5 mm, then scraped using a spatula of each side of the grid so that said dough fills the holes in said grid.
• the grid is then said to be “loaded”. Once the grid is loaded, it is placed under a circulation of hot air at 60°C, which makes it possible to “unload” said grid, the formed objects falling into a container placed under the grid.
• Said objects obtained are in the form of cylinders of average length equal to 0.8 mm and average diameter equal to 1.4 mm.
• step h a starting charge consisting of the paste obtained at the end of step g) and ammonium alginate was produced, the content of said alginate being equal to 1 % by mass based on the mass of the starting charge after drying at 200°C for 16 hours, at atmospheric pressure.
• Said paste and the ammonium alginate were mixed in a planetary mixer under hot air created by a heat gun set to a temperature equal to 100 ° C, for 120 minutes so as to obtain a homogeneous starting charge and having a water content compatible with the shaping technique.
• the starting load was then spread on a metal grid with a thickness equal to 1 mm and perforated with circular holes with a diameter equal to 1.5 mm, then scraped using a spatula on each side of the grid. so that said starting charge fills the holes of said grid.
• the grid is then said to be “loaded”. Once the grid is loaded, it is placed under a circulation of hot air at 60°C, which makes it possible to “unload” said grid, the formed objects falling into a container placed under the grid.
• Said objects obtained are in the form of cylinders of average length equal to 0.8 mm and average diameter equal to 1.4 mm.
• Examples 2 and 3 according to the invention, have a high lithium adsorption capacity.
• Example 4 shows that in Example 4, a time t 5 , time during which the mixture is at a temperature greater than or equal to 50 ° C, equal to 35 minutes for a temperature in step e) of 60°C leads to a product having a cumulative level of aluminum hydroxide and boehmite equal to 30%, which limits its lithium adsorption capacity.

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