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
• • 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
  • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
  • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
• • 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
  • B01J20/28—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
  • B01J20/28016—Particle form
  • B01J20/28019—Spherical, ellipsoidal or cylindrical
• • 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
  • B01J20/28—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
• • 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
  • B01J20/28—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
  • B01J20/28047—Gels
• • 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
  • B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
• • 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
  • B01J20/3071—Washing or leaching
• • 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
  • B01J2220/00—Aspects relating to sorbent materials
  • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
  • B01J2220/48—Sorbents characterised by the starting material used for their preparation
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P10/00—Technologies related to metal processing
  • Y02P10/20—Recycling

Definitions

• TITLE Product comprising a lithium adsorbent Technical area
• the present invention relates to a product comprising a lithium adsorbent and to a method of manufacturing products comprising a lithium adsorbent.
• Brines are sources of lithium, for which an 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 the lithium when the brine comes into contact with it.
• the lithium is then recovered by passing slightly saline and acidified water through these columns. This results in a concentrated lithium solution which will be purified before a precipitation step, generally in the form of lithium carbonate.
• Lithium adsorbents are materials advantageously used as an active material allowing the production of the concentrated lithium solution within the extraction columns.
• Application KR20190078350 describes various lithium adsorbent materials in a lithium capture application.
• Application WO2018002336 describes a material for capturing lithium of formula (LiCI) x .2AI(OH) 3 , nhhO with x between 0.4 and 1 and n between 0.01 and 10.
• Application CN103212388 describes a process for the selective and irreversible extraction of radioactive rubidium and cesium ions in a brine containing such ions, in particular from radioactive nuclear waste, from a solution comprising a hydrosol of sodium alginate and of a powder of potassium tetraphenylborate.
• Lithium uptake is accompanied by an increase in volume of the lithium adsorbent material located in the extraction column. Then, when the lithium is subsequently recovered by passing slightly saline and acidified water through said columns, the volume of the lithium adsorbent material decreases. Said material thus undergoes repeated cycles of increase and decrease in volume which can lead to a degradation of its shape and therefore to a decrease in the efficiency of lithium capture.
• An object of the invention is to respond, at least partially, to this need. Disclosure of Invention
• this object is achieved by means of a product advantageously allowing the facilitated extraction of lithium, said product comprising particles bound by a binder, said binder comprising a gelled polysaccharide comprising a group establishing an ionic bond with a cation divalent, a trivalent cation and mixtures thereof, said particles being essentially, preferably being, particles of a lithium adsorbent.
• the binder consists of said gelled polysaccharide.
• the gelled polysaccharide comprises a group establishing an ionic bond with an alkaline-earth cation, preferably chosen from the cations of Ca, Sr, Ba and their mixtures, preferably with a Ca cation.
• the group is chosen from carboxylate groups (-COO-) or sulphonate groups (-SO 3 ), more preferably said group is a carboxylate group.
• the gelled polysaccharide is an alginate gelled under the action of a divalent cation, a trivalent cation and mixtures thereof, preferably under the action of a divalent cation, more preferably under the action of a cation of calcium.
• the gelled polysaccharide is a pectin gelled under the action of a divalent cation, a trivalent cation and mixtures thereof, preferably under the action of a divalent cation, more preferably under the action of a cation of calcium
• the lithium adsorbent is chosen from:
• lithiated bayerite preferably a material of formula (LiCI) x .2AI(OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10;
• lithium aluminate optionally hydrated and/or doped, said lithium aluminate preferably corresponding to the formula UAIO2, optionally hydrated and/or doped;
• manganese and lithium spinel being preferably chosen from a manganese and lithium spinel of formula Li (i+X) Mn (2 -y ) M'y0 4 with -0.20 ⁇ x ⁇ 0.4 and 0 ⁇ y ⁇ 1, the element M' being chosen from aluminum, cobalt, nickel, chromium, iron, magnesium, titanium, vanadium, copper, zinc, gallium, calcium, niobium, yttrium, barium, silicon, boron, zirconium, lithium and mixtures thereof, the electroneutrality of said lithium manganate being ensured by the content of oxygen;
• a cobalt and lithium spinel optionally hydrated and/or doped, said cobalt and lithium spinel preferably having the formula UCO2O4, optionally hydrated and/or doped;
• lithium titanate optionally hydrated and/or doped, said lithium titanate being preferably chosen from a lithium titanate corresponding to the formula LiTi0 2 , LhTiOs, LÎ2TÎ307, LÎ4TÎ50i2, and mixtures thereof, optionally hydrated and/or or doped(s), preferably LhTiCb, optionally hydrated and/or doped;
• the lithium adsorbent is chosen from:
• lithiated bayerite preferably a material of formula (LiCI) x .2AI(OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10;
• lithium titanate optionally hydrated and/or doped
• said lithium titanate preferably being chosen from a lithium titanate corresponding to the formula LiTiC>2, Li 2 TiC> 3 , Li 2 Ti 3 07, Li 4 Ti 0i 2 , and mixtures thereof, optionally hydrated and/or doped, preferably LhTiCb, optionally hydrated and/or doped ;
• the lithium adsorbent is a lithiated bayerite, preferably a material of formula (LiCI) x .2AI(OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10.
• mass quantity of particles of a lithium adsorbent, after drying at 100°C for 12 hours, is greater than or equal to 95% and less than 99.9%, based on the mass of said product after drying at 100°C for 12 hours.
• the product is in the form of cylinders, polylobes, rings, or spheres, preferably, the largest dimension of which is less than 100 mm, preferably less than 80 mm, preferably less than 50 mm and the small dimension, in a plane perpendicular to the direction of the largest dimension, is greater than 1 ⁇ m.
• Products comprising a lithium adsorbent described above, in particular put in the form of macroscopic objects, have improved resistance to repetitive cycling adsorption-desorption of lithium in particular in lithium extraction columns described above.
• the invention also relates to a process for manufacturing a product comprising a lithium adsorbent, in particular a product as described above, comprising at least the following steps: a) mixing raw materials to form a starting charge, said charge of starting comprising a powder of a lithium adsorbent, and a polysaccharide which can be gelled under the action of a gelling agent, the mass ratio of the quantity of said polysaccharide to the total quantity of said polysaccharide and of the powder of a lithium adsorbent being preferably greater than or equal to 0.1% and preferably less than or equal to 10%, more preferably less than or equal to 5%, b) shaping of said starting charge, so as to obtain a preform, c ) bringing said preform into contact with said gelling agent and gelling said polysaccharide so as to obtain said product comprising a lithium adsorbent, d) optionally, drying said product comprising u n adsorbing lithium.
• the lithium adsorbent is a lithiated bayerite, preferably a material of formula (LiCI) x .2AI(OH ) 3 , nH 2 0, with x between 0.4 and 1 and n between 0.01 and 10.
• the polysaccharide is an alginate or a pectin, preferably an alginate.
• the gelling agent is chosen from Ca, Sr, Ba and mixtures thereof, preferably the gelling agent is Ca.
• the invention also relates to a product capable of being obtained by the method as described above.
• 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 or capable of being obtained by the method according to the invention as described previously.
• lithium adsorbent refers to any material capable of retaining lithium in its structure by adsorption, in particular chemical or physical, and/or by exchange between an ion of its structure with an Li+ ion.
• a lithiated bayerite in particular a material of formula (LiCI) x .2AI(OH) 3 , nhhO with x between 0.4 and 1 and n between 0.01 and 10, is an example of a lithium adsorbent material.
• lithium bayerite The compound of formula LiCI.2AI(0H) 3 .nH 2 0 as indicated in the ICDD PDF 00-031-0700 sheet, but also by extension, is called "lithium bayerite".
• compounds having a ratio of molar amounts of lithium and aluminum, Li/Al different from 0.5 In some modes, it may be less than 0.5. According to other modes, it may be greater than 0.5.
• polysaccharides refers to polymers composed of sequences of saccharide units linked by glycosidic bonds.
• gellable polysaccharide under the action of a gelling agent means a polysaccharide capable of forming a gel under the action of said gelling agent.
• alginate has the formula (O Q HZO Q ) ⁇
• Alginate is a polyosidic chain comprising carboxylate groups (COO- ).
• Calcium Ca 2+ ions (gelling agent) react with two strands of alginate, that is to say with the carboxylate groups COO , leading to the polymerization of the alginate chains and the bonding of the molecules between them. The reaction thus allows the creation of a gel.
• the starting charge comprises at least one powder of a lithium adsorbent.
• the lithium adsorbent powder(s) may or may be provided in a dry form, but also in a wet form, for example in the form of a suspension and /or a paste.
• the starting charge contains a lithiated bayerite powder, preferably a powder of a material of formula (LiCI) x .2AI(OH) 3 , nhhO, with x between 0.4 and 1.0 and n between 0.01 and 10, said powder is supplied in a wet form, preferably in the form of a suspension and/or a paste.
• a lithiated bayerite powder preferably a powder of a material of formula (LiCI) x .2AI(OH) 3 , nhhO, with x between 0.4 and 1.0 and n between 0.01 and 10
• said powder is supplied in a wet form, preferably in the form of a suspension and/or a paste.
• the starting charge comprises at least two powders of a lithium adsorbent, preferably at least two of said powders of a lithium adsorbent are made of a different lithium adsorbent.
• the starting charge comprises a single powder of a lithium adsorbent.
• the lithium adsorbent is chosen from: a lithiated bayerite, preferably a material of formula (LiCI) x .2Al(OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10; a lithium aluminate, optionally hydrated and/or doped, said lithium aluminate preferably corresponding to the formula UAIO 2 , optionally hydrated and/or doped; a manganese and lithium spinel, optionally doped, said manganese and lithium spinel being preferably chosen from a manganese and lithium spinel of formula Li (i+X) Mn (2 -y ) M'y0 4 with - 0.20 ⁇ x ⁇ 0.4 and 0 ⁇ y ⁇ 1, the element M' being chosen from aluminum, cobalt, nickel, chromium, iron, magnesium, titanium, vanadium, copper, zinc, gallium, calcium, niobium, yttrium, bar
• a lithiated magnesium oxide, optionally hydrated and/or doped said lithiated magnesium oxide preferably having the formula LiMg0 2 , optionally hydrated and/or doped;
• a cobalt and lithium spinel optionally hydrated and/or doped, said cobalt and lithium spinel preferably having the formula UC0 2 O 4 , optionally hydrated and/or doped;
• a lithium titanate optionally hydrated and/or doped, said lithium titanate preferably being chosen from a lithium titanate corresponding to the formula LiTi0 2 , LhTiOs, LÎ2TÎ307, Li 4 Ti 5 0i2, and mixtures thereof, optionally hydrated(s ) and/or doped, preferably LhTiCb, optionally hydrated and/or doped; hhTiCb, optionally hydrated and/or doped;
• H2T13O7 optionally hydrated and/or doped
• H4T15O12 optionally hydrated and/or doped
• the lithium adsorbent is chosen from: a lithiated bayerite, preferably a material of formula (LiCI) x .2Al(OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10; a manganese and lithium spinel, optionally doped; a lithium titanate, optionally hydrated and/or doped, said lithium titanate being preferably chosen from a lithium titanate corresponding to the formula LiTi0 2 , L TiOs , Li 2 Ti 3 0 7 , Li 4 Ti 0i 2 , and their mixtures, optionally hydrated and/or doped, preferably Li 2 Ti0 3 , optionally hydrated and/or doped ;
• H2T1O3 optionally hydrated and/or spiked; and their mixtures.
• the lithium adsorbent is a lithiated bayerite, preferably a material of formula (LiCI) x .2AI(OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10
• the median size of the lithium adsorbent powder is greater than 0.1 ⁇ m and/or less than 100 ⁇ m.
• the starting charge contains a polysaccharide comprising a group capable of forming an ionic bond with a gelling agent chosen from divalent cations, trivalent cations (for example an Fe or Al cation) and mixtures thereof for the formation of a gelled polysaccharide, in particular in an amount such that the mass ratio of the amount of said polysaccharide to the total amount of said polysaccharide and lithium adsorbent powder is greater than or equal to 0.1% and preferably less than or equal to 10%, preferably still less than 5%.
• a gelling agent chosen from divalent cations, trivalent cations (for example an Fe or Al cation) and mixtures thereof for the formation of a gelled polysaccharide, in particular in an amount such that the mass ratio of the amount of said polysaccharide to the total amount of said polysaccharide and lithium adsorbent powder is greater than or equal to 0.1% and preferably less than or equal to 10%, preferably still less than 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 at 2%, preferably less than or equal to 1%.
• the polysaccharide group capable of forming an ionic bond with a gelling agent chosen from divalent cations, trivalent cations and mixtures thereof is chosen from a carboxylate group COO or a sulphonate group SO 3 , more preferably said group is a COO- carboxylate group.
• the polysaccharide comprises a group capable of forming an ionic bond with a gelling agent chosen from alkaline-earth cations, preferably chosen from Ca, Sr, Ba cations and mixtures thereof.
• a gelling agent chosen from alkaline-earth cations, preferably chosen from Ca, Sr, Ba cations and mixtures thereof.
• 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, and mixtures thereof.
• the alginate is an ammonium alginate.
• the starting charge contains a powder of a lithium adsorbent and a polysaccharide comprising a group capable of forming an ionic bond with a gelling agent chosen from divalent cations, trivalent cations and mixtures thereof.
• a gelling agent chosen from divalent cations, trivalent cations and mixtures thereof.
• the polysaccharide comprising a group capable of forming an ionic bond with a gelling agent chosen from divalent cations, trivalent cations and mixtures thereof, preferably alginate, can be provided in the form of a solution.
• the starting charge may comprise, in addition to the adsorbent powder(s), lithium and polysaccharide comprising a group capable of forming an ionic bond with a gelation chosen from divalent cations, trivalent cations and mixtures thereof, a solvent and/or an organic binder and/or a plasticizer and/or a lubricant and/or pore-forming particles, the natures and quantities of which are adapted to the method formatting step b).
• the solvent is water.
• the amount of solvent is adapted to the shaping process implemented in step b) as well as to the presence of polysaccharide comprising a group capable of forming an ionic bond with a gelling agent chosen from divalent cations, trivalent cations and their mixtures in the starting charge.
• a step of removing part of the solvent can be carried out, before step b).
• the starting charge optionally contains an organic binder facilitating the constitution of the preform, preferably in a content of between 0.1% and 10%, preferably between 0.2% and 2% by mass based on the mass of the lithium adsorbent powder(s) of the starting charge.
• All the organic binders conventionally used for the manufacture of porous ceramic products can be used, for example polyvinyl alcohol (PVA) or polyethylene glycol (PEG), methylstearate, ethylstearate, waxes, polyolefins, polyolefin oxides, glycerin, propionic acid, maleic acid, benzyl alcohol, isopropanol, butyl alcohol, paraffin and polyethylene dispersion, and mixtures thereof.
• PVA polyvinyl alcohol
• PEG polyethylene glycol
• methylstearate methylstearate
• ethylstearate waxes
• polyolefins polyolefin oxides
• glycerin glycerin
• propionic acid maleic acid
• benzyl alcohol isopropanol
• butyl alcohol paraffin and polyethylene dispersion, and mixtures thereof.
• the starting charge optionally contains a plasticizer, also facilitating the constitution of the preform.
• the content of plasticizer is between 0.1% and 10%, preferably between 0.5% and 5%, by mass based on the mass of the lithium adsorbent powder(s). of the starting load.
• the plasticizer can constitute a binder.
• the 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 optionally contains a lubricant, also facilitating the constitution of the preform.
• the lubricant content is between 0.1% and 10%, preferably between 0.5% and 5% by weight of the lithium adsorbent powder(s) of the starting charge.
• lubricants conventionally used for the manufacture of porous ceramic products can be used, for example petroleum jelly and/or glycerin and/or waxes.
• the starting charge optionally contains pore-forming particles, well known to those skilled in the art, which are intended to be eliminated during the process according to the invention, thus leaving room for pores.
• pore-forming particles well known to those skilled in the art, which are intended to be eliminated during the process according to the invention, thus leaving room for pores.
• Their quantity and their dimensions are chosen so as in particular to adjust the pore volume in the lithium adsorbent-based product obtained at the end of step b) or at the end of step c).
• said pore-forming particles are made of a material soluble in the solvent.
• binder and/or the lubricant and/or the plasticizer depend in particular on the shaping technique used in step b).
• the starting charge does not contain any constituents other than the lithium adsorbent powder(s), the polysaccharide, a solvent, an organic binder, a plasticizer, a lubricant and particles porogens.
• the polysaccharide, preferably the alginate, the solvent, preferably the water are mixed in such a way as to obtain an intimate mixture.
• the other constituents of the starting charge in particular the lithium adsorbent powder(s), the optional binder, lubricant, plasticizer and blowing particles are added with stirring.
• the quantity of solvent preferably water
• the quantity of solvent can be added in several times, in a quantity determined according to the technique chosen for shaping.
• the solvent preferably water, is provided, at least in part, by said suspension and/or said paste .
• the mixing of the various constituents can be carried out according to 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 jar mill with balls, preferably alumina balls.
• the 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 b) can be preceded by a step of removing at least part of the solvent, so as to adapt the amount of solvent, preferably water, to the shaping technique. considered in step b).
• All the known techniques for at least partially eliminating a solvent, preferably water, can be used, preferably drying, preferably in air, at atmospheric pressure.
• 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 holding time at the level is preferably greater than 1 hour, and preferably less than 20 hours, preferably less than 15 hours.
• step b) the starting charge is shaped so as to obtain a preform.
• 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 “tape casting” in English), or drop by drop gelation (or “drip casting” in English).
• the preforms obtained can be in the form of cylinders, polylobes, rings, or spheres.
• step c) the preform is brought into contact with a solution comprising a gelling agent chosen from divalent cations, trivalent cations and mixtures thereof, capable of causing the polysaccharide to gel, so as to obtain the product based on a lithium adsorbent.
• a gelling agent chosen from divalent cations, trivalent cations and mixtures thereof, capable of causing the polysaccharide to gel, so as to obtain the product based on a lithium adsorbent.
• the solution comprising a gelling agent chosen from divalent cations, trivalent cations and mixtures thereof, capable of causing the polysaccharide to gel, is well known to those skilled in the art.
• the gelling agent is preferably chosen from alkaline-earth cations, preferably chosen from Ca, Sr, Ba cations and mixtures thereof.
• the gelling agent is a Ca cation.
• the solution containing the gelling agent chosen from divalent cations, trivalent cations and mixtures thereof is preferably chosen from a solution comprising a divalent cation salt, a solution comprising a trivalent cation salt, or the source of lithium from from which the lithium is extracted, preferably brine, in particular 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 gelation solution is a solution comprising an alkaline earth cation chloride, preferably a solution comprising calcium chloride.
• the gelling solution is the source of lithium from which the lithium is extracted, preferably the brine from which the lithium must be collected, in particular when the latter 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.
• the bringing into contact can for example be carried out by immersing the preform in a bath of gelling solution or by spraying the preform with the gelling solution.
• step b) and step c) are combined, in particular when the preform is implemented by dropwise gelling.
• a product based on lithium adsorbent is obtained.
• Said lithium adsorbent-based product may be in the form of cylinders, polylobes, rings, or spheres.
• the preform is shaped so that the largest dimension of the product based on lithium adsorbent is 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 that the smallest dimension of the lithium adsorbent-based product in a plane perpendicular to the direction of the largest dimension is greater than 1 ⁇ m, or even greater than 10 ⁇ m (micrometers).
• step d) optional, the product based on a lithium adsorbent is dried.
• the maximum temperature reached during said drying is greater than 20°C, and preferably less than 140°C, preferably less than 100°C, preferably less than 80°C.
• the drying cycle has a plateau at said maximum temperature reached.
• the holding time at the plateau is preferably greater than 1 hour, preferably greater than 2 hours, preferably greater than 5 hours and preferably less than 20 hours, preferably less than 15 hours. Drying is preferably carried out in air, at atmospheric pressure.
• step d a dry product based on lithium adsorbent is obtained.
• the invention also relates to a product comprising particles bound by a binder, said binder comprising, preferably consisting of, a gelled polysaccharide comprising a group establishing an ionic bond with a divalent cation, a trivalent cation and mixtures thereof, preferably a gelled alginate, said particles being essentially particles of a lithium adsorbent.
• a binder comprising, preferably consisting of, a gelled polysaccharide comprising a group establishing an ionic bond with a divalent cation, a trivalent cation and mixtures thereof, preferably a gelled alginate, said particles being essentially particles of a lithium adsorbent.
• the binder of the product comprising a lithium adsorbent according to the invention comprises, preferably consists essentially of, a gelled polysaccharide comprising a group establishing an ionic bond with a divalent cation, a trivalent cation and their mixtures, preferably with an alkaline-earth cation, preferably chosen from Ca, Sr, Ba cations and mixtures thereof, preferably a Ca cation.
• said gelled polysaccharide a gelled alginate or a gelled pectin, preferably a gelled alginate.
• the gelled polysaccharide, in particular the gelled alginate, contained in the binder can for example be demonstrated by steric exclusion chromatography.
• the product comprising a lithium adsorbent according to the invention consists essentially, after drying at 100° C. for 12 hours, of particles of a lithium adsorbent, bound by a binder consisting essentially of a gelled alginate.
• the particles of a lithium adsorbent of the product comprising a lithium adsorbent according to the invention are particles of a lithium adsorbent chosen from: a lithiated bayerite, preferably a material of formula (LiCI) x .2AI (OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10; a lithium aluminate, optionally hydrated and/or doped, said lithium aluminate preferably corresponding to the formula UAIO2, optionally hydrated and/or doped; a manganese and lithium spinel, optionally doped, said manganese and lithium spinel being preferably chosen from a manganese and lithium spinel of formula Li (i+X) Mn (2 -y ) M'y0 4 with - 0.20 ⁇ x ⁇ 0.4 and 0 £ y £ 1 , the element M' being chosen from aluminum, cobalt, nickel, chromium, iron, magnesium,
• a lithiated magnesium oxide, optionally hydrated and/or doped said lithiated magnesium oxide preferably having the formula LiMg0 2 , optionally hydrated and/or doped;
• H2T13O7 optionally hydrated and/or doped
• H4T15O12 optionally hydrated and/or doped
• the lithium adsorbent is chosen from: a lithiated bayerite, preferably a material of formula (LiCI) x .2Al(OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10; a manganese and lithium spinel, optionally doped; a lithium titanate, optionally hydrated and/or doped, said lithium titanate preferably being chosen from a lithium titanate corresponding to the formula LiTi0 2 , Li 2 Ti03 , Li 2 Ti 3 07 , Li 4 Ti 0i 2 , and their mixtures, optionally hydrated and/or doped, preferably Li 2 TiO3, optionally hydrated and/or doped ;
• H2T1O3 optionally hydrated and/or spiked; and their mixtures.
• the lithium adsorbent is a lithiated bayerite, preferably a material of formula (LiCI) x .2AI(OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10 .
• the product comprising a lithium adsorbent according to the invention comprises a mixture of at least two populations of particles of a lithium adsorbent, at least two of said populations of particles of a lithium adsorbent are into a different lithium adsorbent.
• the mass ratio of the quantity of gelled polysaccharide to the total quantity of said gelled polysaccharide and of the particles of a lithium adsorbent 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 preferably less than or equal to 10%, more preferably 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 quantity of lithium adsorbent particles in the product is greater for the same volume.
• the mass quantity of particles of a lithium adsorbent, after drying at 100° C. for 12 hours is greater than or equal to 90%, preferably greater than 95%, preferably greater than or equal to 96%, preferably greater than or equal to 97%, preferably greater than or equal to 98%, and less than 99.9%, preferably less than 99.8%, preferably less than 99.7%, based on the mass of the product comprising a lithium adsorbent according to the invention , after drying at 100°C for 12 hours.
• the product comprising a lithium adsorbent according to the invention can be in the form of cylinders, polylobes, rings, or spheres.
• the largest dimension of the product according to the invention (or the macroscopic object according to the invention) comprising a lithium adsorbent according to the invention is 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.
• the smallest dimension of the product according to the invention (or the macroscopic object according to the invention) comprising a lithium adsorbent, in a plane perpendicular to the direction of the largest dimension is greater than 1 ⁇ m, or even greater than 10 pm.
• the invention also relates to a product comprising a lithium adsorbent obtained or capable of being obtained by the process according to the invention.
• This product is remarkable for its ability to retain its physical integrity during repetitive lithium adsorption-desorption cycling. This property moreover constitutes a signature of the method according to the invention.
• the water content of a dough is determined as being the loss of mass, expressed as a percentage, after drying in air at 200°C for 16 hours.
• the pastes of the examples are previously air-dried for 170 hours at 25°C.
• the acquisitions are carried out using an X'Pert type device from Panalytical, equipped with a copper anode, over an angular range 2Q between 5° and 80°, with a pitch of 0.017°, and a counting time of 300 s/step.
• the front optic has a fixed 0.25° divergence slit, a 0.02 rad Soller slit, a 10 mm mask and a fixed 0.5° anti-scatter slit.
• the sample is rotating on itself.
• the rear optic has a fixed anti-scattering slit of 0.25°, a Soller slit of 0.02 rad 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 of the ICDD2016 database is used to identify the phase (UCI).2AI(OH) 3 , xH 2 0.
• the crystallized phase of lithiated bayerite highlighted may present a slight angular offset of the peaks compared to said data sheet, a consequence in particular of the quantity of Li inserted into the structure of the lithiated bayerite.
• the content of elements other than H and O, partly Li, Cl and Al, is determined on pasta dried at 200°C for 16 hours in air, by inductively coupled plasma spectrometry, using a 5800 ICP device -OES from Agilent.
• Aluminum trichloride hexahydrate AICl 3.6H 2 0 of purity greater than 99% by mass, marketed by the company Merck, for example 1,
• Oxalic acid of purity greater than 99% by mass, marketed by the company Merck, for example 1,
• Lithium hydroxide monohydrate LiOH, H 2 0
• LiOH, H 2 0 Lithium hydroxide monohydrate
• Lithium chloride LiCI of purity greater than 99.5%% by mass, for examples 1 and 2,
• Hydrochloric acid HCl of purity greater than 99% by mass, in aqueous solution at 16M, for example 2,
• Example 1 The product of Example 1 (comparative) was obtained as follows:
• Boehmite precipitation is carried out in the following manner. 2500 g of aluminum trichloride hexahydrate (AICl 3.6H 2 0 ) are added to 3950 g of demineralized water, the whole being kept under stirring in a 30 liter stainless steel jacketed reactor. Then, still with stirring, a solution of 1200 g of sodium hydroxide (NaOH) and 3 liters of demineralized water are added gradually, so as to adjust the pH. The pH reached at the end of the synthesis is equal to 8. The temperature is maintained at 20° C. for the duration of the boehmite precipitation step. Then the boehmite precipitate is washed and filtered using a filter press.
• Al 3.6H 2 0 aluminum trichloride hexahydrate
• the water content of the boehmite precipitate at the end of this step is 85% by mass. Then, 2500 g of said boehmite precipitate are replumped in 1600 g of demineralised water at ambient temperature, then a solution containing 170 g of LiCl and 16.7 liters of demineralised water is added (which corresponds to a Li/ AI equal to 0.39), the mixture being stirred and heated at 80° C. for 1 hour.
• the mixture thus obtained is cooled to 60° C., then filtered in a filter press so as to obtain a paste.
• the paste thus obtained has the characteristics shown in Table 1 below.
• Said paste is then dried at 50°C in air until it has a water content equal to 50%. Then, 120 g of said dried paste, still at a temperature equal to 50° C., are introduced into a Z-arm mixer. Then 2.38 g of a 10 g/l oxalic acid solution are added to said dough under stirring. A homogeneous mixture is obtained, which is 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 with a spatula on each side of the grid. so that said mixture fills the holes of said grid. The grid is then said to be “loaded”.
• the grid is placed under a circulation of hot air at 60°C, which makes it possible to “unload” said grid, the objects formed falling into a container placed under the grid.
• Said objects obtained are in the form of cylinders with an average length equal to 0.8 mm and an average diameter equal to 1.4 mm.
• Example 2 The product of Example 2 (according to the invention) was obtained as follows:
• LiCI is added, so that the molar ratio between the Cl provided by LiCI and GAI present initially in the mixture is equal to 1, the whole is mixed for a time equal to 5 minutes, the temperature being maintained at 25°C.
• the Li/Al molar ratio is equal to 1.5.
• the mixture is then heated using a hot plate, to a temperature equal to 60°C, the time during which said mixture is at a temperature greater than or equal to 50°C being equal to 15 minutes.
• the mixture is then maintained at a temperature equal to 60° C. for a time equal to 45 minutes.
• HCl is added to the mixture, so that the pH of the mixture is lowered to a value equal to 3, the value of the Cl/Al molar ratio in the mixture after addition of HCl being equal to 1.6, the duration of mixing being equal to 15 minutes, and the temperature being maintained equal to 60°C.
• the mixture thus obtained is filtered through a Buchner filter, at ambient temperature (below 50° C.), with filter papers of permeability equal to 2 ⁇ m so as to obtain a paste.
• the time during which the mixture is at a temperature greater than or equal to 50° C. is equal to 5 minutes.
• the paste obtained consists for more than 99% by mass of water, lithiated bayerite, and LiCI.
• a starting charge in accordance with the object of the present invention was produced, formed from a mixture of said paste obtained after filtration and ammonium alginate, the content of said alginate being equal to 1% by mass based on the mass of the starting batch, after drying at 200°C for 16 hours.
• Said paste containing lithiated bayerite and ammonium alginate was mixed in a planetary mixer under hot air created by a heat gun set on 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 charge was then 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 on each side of the grid of so that said starting charge fills the holes of said grid.
• the grid is then said to be “loaded”.
• the grid is placed under a circulation of hot air at 60° C., which makes it possible to “unload” said grid, the objects formed falling into a container placed under the grid.
• Said objects obtained are in the form of cylinders with an average length equal to 0.8 mm and an average diameter equal to 1.4 mm.
• the desorption step followed by the adsorption step corresponds to a simulation of a lithium adsorption-desorption cycle.
• the product undergoes a total of 10 lithium adsorption-desorption cycles.
• the product of Example 2 does not generate this phenomenon, even after 10 adsorption-desorption cycles of lithium: the aqueous solution of lithium chloride and the brine remain perfectly clear at the end of the desorption stage and at the end of the adsorption stage, respectively.
• the product of Example 2 according to the invention therefore has better resistance to repetitive cycling of adsorption-desorption of lithium than the product of example 1, comparative.

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• 2022
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