FR3141456A1 - Product comprising lithiated bayerite and process for manufacturing such a product - Google Patents

Abstract

The present invention relates to a product comprising: - water, and - crystallites, at least a part, preferably substantially all of said crystallites being made up of lithiated bayerite, the average size of the lithiated bayerite crystallites being greater than or equal to 10 nm and less than or equal to 25 nm, and said product having a cumulative level of aluminum hydroxide and boehmite less than or equal to 10%, said product comprising at least the elements Li, Cl, Al, O and H, the elements Li, Cl and Al being present in said dry product in the following contents, determined by inductively coupled plasma spectrometry, in weight percentages: - 2% < Li < 5%, - 10% < Cl < 26%, - 15% < Al < 30%.

Description

Product comprising lithiated bayerite and method of manufacturing such a product

The present invention relates to a product comprising lithiated bayerite and to a method of manufacturing a product comprising lithiated bayerite.

The use of lithium, particularly in batteries, is constantly increasing.

Brines are sources of lithium, for which lithium extraction 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.

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 crystalline solid material of formula (LiCl) _x .2Al(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 method for manufacturing LiX.2Al(OH) ₃ , _nH2O , X being an anion forming an acid in molecular combination with H or forming a salt in combination with a metal ion, said method comprising a step of reacting a hydrated alumina with a concentrated solution of LiX at a temperature above 85°C. However, the material obtained by this method has a limited lithium adsorption capacity.

There is a need for a method of manufacturing a product comprising lithiated bayerite, and which makes it possible to obtain a product having a high lithium adsorption capacity. The aim of the invention is to satisfy this need.

According to the invention, this aim is achieved by means of a product comprising, and preferably essentially consisting of:

- water, and

- crystallites, at least a portion, preferably substantially all, of said crystallites being constituted of lithiated bayerite,

the average size of the lithiated bayerite crystallites being greater than or equal to 10 nm and less than or equal to 25 nm, and

said product having a cumulative rate of aluminum hydroxide and boehmite less than or equal to 10%,

said product comprising at least the elements Li, Cl, Al, O and H,

the elements Li, Cl and Al being present in said dry product in the following contents, determined by inductively coupled plasma spectrometry, in weight percentages:

- 2% < Li < 5%,

- 10% < Cl < 26%,

- 15% < Al < 30%.

The average size of lithiated bayerite crystallites and the cumulative content of aluminum hydroxide and boehmite are measured on said product after exposure to air for 170 hours at 25°C, at atmospheric pressure.

The said dry product is obtained after drying in air at 200°C for 16 hours, at atmospheric pressure.

• le produit présente une analyse chimique suivante, déterminée sur le produit sec par spectrométrie à plasma à couplage inductif, en pourcentages poids :
  • Li en une teneur supérieure à 2 % et inférieure à 5%, et
  • Cl en une teneur supérieure 10 % et inférieure à 26%, et
  • Al en une teneur supérieure à 15% et inférieure à 30%, et
  • Eléments autres que Li, Cl, Al, O et H en une teneur inférieure à 3%, et
  • O et H en une teneur correspondant au complément à 100% ;
• la taille moyenne des cristallites de bayérite lithiée inférieure à 23 nm ;
• la teneur en eau est supérieure à 1%, de préférence supérieure à 5%, de préférence supérieure à 10% et/ou de préférence inférieure à 95%, de préférence inférieure à 80%, de préférence inférieure à 70% ;
• le taux cumulé d’hydroxyde d’aluminium et de boehmite est inférieur ou égal à 8%, de préférence inférieur ou égal à 5% ;
• les phases cristallisées du produit comportent la bayérite lithiée, la boehmite et/ou un hydroxyde d’aluminium choisi parmi la gibbsite, la bayérite, la doyleite, la nordstrandite et leurs mélanges, de préférence les phases cristallisées du produit comportent la bayérite lithiée et un hydroxyde d’aluminium choisi parmi la gibbsite, la bayérite, la doyleite, la nordstrandite et leurs mélanges ;
• la seule phase cristallisée présente dans le produit est la bayérite lithiée ;
• le produit est constitué pour au moins 80%, en masse, d’eau et des cristallites de bayérite lithiée, et d’hydroxyde d’aluminium et/ou de boehmite, et de LiCl, et d’un liant, de préférence le produit est constitué pour au moins 80%, en masse, d’eau et des cristallites de bayérite lithiée, et d’hydroxyde d’aluminium, et de LiCl, et d’un liant, de préférence le produit est constitué pour au moins 80%, en masse, d’eau et des cristallites de bayérite lithiée, et de LiCl, et d’un liant, ledit liant étant de préférence un polysaccharide, de préférence un alginate.

According to preferred but non-limiting embodiments of the present invention, which may, where appropriate, be combined with each other:

• the product has the following chemical analysis, determined on the dry product by inductively coupled plasma spectrometry, in weight percentages:
  • Li in a content greater than 2% and less than 5%, and
  • Cl in a content greater than 10% and less than 26%, and
  • Al in a content greater than 15% and less than 30%, and
  • Elements other than Li, Cl, Al, O and H in a content of less than 3%, and
  • O and H in a content corresponding to the complement to 100%;
• the average size of lithiated bayerite crystallites less than 23 nm;
• 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 rate 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 selected from gibbsite, bayerite, doyleite, nordstrandite and mixtures thereof, preferably the crystallized phases of the product comprise lithiated bayerite and an aluminum hydroxide selected 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 LiCl, 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 of LiCl, and of a binder, said binder preferably being a polysaccharide, preferably an alginate.

1. Mise en suspension aqueuse d’une source d’aluminium, de préférence d’une unique source d’aluminium, choisie parmi une boehmite ou un hydroxyde d’aluminium et leurs mélanges, de préférence un hydroxyde d’aluminium, broyage de ladite suspension aqueuse de manière à obtenir une taille médiane inférieure ou égale à 3 µm si la taille médiane de ladite source d’aluminium est supérieure à 3 µm, ladite suspension étant maintenue lors de cette étape a) à une température inférieure à 50°C,
2. Augmentation du pH par l’ajout d’une base, de telle manière que le rapport molaire entre le OH apporté par ladite base et l’Al présent dans le mélange soit supérieur à 0,20, ledit mélange étant maintenu en agitation après introduction de ladite base, à une température inférieure à 50°C ;
3. Ajout d’un sel de chlore, de telle manière que le rapport molaire entre le Cl apporté par ledit sel de chlore et l’Al présent dans le mélange, soit supérieur à 0,25, ledit mélange étant maintenu en agitation après introduction dudit sel de chlore à une température inférieure à 50°C ; la base à l’étape b), le sel de chlore à l’étape c) et leurs quantités respectives étant choisis de manière à apporter une quantité de lithium dans le mélange telle que le rapport molaire Li/Al soit supérieur ou égal à 1 ;
4. Elévation de la température du mélange jusqu’à une température supérieure ou égale à 50°C et inférieure ou égale à 60°C, le temps t₁étant le temps pendant lequel ledit mélange est à une température supérieure ou égale à 50°C ;
5. Maintien du mélange à une température supérieure ou égale à 50°C et inférieure ou égale à 60°C pendant un temps t₂;
6. Optionnellement, ajout d’un acide dans le mélange, sous agitation, de manière à diminuer le pH du mélange à une valeur inférieure ou égale à 8, le sel de chlore à l’étape c), ledit acide, et leurs quantités respectives étant choisis de manière à ce que le rapport molaire Cl/Al dans le mélange soit supérieur ou égal à 1, le mélange étant maintenu à une température inférieure ou égale à 60°C, le temps t₃étant le temps pendant lequel le mélange est à une température supérieure ou égale à 50°C, le rapport molaire entre le Cl apporté par le sel de chlore et l’Al présent dans le mélange à l’étape c) étant supérieur ou égal à 0,5 si le procédé ne comporte pas ladite étape f) ;
7. Optionnellement, et de préférence, filtration du mélange de manière à obtenir une pâte, le mélange étant maintenu à une température inférieure ou égale à 60°C, le temps t₄étant le temps pendant lequel le mélange est à une température supérieure ou égale à 50°C ;

The invention also relates to a method of manufacturing a product according to the invention and as previously described, comprising the following steps:

1. Aqueous suspension of an aluminum source, preferably a single aluminum source, chosen from a boehmite or an aluminum hydroxide and their mixtures, preferably an aluminum hydroxide, grinding said aqueous suspension so as to obtain a median size less than or equal to 3 µm if the median size of said aluminum source is greater than 3 µm, said suspension being maintained during this step a) at a temperature below 50°C,
2. Increasing the pH by adding a base, such that the molar ratio between the OH provided by said base and the Al 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;
3. Addition of a chlorine salt, such that the molar ratio between the Cl provided by said chlorine salt and the Al 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; the base in step b), the chlorine salt in step c) and their respective quantities being 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;
4. Raising the temperature of the mixture to a temperature greater than or equal to 50°C and less than or equal to 60°C, the time t ₁ being the time during which said mixture is at a temperature greater than or equal to 50°C;
5. Maintaining the mixture at a temperature greater than or equal to 50°C and less than or equal to 60°C for a time t ₂ ;
6. Optionally, adding an acid to the mixture, with stirring, so as to reduce the pH of the mixture to a value less than or equal to 8, the chlorine salt in step c), said acid, and their respective amounts being chosen so that the Cl/Al molar ratio in the mixture is greater than or equal to 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, the molar ratio between the Cl provided by the chlorine salt and the Al present in the mixture in step c) being greater than or equal to 0.5 if the process does not include said step f);
7. Optionally, and preferably, filtration of the mixture so as to obtain a paste, the 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;

the cumulative time t ₁ + t ₂ + t ₃ + t ₄ = t ₅ being greater than or equal to 45 minutes and less than 15 hours.

• L’étape a) comprend la mise en œuvre d’un broyage de la suspension aqueuse d’une source d’aluminium choisie parmi une boehmite ou un hydroxyde d’aluminium et leurs mélanges, de manière à obtenir une taille médiane ≤ 1 µm ;
• le temps t₅est tel que les temps t₁, t_2,t₃et t₄satisfont les relations suivantes : [t₁/(-1,2T₁+75)] + [t₂/(-1,2T₂₀+75)] + [t₃/(-1,2T₃₀+75)] + [t₄/(-1,2T₄₀+75)] ≤ 1, de préférence [t₁/(-0,8T₁+50)] + [t₂/(-0,8T₂₀+50)] + [t₃/(-0,8T₃₀+50)] + [t₄/(-0,8T₄₀+50)] ≤ 1, de préférence [t₁/(-0,55T₁+34,5)] + [t₂/(-0,55T₂₀+34,5)] + [t₃/(-0,55T₃₀+34,5)] + [t₄/(-0,55T₄₀+34,5)] ≤ 1, et [t₁/(-0,225T₁+14,25)] + [t₂/(-0,225T₂₀+14,25)] + [t₃/(-0,225T₃₀+14,25)] + [t₄/(-0,225T₄₀+14,25)] ≥ 1, de préférence [t₁/(-0,2T₁+13)] + [t₂/(-0,2T₂₀+13)] + [t₃/(-0,2T₃₀+13)] + [t₄/(-0,2T₄₀+13)] ≥ 1, avec T₁étant la température atteinte par le mélange à l’étape d), T₂₀étant la température moyenne lors de l’étape e), T₃₀étant la température moyenne lors de l’étape f), T₄₀étant la température moyenne du mélange pendant le temps t₄;
• l’hydroxyde d’aluminium, la boehmite et leurs mélanges sont les seules sources d’aluminium utilisées dans l’ensemble des étapes du procédé, de préférence l’hydroxyde d’aluminium est la seule source d’aluminium utilisée dans l’ensemble des étapes du procédé ;
• à l’étape b), le rapport molaire entre le OH apporté par la base et l’Al présent dans le mélange est supérieur à 0,25 et inférieur à 10 ;
• à l’étape b), le pH du mélange après ajout de la base est supérieur à 9 et inférieur à 13 ;
• à l’étape c), le rapport molaire entre le Cl apporté par le sel de chlore et l’Al présent dans le mélange est inférieur à 10 ;
• la base à l’étape b), le sel de chlore à l’étape c), et leurs quantités respectives sont choisis de manière à apporter une quantité de lithium dans le mélange telle que le rapport molaire Li/Al soit supérieur à 1,1 et inférieur à 4 ;
• à l’étape d), le temps t₁est supérieur à 5 minutes ;
• à l’étape e), la température du mélange est sensiblement constante ;
• à l’étape e), le temps t₂est supérieur à 40 minutes ;
• à l’étape f) optionnelle, au moins une partie de la quantité de Cl nécessaire pour obtenir un rapport molaire Cl/Al supérieur ou égal à 1 est apportée par l’acide ;
• à l’étape f) optionnelle, le pH du mélange est diminué à une valeur inférieure à 7,5, et supérieure à 6,5 ;
• à l’étape f) optionnelle, le rapport molaire Cl/Al dans le mélange est réglé à une valeur inférieure à 3 ;
• à l’étape f) optionnelle, la température du mélange est sensiblement constante ;
• à l’étape f) optionnelle, le temps t₃est supérieur à 5 minutes ;
• à l’étape g), le temps t₄est inférieur à 15 minutes ;
• les étapes a) et b) sont réalisées de manière simultanée ;
• les étapes a), b) et c) sont réalisées de manière simultanée ;
• le procédé comporte, après l’étape g), une étape h) de mise en forme d’une charge de départ comportant la pâte obtenue en fin d’étape g), sous la forme d’un objet ou d’un revêtement, de préférence sous la forme d’un objet, et une étape optionnelle i) de réduction de la teneur en eau dudit objet ou dudit revêtement ;
• à l’étape h), la charge de départ comporte un liant, de préférence un polysaccharide comprenant un groupement apte à former une liaison ionique avec un agent de gélification pour la formation d’un polysaccharide gélifié, de préférence un polysaccharide choisi parmi les alginates ;
• les étapes h) et i) sont réalisées, au moins partiellement, de manière simultanée.

According to preferred but non-limiting embodiments of the present invention, which may, where appropriate, be combined with each other:

• Step a) comprises the implementation of a grinding of the aqueous suspension of an aluminum source chosen from a boehmite or an aluminum hydroxide and their mixtures, so as to obtain a median size ≤ 1 µm;
• time t ₅ is such that times t ₁ , t _2, t ₃ and t ₄ satisfy the following relations: [t ₁ /(-1.2T ₁ +75)] + [t ₂ /(-1.2T ₂₀ +75)] + [t ₃ /(-1.2T ₃₀ +75)] + [t ₄ /(-1.2T ₄₀ +75)] ≤ 1, preferably [t ₁ /(-0.8T ₁ +50)] + [t ₂ /(-0.8T ₂₀ +50)] + [t ₃ /(-0.8T ₃₀ +50)] + [t ₄ /(-0.8T ₄₀ +50)] ≤ 1, preferably [t ₁ /(-0.55T ₁ +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 [t ₁ /(-0.225T ₁ +14.25)] + [t ₂ /(-0.225T ₂₀ +14.25)] + [t ₃ /(-0.225T ₃₀ +14.25)] + [t ₄ /(-0.225T ₄₀ +14.25)] ≥ 1, preferably [t ₁ /(-0.2T ₁ +13)] + [t ₂ /(-0.2T ₂₀ +13)] + [t ₃ /(-0.2T ₃₀ +13)] + [t ₄ /(-0.2T ₄₀ +13)] ≥ 1, with T ₁ being the temperature reached by the mixture in step d), T ₂₀ being the average temperature during step e), T ₃₀ being the average temperature during step f), T ₄₀ being the average temperature of the mixture during time t ₄ ;
• aluminum hydroxide, boehmite and mixtures thereof are the only sources of aluminum used in all process steps, preferably aluminum hydroxide is the only source of aluminum used in all process steps;
• in step b), the molar ratio between the OH provided by the base and the Al present in the mixture is greater than 0.25 and less than 10;
• in step b), the pH of the mixture after addition of the base is greater than 9 and less than 13;
• in step c), the molar ratio between the Cl provided by the chlorine salt and the Al present in the mixture is less than 10;
• 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 1.1 and less than 4;
• in step d), time t ₁ is greater than 5 minutes;
• in step e), the temperature of the mixture is substantially constant;
• in step e), time t ₂ is greater than 40 minutes;
• in optional step f), at least part of the quantity of Cl necessary to obtain a Cl/Al molar ratio greater than or equal to 1 is provided by the acid;
• in optional step f), the pH of the mixture is reduced to a value less than 7.5, and greater than 6.5;
• in optional step f), the Cl/Al molar ratio in the mixture is set to a value less than 3;
• in optional step f), the temperature of the mixture is substantially constant;
• in optional step f), time t ₃ is greater than 5 minutes;
• in step g), time t ₄ is less than 15 minutes;
• steps a) and b) are carried out simultaneously;
• steps a), b) and c) are carried out simultaneously;
• 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;
• in step h), 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 above.

Definitions

• The term "lithiated bayerite" refers to the compound with the formula LiCl.2Al(OH) ₃ .xH ₂ O as indicated in the ICDD PDF 00-031-0700, but also by extension, compounds with a ratio of the molar quantities of lithium and aluminum, Li/Al, 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 with the formula Al(OH) ₃ is called "aluminum hydroxide". Gibbsite, bayerite, doyleite, and nordstrandite are aluminum hydroxides.
• The compound with the formula γ-AlO(OH) is called "boehmite".
• The “cumulative rate of aluminium hydroxide and boehmite”, in %, in a product, is calculated according to the following formula (1):

T = 100* (A _HA + A _BO )/ (A _HA + A _BO + A _BL ) (1)

• A_HAest la somme des aires des phases hydroxydes d’aluminium, mesurées sur un diagramme de diffraction X dudit produit, par exemple obtenu à partir d’un appareil du type diffractomètre X’Pert de la société Panalytical, pourvu d’un tube DX en cuivre, sans traitement de déconvolution, après avoir éliminé la raie Kα2. L’aire d’une phase hydroxyde d’aluminium est celle de son pic de diffraction se trouvant dans un domaine angulaire 2θ sensiblement égal à 18,3° ;
• A_BOest l’aire du pic de diffraction de la boehmite se trouvant dans un domaine angulaire 2θ sensiblement égal à 14°, mesurée sur le même diagramme, sans traitement de déconvolution, après avoir éliminé la raie Kα2 ;
• A_BLest l’aire du pic de diffraction du plan (003) de la bayérite lithiée se trouvant dans un domaine angulaire 2θ sensiblement égal à 11,3°, mesurée sur le même diagramme, sans traitement de déconvolution, après avoir éliminé la raie Kα2.
• On appelle « polysaccharides », selon la définition classique, des polymères composés d’enchaînements d’unités osidiques reliées par des liaisons glycosidiques.
• On appelle « polysaccharide gélifiable » sous l’action d’un agent de gélification, un polysaccharide apte à former un gel sous l’action dudit agent de gélification.
• Un polysaccharide gélifié résulte de l’association de chaînes du polysaccharide sous l’action d’un agent gélifiant. A titre d’exemple, l’alginate a pour formule (C₆H₇O₆ ^-)_n. L’alginate est une chaîne polyosidique comprenant des groupements carboxylates COO^-. Des ions calcium Ca²⁺(agent de gélification) réagissent avec deux brins d’alginate, c’est-à-dire avec les groupements carboxylates COO^-, entraînant la polymérisation des chaînes d’alginate et la liaison des molécules entre elles. La réaction permet ainsi la création d’un gel.
• On entend par « produit sec », un produit obtenu après séchage sous air à 200°C pendant 16 heures (à la pression atmosphérique), ce séchage étant par exemple classiquement effectué dans une étuve.
• On appelle « taille médiane » d’une poudre de particules ou d’une suspension de particules, la taille divisant lesdites particules de la poudre ou de la suspension, en première et deuxième populations égales en masse, ces première et deuxième populations ne comportant que des particules présentant une taille supérieure ou égale, ou inférieure respectivement, à la taille médiane. La taille médiane peut par exemple être déterminée à l’aide d’un granulomètre laser.

Or

• A _HA is the sum of the areas of the aluminum hydroxide phases, measured on an X-ray diffraction diagram of said product, for example obtained from a device of the X'Pert diffractometer type from the company Panalytical, equipped with a copper DX tube, without deconvolution treatment, after having eliminated the Kα2 line. The area of an aluminum hydroxide phase is that of its diffraction peak located in an angular domain 2θ substantially equal to 18.3°;
• A _BO is the area of the diffraction peak of boehmite located in an angular domain 2θ approximately equal to 14°, measured on the same diagram, without deconvolution treatment, after eliminating the Kα2 line;
• A _BL is the area of the diffraction peak of the (003) plane of lithiated bayerite located in an angular domain 2θ approximately equal to 11.3°, measured on the same diagram, without deconvolution treatment, after eliminating the Kα2 line.
• According to the classical definition, "polysaccharides" are polymers composed of chains of osidic units linked by glycosidic bonds.
• A "gellable polysaccharide" under the action of a gelling agent is a polysaccharide capable of forming a gel under the action of said gelling agent.
• A gelled polysaccharide results from the association of polysaccharide chains under the action of a gelling agent. For example, alginate has the formula (C ₆ H ₇ O ₆ ^- ) _n . Alginate is a polysaccharide chain comprising carboxylate groups COO ^- . Calcium ions Ca ²⁺ (gelling agent) react with two strands of alginate, i.e. with the carboxylate groups COO ^- , leading to the polymerization of the alginate chains and the bonding of the molecules together. The reaction thus allows the creation of a gel.
• The term “dry product” means a product obtained after drying in air at 200°C for 16 hours (at atmospheric pressure), this drying being, for example, conventionally carried out in an oven.
• The term "median size" of a powder of particles or a suspension of particles is the size dividing said particles of the powder or suspension into first and second populations equal in mass, these first and second populations 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 granulometer.

All percentages in this description are percentages by mass unless otherwise indicated.

The verbs “contain,” “include,” and “present” should be interpreted broadly, without limitation, unless otherwise indicated.

Detailed description

• Une teneur en eau supérieure à 1%, de préférence supérieure à 5%, de préférence supérieure à 10% et/ou de préférence inférieure à 95%, de préférence inférieure à 90%, de préférence inférieure à 80%, de préférence inférieure à 70%, voire inférieure à 60%. La teneur en eau est la perte de masse, exprimée en pourcentage, après séchage à 200°C pendant 16 heures sous air, à la pression atmosphérique ;
• Une taille moyenne des cristallites de bayérite lithiée inférieure à 23 nm, de préférence inférieure à 20 nm ;
• Un taux cumulé d’hydroxyde d’aluminium et de boehmite inférieur ou égal à 8%, de préférence inférieur ou égal à 5%, de préférence sensiblement nul ;
• Les phases cristallisées comportent, de préférence consistent en la bayérite lithiée, la boehmite et/ou un hydroxyde d’aluminium choisi parmi la gibbsite, la bayérite, la doyleite, la nordstrandite et leurs mélanges, de préférence la gibbsite. De préférence, Les phases cristallisées comportent, de préférence consistent en la bayérite lithiée et un hydroxyde d’aluminium choisi parmi la gibbsite, la bayérite, la doyleite, la nordstrandite et leurs mélanges, de préférence la gibbsite. De préférence, la seule phase cristallisée est la bayérite lithiée. La détermination des phases cristallisées, la détermination du taux cumulé d’hydroxyde d’aluminium et de boehmite et la mesure de la taille des cristallites de bayérite lithiée sont réalisées sur le produit après exposition à l’air pendant 170 heures à 25°C, à la pression atmosphérique ;
• les éléments Li, Cl et Al sont présents dans ledit produit, après séchage sous air à 200°C pendant 16 heures, à la pression atmosphérique, dans les teneurs suivantes, en pourcentages poids :
  • Li : de préférence supérieure à 2,5%, de préférence supérieure à 3%, et/ou de préférence inférieure à 4,5%, de préférence inférieure à 4%, et
  • Cl : de préférence supérieure à 11%, de préférence supérieure à 13% et/ou de préférence inférieure à 24%, de préférence inférieure à 22%, et
  • Al : de préférence supérieure à 17%, de préférence supérieure à 19% et/ou de préférence inférieure à 28%, de préférence inférieure à 26% ;
• Après séchage sous air à 200°C pendant 16 heures, à la pression atmosphérique, une analyse chimique suivante, déterminée par spectrométrie à plasma à couplage inductif, en pourcentages poids :
  • Li en une teneur supérieure à 2 %, de préférence supérieure à 2,5%, de préférence supérieure à 3% et inférieure à 5%, de préférence inférieure à 4,5%, de préférence inférieure à 4%, et
  • Cl en une teneur supérieure 10 %, de préférence supérieure à 11%, de préférence supérieure à 13% et inférieure à 26%, de préférence inférieure à 24%, de préférence inférieure à 22%, et
  • Al en une teneur supérieure à 15%, de préférence supérieure à 17%, de préférence supérieure à 19% et inférieure à 30%, de préférence inférieure à 28%, de préférence inférieure à 26%, et
  • Eléments autres que Li, Cl, Al, O et H en une teneur inférieure à 3%, de préférence inférieure à 2%, de préférence inférieure à 1%, et
  • O et H en une teneur correspondant au complément à 100% ;
• Après séchage sous air à 200°C pendant 16 heures, à la pression atmosphérique, le produit présente un rapport massique Li/Al supérieur à 0,1, de préférence supérieur à 0,15 et/ou de préférence inférieur à 0,3, de préférence inférieur à 0,25 ;
• Après séchage sous air à 200°C pendant 16 heures, à la pression atmosphérique, le produit présente un rapport massique Li/Cl supérieur à 0,08, de préférence supérieur à 0,1, de préférence supérieur à 0,13, de préférence supérieur à 0,15 et/ou de préférence inférieur à 0,4, de préférence inférieur à 0,3, de préférence inférieur à 0,25 ;
• Le produit est constitué, pour au moins 80%, de préférence pour plus de 85%, de préférence pour plus de 90%, de préférence pour plus de 95%, de préférence pour plus de 99% en masse, d’eau et des cristallites de bayérite lithiée, et d’hydroxyde d’aluminium et/ou de boehmite, et de LiCl, et d’un liant, de préférence un polysaccharide, de préférence un polysaccharide gélifié, de préférence un alginate, de préférence un alginate gélifié. De préférence, le produit est constitué pour au moins 80%, de préférence pour plus de 85%, de préférence pour plus de 90%, de préférence pour plus de 95%, de préférence pour plus de 99% en masse, d’eau et desdits cristallites et d’hydroxyde d’aluminium et de LiCl et d’un liant, de préférence un polysaccharide, de préférence un polysaccharide gélifié, de préférence un alginate, de préférence un alginate gélifié. De préférence, le produit est constitué pour au moins 80%, de préférence pour plus de 85%, de préférence pour plus de 90%, de préférence pour plus de 95%, de préférence pour plus de 99% en masse, d’eau et desdits cristallites et de LiCl et d’un liant, de préférence un polysaccharide, de préférence un alginate ;
• Le produit se présente sous la forme d’objets ayant la forme de cylindres, de polylobes, d’anneaux, ou de sphères. De préférence, lesdits objets présentent une plus grande dimension inférieure à 100 mm, de préférence inférieure à 80 mm, de préférence inférieure à 50 mm, de préférence inférieure à 30 mm, voire inférieure à 10 mm et/ou une plus petite dimension, mesurée dans un plan perpendiculaire à la direction de la plus grande dimension, supérieure à 1µm, voire supérieure à 10 µm (micromètres) ;
• Le produit se présente sous la forme d’un revêtement déposé sur un support. De préférence, l’épaisseur dudit revêtement est supérieure à 10 µm, de préférence supérieure à 50 µm, de préférence supérieure à 100 µm, de préférence supérieure à 200 µm, et de préférence inférieure à 1 mm, de préférence inférieure à 500 µm. De préférence le support est en un matériau choisi parmi les céramiques, les métaux, les produits organiques, en particulier les polymères, et leurs mélanges ;
• Lorsque le produit contient un polysaccharide, de préférence un polysaccharide gélifié, de préférence un alginate ou une pectine, de préférence un alginate gélifié ou une pectine gélifiée, de préférence un alginate, de préférence un alginate gélifié, la quantité massique du polysaccharide, de préférence du polysaccharide gélifié est supérieure ou égal à 0,1%, de préférence supérieure ou égal à 0,2%, de préférence supérieure ou égal à 0,3% et inférieure ou égal à 5%, de préférence inférieure ou égal à 4%, de préférence inférieure ou égal à 3%, de préférence inférieure ou égal à 2%, de préférence inférieure ou égal à 1%. Le polysaccharide, l’alginate, contenu dans le liant peut être par exemple mis en évidence par chromatographie d’exclusion stérique.

A product according to the invention has one or more of the following optional characteristics:

• A water content greater than 1%, preferably greater than 5%, preferably greater than 10% and/or preferably less than 95%, preferably less than 90%, preferably less than 80%, preferably less than 70%, or even less than 60%. 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 less than 23 nm, preferably less than 20 nm;
• A cumulative rate 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 selected from gibbsite, bayerite, doyleite, nordstrandite and their mixtures, preferably gibbsite. Preferably, the crystallized phases comprise, preferably consist of lithiated bayerite and an aluminum hydroxide selected from gibbsite, bayerite, doyleite, nordstrandite and their mixtures, preferably gibbsite. Preferably, the only crystallized phase is lithiated bayerite. The determination of the crystallized phases, the determination of the cumulative content of aluminum hydroxide and boehmite and the measurement of the size of the crystallites of lithiated bayerite are carried out on the product after exposure to air for 170 hours at 25°C, at atmospheric pressure. ;
• the elements Li, Cl and Al are present in said product, after drying in air at 200°C for 16 hours, at atmospheric pressure, in the following contents, in weight percentages:
  • 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%;
• After drying in air at 200°C for 16 hours, at atmospheric pressure, the following chemical analysis, determined by inductively coupled plasma spectrometry, in weight percentages:
  • 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
  • Al in a content greater than 15%, preferably greater than 17%, preferably greater than 19% and less than 30%, preferably less than 28%, preferably less than 26%, and
  • Elements other than Li, Cl, Al, O and H in a content of less than 3%, preferably less than 2%, preferably less than 1%, and
  • O and H in a content corresponding to the complement at 100%;
• 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. ;
• After drying in air at 200°C for 16 hours, at atmospheric pressure, the product has a Li/Cl 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 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 crystallites of lithiated bayerite, and aluminum hydroxide and/or boehmite, and LiCl, and a binder, preferably a polysaccharide, preferably a gelled polysaccharide, preferably an alginate, preferably a gelled alginate. Preferably, 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. Preferably, 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 LiCl and a binder, preferably a polysaccharide, preferably an alginate;
• The product is in the form of objects having the shape of cylinders, polylobes, rings, or spheres. Preferably, said objects have a largest dimension of 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 smallest dimension, measured in a plane perpendicular to the direction of the largest dimension, of greater than 1 µm, or even greater than 10 µm (micrometers);
• The product is in the form of a coating deposited on a support. Preferably, the thickness of said coating is greater than 10 µm, preferably greater than 50 µm, preferably greater than 100 µm, preferably greater than 200 µm, and preferably less than 1 mm, preferably less than 500 µm. Preferably, the support is made of a material chosen from ceramics, metals, organic products, in particular polymers, and their mixtures;
• When 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 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, the alginate, contained in the binder can for example be detected by size exclusion chromatography.

A product according to the invention can be manufactured according to a method according to the invention comprising steps a) to g), in particular and preferably steps a) to i). mentioned above.

In step a) , an aluminum source selected 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 aluminum source is greater than 3 µm, said aqueous suspension is ground so as to obtain a median size less than or equal to 3 µm, preferably less than or equal to 2 µm, preferably less than or equal to 1 µm, preferably less than or equal to 0.7 µm, preferably less than or equal to 0.5 µm,

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.

Preferably, the grinding of the aqueous suspension is carried out if the median size of the aluminum source is greater than 2 µm, greater than 1 µm.

In a preferred embodiment, an aqueous suspension of an aluminum source selected from a boehmite or an aluminum hydroxide and their mixtures, preferably an aluminum hydroxide, is ground so as to obtain a median size ≤ 1 µm, said suspension being maintained during this step at a temperature below 50°C.

Preferably the aluminum hydroxide is gibbsite.

Preferably, aluminum hydroxide, boehmite and their mixtures are the only sources of aluminum used in all the steps of the process according to the invention. Preferably, aluminum hydroxide is the only source of aluminum used in all the steps of the process according to the invention.

Preferably, the median size obtained after grinding is less than or equal to 0.7 µm, preferably less than or equal to 0.5 µm.

Preferably, the suspension is maintained during step a) at a temperature above 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.

In 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 Al 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.

Preferably, the molar ratio between the OH provided by said base and the Al 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 than 2, preferably less than 1.5.

Preferably, particularly when the aluminium source used in step a) is an aluminium hydroxide, 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.

Preferably, the base does not contain the aluminum element.

More preferably, the base used is selected from NaOH, LiOH, NH ₄ OH, KOH, Ca(OH) ₂ , RbOH, CsOH, Sr(OH) ₂ , Ba(OH) ₂ , Mg(OH) ₂ , and mixtures thereof. More preferably, the base is selected from NaOH, LiOH, NH ₄ OH, and mixtures thereof. More preferably, the base is LiOH.

Preferably, the stirring time is greater than 5 minutes, preferably greater than 10 minutes, preferably greater than 15 minutes, and preferably less than 5 hours.

Preferably, the mixture is kept stirring at a temperature above 15°C, preferably above or equal to 20°C, preferably above or equal to 25°C.

In one embodiment, steps a) and b) are performed simultaneously.

In 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 Al 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 Al 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).

In one embodiment, the method comprises step f).

Preferably, the molar ratio between the Cl provided by said chlorine salt and the Al present in the mixture is greater than 0.25, preferably greater than 0.4, preferably greater than 0.5, and 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 than 2, preferably less than 1.5.

Preferably the chlorine salt does not contain the element aluminum.

More preferably, the chlorine salt is selected from LiCl, NaCl, KCl, CaCl ₂ , NH ₄ Cl, MgCl ₂ and mixtures thereof, preferably selected from LiCl, NaCl, KCl, CaCl ₂ and mixtures thereof. Preferably the chlorine salt is LiCl.

Preferably, the stirring time is greater than 5 minutes, preferably greater than 10 minutes, preferably greater than 15 minutes, and preferably less than 48 hours.

Preferably, the mixture is kept stirring at a temperature above 15°C, preferably above or equal to 20°C, preferably above 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. Preferably, said molar ratio is greater than 1.1, preferably greater than 1.2, and preferably less than 4, preferably less than 2.

In one embodiment, steps a), b) and c) are performed simultaneously.

In step d) , the temperature of the mixture is increased to a temperature T ₁ greater than or equal to 50°C and less than or equal to 60°C, the time t ₁ being the time during which said mixture is at a temperature greater than or equal to 50°C.

Preferably, the mixture is kept stirring during step d).

Preferably, the time t ₁ is greater than 5 minutes, preferably greater than 10 minutes, and preferably less than 15 hours, preferably less than 10 hours.

In 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 .

Preferably, the mixture is kept stirring during step e).

Let T ₂₀ be the average temperature during step e)

Preferably, during step e), the temperature of the mixture is substantially constant and equal to T ₂₁ .

Preferably, 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.

In step f) , optional, 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 6, preferably greater than or equal to 6.5, the chlorine salt in step c), said acid, and their respective amounts being chosen so that the Cl/Al molar ratio in the mixture is greater than 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.

In a preferred embodiment, at least part of the amount of Cl necessary to obtain a Cl/Al molar ratio greater than or equal to 1, preferably greater than 1, is provided by said acid.

In one embodiment, multiple acids are added to the mixture. In this embodiment, one of the acids may comprise Cl, preferably comprises Cl.

Preferably the acid is selected from HCl, _H2SO4 , _HNO3 , _HI , HBr, _HClO4 , _HClO3 , _HMnO4 , _H2MnO4 and mixtures thereof, preferably from HCl, _HNO3 , HBr, _HClO4 , _HClO3 and mixtures thereof. Preferably the acid is _HCl .

Preferably the Cl/Al molar ratio in the mixture is set to a value less than 3, preferably less than 2.

Let T ₃₀ be the average temperature during step f).

Preferably, during step f), the temperature of the mixture is substantially constant and equal to T ₃₁ .

Preferably, 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.

The implementation of step f) depends in particular on the nature of the lithium source for which the extraction of lithium is envisaged, in particular its pH. For example, if said lithium source has a pH of less than 7, the method according to the invention preferably comprises step f).

The mixture produced in steps b), c), d), e) and possibly f) can be produced using any known technique, such as using a mixer or grinder, preferably using a wet process with control and adjustment of the temperature of the mixture.

In 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.

We call T ₄₀ the average temperature of the mixture during time t ₄ .

Preferably, during step g), the temperature of the mixture during time t ₄ is substantially constant and equal to T ₄₁ .

In one embodiment, the temperature of the mixture is lowered below 50°C before the start of filtration.

In a preferred embodiment, 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 stage, in particular a filter press, a centrifuge, a belt filter, a drum filter.

At the end of optional step g), the cumulative time t ₁ + 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.

Preferably, the time t ₅ is greater than 50 minutes, preferably greater than 55 minutes, preferably greater than 1 hour.

The time t ₅ is a function of the temperature and the median size of the aluminum source. The person skilled in the art knows how to adjust the time t ₅ as a function of the temperature and the median size of the aluminum source. For example, if the median size of the aluminum source is less than 1 µm, and if in step g), t ₄ is equal to 0, and if the temperature in steps d), e) and f) is equal to 50°C (i.e. T ₁ =T ₂₁ =T ₃₁ =50°C), the time t ₅ is greater than 3 hours and less than 15 hours, preferably less than 10 hours, preferably less than 7 hours. For example, if the median size of the aluminum source is less than 1 µm, and if the temperature in steps d), e) and f) is equal to 60°C (i.e. T ₁ =T ₂₁ =T ₃₁ = 60°C), and if preferably the time t ₄ is less than 15 minutes, preferably less than 10 minutes, preferably less than 5 minutes, the time t ₅ is greater than or equal to 45 minutes, preferably greater than 1 hour and less than 3 hours, preferably less than 2 hours, preferably less than 1.5 hours.

Preferably the time t ₅ is such that the times t ₁ , t _2, t ₃ and t ₄ satisfy the following relations:

[t ₁ /(-1.2T ₁ +75)] + [t ₂ /(-1.2T ₂₀ +75)] + [t ₃ /(-1.2T ₃₀ +75)] + [t ₄ /( -1.2T ₄₀ +75)] ≤ 1 and [t ₁ /(-0.225T ₁ +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, time t ₅ is such that times t ₁ , t _2, t ₃ and t ₄ satisfy the following relations:

[t ₁ /(-0.8T ₁ +50)] + [t ₂ /(-0.8T ₂₀ +50)] + [t ₃ /(-0.8T ₃₀ +50)] + [t ₄ /(-0.8T ₄₀ +50)] ≤ 1, preferably [t ₁ /(-0.55T ₁ +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/or [t ₁ /(-0.2T ₁ +13)] + [t ₂ /(-0.2T ₂₀ +13)] + [t ₃ /(-0.2T ₃₀ +13)] + [t ₄ /(-0.2T ₄₀ +13)] ≥ 1.

In one embodiment, the temperatures in steps d), e) and optionally f) are substantially constant and equal to T ₁ , T ₂₁ and T ₃₁ , respectively, and the time t ₅ is such that the times t ₁ , t ₂ , t ₃ and t ₄ satisfy the following relationships:

[t ₁ /(-1.2T ₁ +75)] + [t ₂ /(-1.2T ₂₁ +75)] + [t ₃ /(-1.2T ₃₁ +75)] + [t ₄ /( -1.2T ₄₀ +75)] ≤ 1 and [t ₁ /(-0.225T ₁ +14.25)] + [t ₂ /(-0.225T ₂₁ +14.25)] + [t ₃ /(-0.225T ₃₁ +14.25)] + [t ₄ /(-0.225T ₄₀ +14.25)] ≥ 1.

Preferably, in said embodiment, the time t ₅ is such that the times t ₁ , t ₂ , t ₃ and t ₄ satisfy the following relationships:

[t ₁ /(-0.8T ₁ +50)] + [t ₂ /(-0.8T ₂₁ +50)] + [t ₃ /(-0.8T ₃₁ +50)] + [t ₄ /(-0.8T ₄₀ +50)] ≤ 1, preferably [t ₁ /(-0.55T ₁ +34.5)] + [t ₂ /(-0.55T ₂₁ +34.5)] + [t ₃ /(-0.55T ₃₁ +34.5)] + [t ₄ /(-0.55T ₄₀ +34.5)] ≤ 1 and/or [t ₁ /(-0.2T ₁ +13)]+[t ₂ /(-0.2T ₂₁ +13)]+ [t ₃ /(-0.2T ₃₁ +13)] +13)] + [t ₄ /(-0.2T ₄₀ +13)] ≥ 1.

These relationships advantageously make it possible to improve the lithium adsorption capacity of the product according to the invention.

In one embodiment, the temperature in steps d), e) and f) is equal to 60°C (in other words T ₁ =T ₂₁ =T ₃₁ =60°C), the time t ₄ being preferably less than 15 minutes, preferably less than 10 minutes, preferably less than 5 minutes, and the cumulative time t ₁ +t ₂ +t ₃ +t ₄ , in other words t ₅ , time during which the mixture has been 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, preferably greater than 1 hour and less than 3 hours, preferably less than 2 hours, preferably less than 1.5 hours.

In one embodiment, the temperature in steps d), e) and f) is equal to 50°C (i.e. T ₁ =T ₂₁ =T ₃₁ =50°C), the time t ₄ is equal to 0, and the cumulative time t ₁ +t ₂ +t ₃ , i.e. t ₅ , time during which the mixture was exposed to a temperature equal to 50°C is greater than 3 hours and less than 15 hours, preferably less than 10 hours, preferably less than 7 hours.

In a preferred embodiment, the method according to the invention 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, and an optional step i) of reducing the water content of said object.

In step h) , a starting charge comprising the paste obtained at the end of step g) is shaped into an object or a coating deposited on a support.

The shaping may be carried out using any technique known to those skilled in the art, for example extrusion, granulation, pressing, casting, atomization, screen printing, tape casting, or drip casting, in particular when an object is obtained, or by stamping, lamination, coating, granulation, in particular when a coating deposited on a support is obtained.

In one embodiment, the starting charge does not include a binder.

In one embodiment, 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 an amount such that the mass ratio of the amount of said polysaccharide to the total amount of said polysaccharide and 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%. Preferably, 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 2%, preferably less than or equal to 1%.

Preferably, the group of the polysaccharide capable of forming an ionic bond with a gelling agent is a carboxylate group COO ^- .

Preferably, the polysaccharide comprises a group capable of forming an ionic bond with a gelling agent chosen from divalent cations, trivalent cations (for example a cation of Fe or Al) and mixtures thereof, preferably chosen from alkaline earth cations, preferably chosen from cations of Ca, Sr, Ba, Mg and mixtures thereof. Preferably, the polysaccharide comprises a group capable of forming an ionic bond with a cation of Ca.

Preferably, the polysaccharide comprising a group capable of forming an ionic bond with a gelling agent is chosen from alginates and pectins.

Preferably, 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 mixtures thereof, preferably from sodium alginates, potassium alginates, ammonium alginates, and mixtures thereof. Preferably, the alginate is an ammonium alginate.

In the method according to the invention, the polysaccharide comprising a group capable of forming an ionic bond with a gelling agent, preferably alginate, can be provided in the form of a solution.

As is well known to those skilled in the art, the starting charge may 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).

Preferably the solvent is water. The amount 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.

In one embodiment, in particular when the starting charge contains a quantity of solvent, preferably water, which is too large with respect to the shaping process envisaged in step h), a step of eliminating part of the solvent can be carried out, before step h).

In one embodiment, step f) makes it possible to obtain a paste having a solvent content, preferably water, suitable for the shaping process envisaged in step h).

The starting charge optionally contains a plasticizer.

Preferably, 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.

All 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 their mixtures.

In a preferred embodiment, the starting charge does not contain plasticizers.

The feedstock optionally contains a lubricant. Preferably, 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 feedstock.

All lubricants conventionally used for the manufacture of porous ceramic products can be used, for example petroleum jelly and/or glycerin and/or waxes.

The presence and nature of the lubricant and/or plasticizer depend in particular on the shaping technique used in step h).

In a preferred embodiment, the starting charge does not contain lubricants.

In a preferred embodiment, the starting charge does not contain any other constituents than the paste obtained at the end of step g), the binder, preferably a polysaccharide, and a solvent.

The mixing of the various 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 turbulator, in a jar mill with balls, preferably alumina balls. Preferably, 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 h) may 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 envisaged in step h). All known techniques for removing at least part of a solvent, preferably water, may be used, preferably drying, preferably in air, at atmospheric pressure. Preferably, the maximum temperature reached during said drying is greater than 20°C, and preferably less than 100°C.

The objects obtained after shaping may be in the form of cylinders, polylobes, rings or spheres. Preferably, said objects have a largest dimension of 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 a smallest dimension, measured in a plane perpendicular to the direction of the largest dimension, greater than 1 µm, or even greater than 10 µm (micrometers).

The coating obtained after shaping may have a thickness greater than 10 µm, preferably greater than 50 µm, preferably greater than 100 µm, preferably greater than 200 µm, and preferably less than 1 mm, preferably less than 500 µm. Preferably the support is made of a material chosen from ceramics, metals, organic products, in particular polymers, and their mixtures.

• Dans ledit mode de réalisation préféré, à l’étape h), la charge de départ contient un polysaccharide, de préférence un alginate, et est mise en forme de manière à obtenir une préforme, ladite mise en forme étant effectuée suivant toute technique connue de l’homme du métier, par exemple l’extrusion, la granulation, le pressage, le coulage, l’atomisation, la sérigraphie (ou « screen printing » en anglais), le coulage en bande (ou « tape casting » en anglais), ou la gélification en goutte à goutte (ou « drip casting » en anglais). De préférence dans ledit mode de réalisation, la mise en forme est effectuée par sérigraphie.
• Puis, toujours selon ce mode de réalisation préféré, la préforme est mise en contact avec une solution comprenant un agent de gélification, apte à faire gélifier le polysaccharide, de préférence l’alginate.

A preferred embodiment will now be described.

• In said preferred embodiment, in step h), the starting charge contains a polysaccharide, preferably an alginate, and is shaped so as to obtain a preform, said shaping being carried out according to any technique known to those skilled in the art, for example extrusion, granulation, pressing, casting, atomization, screen printing, tape casting, or drip casting. Preferably in said embodiment, the shaping is carried out by screen printing.
• Then, still according to this preferred embodiment, the preform is placed in contact with a solution comprising a gelling agent, capable of gelling the polysaccharide, preferably alginate.

The solution comprising a gelling agent capable of gelling the polysaccharide, preferably alginate, is well known to those skilled in the art.

The gelling agent is preferably selected from divalent cations, trivalent cations and mixtures thereof, preferably selected from alkaline earth cations, preferably selected from Ca, Sr, Ba, Mg cations and mixtures thereof. Preferably the gelling agent is a Ca cation.

The solution containing the gelling agent is preferably selected from a solution comprising a divalent cation salt, a solution comprising a trivalent cation salt, or the lithium source from which the lithium is extracted, preferably brine, particularly when it contains such a cation.

Preferably, 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.

Preferably 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.

In a preferred embodiment, the gelling solution is the lithium source from which the lithium is extracted, preferably the brine from which the lithium is to be captured, especially when the latter comprises a divalent and/or trivalent cation.

• La mise en contact de la préforme avec la solution gélifiante peut par exemple être effectuée par immersion de la préforme dans un bain de solution gélifiante ou par aspersion de la préforme par la solution gélifiante.

In another possible embodiment, 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 contacting of the preform with the gelling solution 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.

In one embodiment, the shaping and the contacting of the preform with the gelling solution are combined, in particular when the preform is implemented by drop-by-drop gelling.

In 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 by drying.

Preferably, 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.

More preferably, the drying cycle has a plateau at said maximum temperature reached. The holding time at the plateau is preferably greater than 5 seconds and preferably less than 20 hours. Drying is preferably carried out in air, at atmospheric pressure.

Preferably, the water content of the product from step i) is greater than 1%, preferably greater than 5%, preferably greater than 10% and preferably less than 60%, based on the mass of the product.

In one embodiment, steps h) and i) may be performed, 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 following non-limiting examples are given for the purpose of illustrating the invention.

The nature of the crystallized phases of the objects in the examples is determined by the following classical method:

The products of the examples are previously exposed to air for 170 hours at 25°C, at atmospheric pressure.

Acquisitions are made using an X’Pert type device from Panalytical, equipped with a copper anode, over an angular range 2θ between 5° and 80°, with a step of 0.017°, and a counting time of 300 s/step. The front optics have a fixed divergence slit of 0.25°, a Soller slit of 0.02 rad, a 10 mm mask and a fixed anti-diffusion slit of 0.5°. The sample is rotated on itself. The rear optics have a fixed anti-diffusion 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 from the ICDD2016 database allows the identification of the phase (LiCl).2Al(OH) ₃ , xH ₂ O.

The crystallized phase of lithiated bayerite highlighted may present a slight angular shift of the peaks compared to said data sheet, in particular a consequence of the quantity of Li inserted into the structure of the lithiated bayerite.

The average size of the lithiated bayerite crystallites , 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, using an X'Pert type device from the company Panalytical, using the following Debye-Scherrer equation:

• K being equal to 0.89,
• λ being the wavelength of X-rays, here equal to that of copper, i.e. 1.54 Angstroms,
• B being the half-height width of the peak of the (003) plane of lithiated bayerite (PDF data sheet 00-031-0700 of 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°, and
• 2θ being the angle of the maximum intensity of the peak corresponding to the (003) plane of lithiated bayerite, in degrees.

The acquisition of the diffraction patterns of the monocrystalline silicon standard and the example is carried out, over an angular domain 2θ 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 optics have a fixed divergence slit of 0.25°, a Soller slit of 0.02 rad, a 10 mm mask and a fixed anti-diffusion slit of 0.5°. The sample is rotated on itself. The rear optics have a fixed anti-diffusion slit of 0.25°, a Soller slit of 0.02 rad and a nickel filter.

After removing the Kα2 line, the full width at half maximum of the peaks is determined using 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 from the same X-ray diffraction diagrams used to highlight the crystallized phases present. After eliminating the Kα2 line and using the EVA software, it is possible to measure the area A _HA of the diffraction peak of aluminum hydroxide present in an angular range 2θ substantially equal to 18.3°, the area A _BO of the diffraction peak of boehmite located in an angular range 2θ substantially equal to 14°, and the area A _BL of the diffraction peak of lithiated bayerite located in an angular range 2θ substantially equal to 11.3°. The cumulative rate of aluminum hydroxide and boehmite is then calculated according to the formula (1) given previously:

T = 100* (A _HA + A _BO )/ (A _HA + A _BO + A _BL ) (1)

Thus, when the product does not contain aluminum hydroxide or boehmite, the cumulative rate of aluminum hydroxide and boehmite is equal to 0.

With the exception of the elements O and H, the contents of the various elements present in the products of the examples are determined, on products dried in air at 200°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 200°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 an Agilent 5800 ICP-OES device.

The median size of a powder or suspension is measured using a laser granulometer model LA950V2 marketed by the Horiba company.

Manufacturing protocol

• Une poudre de gibbsite Al(OH)₃, présentant une taille médiane égale à 1,6 µm, de pureté supérieure à 99,5% en masse et une surface spécifique égale à 5 m²/g, pour les exemples 1 à 5,
• De l’hydroxyde de lithium monohydraté (LiOH,H₂O), de pureté supérieure à 99,5% en masse, pour les exemples 2 à 5,
• Du chlorure de lithium LiCl, de pureté supérieure à 99,5%% en masse, pour les exemples 1 à 5,
• De l’acide chlorhydrique HCl, de pureté supérieure à 99% en masse, en solution aqueuse à 16M, pour les exemples 2 à 5,
• Un alginate d’ammonium de pureté supérieur à 99% en masse, pour les exemples 2 à 5.

The following raw materials were used for the examples.

• A gibbsite Al(OH) ₃ powder, having a median size equal to 1.6 µm, a purity greater than 99.5% by mass and a specific surface area equal to 5 m²/g, for examples 1 to 5,
• Lithium hydroxide monohydrate (LiOH,H ₂ O), of purity greater than 99.5% by mass, for examples 2 to 5 ,
• Lithium chloride LiCl, of purity greater than 99.5% by mass, for examples 1 to 5,
• Hydrochloric acid HCl, of purity greater than 99% by mass, in 16M aqueous solution, for examples 2 to 5,
• An ammonium alginate of purity greater than 99% by mass, for examples 2 to 5.

The product of Example 1, outside the invention and in accordance with the teaching of US4,348,295, is the product of Example 1 of US 4,348,295 and was obtained in the following manner:

50 g of gibbsite are added to 200 ml of a 20% mass LiCl solution, then the mixture obtained is stirred for 2 hours at 115°C.

The mixture obtained is filtered on Büchner, at room temperature (below 50°C), with filter papers with a permeability equal to 2 µm. so as to obtain a paste.

The products of Examples 2 to 5 were obtained as follows:

In 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 marketed by the company Netzsch and ground for 75 minutes. At the end of step a), the aluminum hydroxide suspended in the water has a median size equal to 0.55 µm.

In 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 Al initially present in the mixture is as described in Table 1. For each example, the temperature at which this step took place, the mixing time and the pH of the mixture measured at the end of this step are also described in Table 1.

In step c), for each example, LiCl is added to the mixture obtained at the end of step b), so that the molar ratio between the Cl provided by LiCl and the Al initially present in the mixture is as described in Table 1. For each example, the temperature at which this step took place and the mixing time are described in Table 1.

At the end of step c), the quantity of lithium in the mixture, expressed by the Li/Al molar ratio, is as described in table 1.

In step d), the mixture is heated using a hot plate, to a temperature T ₁ , the time t ₁ 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 T ₁ and the time t ₁ .

In step e), for each example, the mixture is maintained at a constant temperature T ₂₁ for a time t ₂ . Table 1 describes for each example the temperature T ₂₁ and the time t ₂ .

In 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 Cl/Al molar ratio in the mixture after addition of HCl being as described in Table 1, the introduction of the acid being carried out at a temperature equal to T ₃₁ 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. T ₃₁ and t ₃ are described in Table 1.

In step g), for each example, the mixture is filtered on Büchner, at room temperature (below 50°C), with filter papers with a permeability equal to 2 µm. so as to obtain a paste. The time t₄during 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 t ₁ + t ₂ + t ₃ + t ₄ , is also described, for each example, in Table 1.

The following Table 1 summarizes the parameters used in the manufacturing steps of Examples 2 to 5.

Example 2 Example 3 Example 4 (*) Example 5 Step b), quantity of LiOH, _H2O added, in g 134.15 134.15 134.15 134.15 Step b), OH/Al molar ratio 0.5 0.5 0.5 0.5 Temperature at which step b) took place 25°C 25°C 25°C 25°C Step b), mixing time 15 min 5 min 15 min 15 min Step c), Cl/Al molar ratio 1 1 1 1 Temperature at which step c) took place 25°C 25°C 25°C 25°C Step c), mixing time 15 min 37 min 15 min 15 min Li/Al molar ratio in the mixture at the end of step c) 1.5 1.5 1.5 1.5 Step d), temperature T ₁ 50°C 60°C 60°C 60°C Step d), time t ₁ 0 min 15 min 15 min 15 min Step e), temperature T ₂₁ 50°C 60°C 60°C 60°C Step e), time t ₂ 4:45 a.m. 45 min 10 min 20 min Step f), pH after addition of HCl 3 3 3 3 Step f), Cl/Al molar ratio after addition of HCl 1.6 1.6 1.6 1.6 Step f), temperature T ₃₁ 50°C 60°C 60°C 60°C Step f), time t ₃ 15 min 15 min 5 min 5 min Step g), time t ₄ 0 5 min 5 min 5 min Time t ₅ = t ₁ +t ₂ +t ₃ +t ₄ 5 a.m. 1 h 20 35 min 45 min

(*) : excluding invention

The different pastes obtained have the characteristics shown in the following table 2.

Example 1 (*) Example 2 Example 3 Example 4 (*) Example 5 Amount of water, in mass percentage 60% 60% 65% 65% 70% Average crystallite size of lithiated bayerite (nm) 55 15.4 16.8 18.2 17.3 Crystallized phases highlighted Lithiated bayerite Lithiated bayerite Lithiated bayerite Lithiated bayerite, gibbsite Lithiated bayerite, gibbsite Cumulative rate of aluminum hydroxide and boehmite (%) Not determined 0 0 30 10 Chemical analysis by inductively coupled plasma spectrometry, after drying in air at 200°C for 16 hours, at atmospheric pressure, in weight percentage Li content (%) 4.31 4.21 3.83 3.13 4.23 Cl content (%) 22.02 21.51 19.56 15.99 21.61 Al content (%) 21.1 19.1 21.9 20.5 20.3 Content of elements other than Li, Al, Cl, O and H (%) 0.1 0.1 0.1 0.1 0.1 Elements O and H (%) Complement to 100 Complement to 100 Complement to 100 Complement to 100 Complement to 100

(*) : excluding invention

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.

For each example, the resulting paste was then shaped as follows.

For example 1, the paste obtained after filtration was spread on a metal grid with a thickness of 1 mm and perforated with circular holes with a diameter of 1.5 mm, then scraped using a spatula on each side of the grid so that said paste filled 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 objects formed falling into a container placed under the grid. Said objects obtained are in the form of cylinders with an average length of 0.8 mm and an average diameter of 1.4 mm.

For examples 2 to 5, in 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.

The 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 with a water content compatible with the shaping technique.

The starting charge was then spread on a metal grid with a thickness of 1 mm and perforated with circular holes with a diameter of 1.5 mm, then scraped using a spatula on each side of the grid so that said starting charge filled 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 objects formed falling into a container placed under the grid. Said objects obtained are in the form of cylinders with an average length of 0.8 mm and an average diameter of 1.4 mm.

Examples 2 and 3, according to the invention, have a high lithium adsorption capacity.

The shaped objects of Examples 2 and 3, according to the invention, have a lithium adsorption capacity greater than that of Example 1, in accordance with the prior art. This comparison also highlights the importance of limiting the temperature to 60°C during the product manufacturing process.

A comparison of example 4, outside the invention, and example 3, according to the invention, 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 rate of aluminum hydroxide and boehmite equal to 30%, which limits its lithium adsorption capacity.

Of course, the invention is not limited to the embodiments described, provided only for illustration purposes.

Claims (28)

Product including:
- water, and
- crystallites, at least a portion, preferably all, of said crystallites being constituted of lithiated bayerite,
the average size of the lithiated bayerite crystallites being greater than or equal to 10 nm and less than or equal to 25 nm, and
said product having a cumulative rate of aluminium hydroxide and boehmite less than or equal to 10%,
said product comprising at least the elements Li, Cl, Al, O and H,
the elements Li, Cl and Al being present in said dry product in the following contents, determined by inductively coupled plasma spectrometry and in weight percentages:
- 2% < Li < 5%,
- 10% < Cl < 26%,
- 15% < Al < 30%. Product according to the preceding claim having the following chemical analysis, determined on the dry product by inductively coupled plasma spectroscopy, in weight percentage:
- 2% < Li < 5%,
- 10% < Cl < 26%,
- 15% < Al < 30%,
- elements other than Li, Cl, Al, O and H: < 3%,
- O and H: complement to 100%. Product according to one of the preceding claims in which:
- the water content is greater than 1% and less than 95%, and/or
- the average size of lithiated bayerite crystallites is less than 23 nm Product according to one of the preceding claims in which:
- the cumulative rate of aluminum hydroxide and boehmite is less than or equal to 8%, and/or
- the crystallized phases comprise lithiated bayerite, boehmite and/or an aluminum hydroxide chosen from gibbsite, bayerite, doyleite, nordstrandite and their mixtures. Product according to one of claims 3 or 4 in which:
- the water content is greater than 5%, and/or
- the water content is less than 80%, and/or
- the crystallized phases comprise lithiated bayerite and an aluminum hydroxide chosen from gibbsite, bayerite, doyleite, nordstrandite and their mixtures. Product according to the preceding claim in which:
- the water content is greater than 10%, and/or
- the water content is less than 70%, and/or
- the only crystallized phase is lithiated bayerite. Product according to one of the preceding claims, consisting of at least 80% by mass of water, and crystallites of lithiated bayerite, and of aluminum hydroxide and/or boehmite, and of LiCl, and of a binder. Product according to the preceding claim, consisting of at least 80%, by mass, of water, and of crystallites of lithiated bayerite, and of aluminum hydroxide, and of LiCl, and of a binder. Product according to the preceding claim, consisting of at least 80% by mass in total of water, lithiated bayerite crystallites, LiCl and a binder. Product according to one of the three immediately preceding claims in which the binder is a polysaccharide, preferably an alginate. Method of manufacturing a product according to one of the preceding claims comprising the following steps:

1. Aqueous suspension of an aluminum source, preferably a single aluminum source, selected from a boehmite or an aluminum hydroxide and mixtures thereof, preferably an aluminum hydroxide,
   grinding said aqueous suspension so as to obtain a median size less than or equal to 3 µm if the median size of the aluminum source is greater than 3 µm,
   said suspension being maintained during this step a) at a temperature below 50°C;
2. Increasing the pH by adding a base, such that the molar ratio between the OH provided by said base and the Al 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;
3. Addition of a chlorine salt, such that the molar ratio between the Cl provided by said chlorine salt and the Al 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; the base in step b), the chlorine salt in step c) and their respective quantities being 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;
4. Raising the temperature of the mixture to a temperature greater than or equal to 50°C and less than or equal to 60°C, the time t ₁ being the time during which said mixture is at a temperature greater than or equal to 50°C;
5. Maintaining the mixture at a temperature greater than or equal to 50°C and less than or equal to 60°C for a time t ₂ ;
6. Optionally, adding an acid to the mixture, with stirring, so as to reduce the pH of the mixture to a value less than or equal to 8, the chlorine salt in step c), said acid, and their respective amounts being chosen so that the Cl/Al molar ratio in the mixture is greater than or equal to 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, the molar ratio between the Cl provided by the chlorine salt and the Al present in the mixture being greater than or equal to 0.5 if the process does not include said step f);
7. Optionally, and preferably, filtration of the mixture so as to obtain a paste, the 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;

the cumulative time t₁+t₂+t₃+ t₄= t₅being greater than or equal to 45 minutes and less than 15 hours. Method for manufacturing a product according to the preceding claim, in which step a) involves grinding the aqueous suspension of an aluminum source chosen from a boehmite or an aluminum hydroxide and their mixtures, so as to obtain a median size ≤ 1 µm. Method according to one of claims 11 to 12, in which the time t ₅ is such that the times t ₁ , t ₂ , t ₃ and t ₄ satisfy the following relations: [t ₁ /(-1.2T ₁ +75)] + [t ₂ /(-1.2T ₂₀ +75)] + [t ₃ /(-1.2T ₃₀ +75)] + [t ₄ /(-1.2T ₄₀ +75)] ≤ 1 and [t ₁ /(-0.225T ₁ +14.25)] + [t ₂ /(-0.225T ₂₀ +14.25)] + [t ₃ /(-0.225T ₃₀ +14.25)] + [t ₄ /(-0.225T ₄₀ +14.25)] ≥ 1, with T ₁ being the temperature reached by the mixture in step d), T ₂₀ being the average temperature during step e), T ₃₀ being the average temperature during step f), T ₄₀ being the average temperature of the mixture during time t _4. Method according to the preceding claim, in which the time t ₅ is such that the times t ₁ , t ₂ , t ₃ and t ₄ satisfy the following relations: [t ₁ /(-0.8T ₁ +50)] + [t ₂ /(-0.8T ₂₀ +50)] + [t ₃ /(-0.8T ₃₀ +50)] + [t ₄ /(-0.8T ₄₀ +50)] ≤ 1, and/or
- time t ₅ is such that times t ₁ , t ₂ , t ₃ and t ₄ satisfy the following relation: [t ₁ /(-0.2T ₁ +13)] + [t ₂ /(-0.2T ₂₀ +13)] + [t ₃ /(-0.2T ₃₀ +13)] + [t ₄ /(-0.2T ₄₀ +13)] ≥ 1 Method according to the preceding claim, in which the time t ₅ is such that the times t ₁ , t ₂ , t ₃ and t ₄ satisfy the following relation: [t ₁ /(-0.55T ₁ +34.5)] + [t ₂ /(-0.55T ₂₀ +34.5)] + [t ₃ /(-0.55T ₃₀ +34.5)] + [t ₄ /(-0.55T ₄₀ +34.5)] ≤ 1. Method according to one of claims 11 to 15 in which:
- aluminium hydroxide, boehmite and their mixtures are the only sources of aluminium used in all the steps of said process, and/or
- in step b), the molar ratio between the OH provided by the base and the Al present in the mixture is greater than 0.25 and less than 10, and/or
- in step b), the pH of the mixture after addition of the base is greater than 9 and less than 13. Method according to one of claims 11 to 16 in which:
- in step c), the molar ratio between the Cl provided by the chlorine salt and the Al present in the mixture is less than 10, and/or
- 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 1.1 and less than 4, and/or
- in step d), time t ₁ is greater than 5 minutes. Method according to one of claims 11 to 17 in which:
- in step e), the temperature of the mixture is substantially constant, and/or
- in step e), time t ₂ is greater than 40 minutes, and/or
- in optional step f), at least part of the quantity of Cl necessary to obtain a Cl/Al molar ratio greater than 1 is provided by the acid. Method according to one of claims 11 to 18 in which:
- in optional step f), the pH of the mixture is reduced to a value less than 7.5 and greater than 6.5, and/or
- in optional step f), the Cl/Al molar ratio in the mixture is set to a value less than 3, and/or
- in optional step f), the temperature of the mixture is substantially constant. Method according to one of claims 12 to 19 in which:
- in optional step f), time t ₃ is greater than 5 minutes, and/or
- in step g), time t ₄ is less than 15 minutes. The method of claim 16, wherein aluminum hydroxide is the sole source of aluminum used in all steps of said method. Method according to one of claims 11 to 21, in which
- steps a) and b) are carried out simultaneously, and/or
- steps a), b) and c) are carried out simultaneously. Method according to one of claims 11 to 22, comprising, 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. Method according to the preceding claim, in which in step h), the starting charge comprises a binder. Method according to the preceding claim in which the binder is a polysaccharide comprising a group capable of forming an ionic bond with a gelling agent for the formation of a gelled polysaccharide. Method according to the preceding claim in which the polysaccharide is chosen from alginates. Method according to one of claims 23 to 26, in which steps h) and i) are carried out, at least partially, simultaneously. Lithium capture device, comprising a product according to one of claims 1 to 10 or a product obtained by a method according to one of claims 11 to 27.