Method for preparing an adsorbent material comprising a step of basic mixing, and method for extracting lithium from saline solutions using said material

Patent metadata

Field	Value
Publication number	US-10850254-B2
Application number	US-201615778768-A
Country	US
Kind code	B2
Filing date	Nov 24, 2016
Priority date	Nov 24, 2015
Publication date	Dec 1, 2020
Grant date	Dec 1, 2020

Abstract

The present invention relates to the field of solid materials for the adsorption of lithium. In particular, the present invention relates to a new method for the preparation of a crystallized and shaped solid material, preferably in extruded form, of formula LiXx.2Al(OH)3,nH2O, wherein n is between 0.01 and 10, x is 1 when X is an anion selected from among chloride, hydroxide and nitrate anions, and x is 0.5 when X is an anion selected from among sulfate and carbonate anions, comprising a boehmite precipitation step a) under specific temperature and pH conditions, at least one basic mixing shaping step, wherein the method also comprises a final hydrothermal treatment step, all to increase the lithium adsorption capacity and the kinetics of adsorption of the materials obtained, compared with the materials of the prior art when it is used in a method for lithium extraction from saline solutions.

First claim

The invention claimed is:

1. Method for preparing a crystallized solid material of formula Li x .2Al(OH) 3 ,nH 2 O, wherein n is between 0.01 and 10, and x is equal to 1 when X is an anion selected from the group consisting of chloride, hydroxide and nitrate anions, and x is 0.5 when X is an anion selected from the group consisting of sulfate and carbonate anions, wherein the method comprises:
a) precipitating boehmite, in an aqueous medium, of at least one basic precursor selected from the group consisting of among sodium aluminate, potassium aluminate, aqueous ammonia, sodium hydroxide and potassium hydroxide; and at least one acidic precursor selected from the group consisting of aluminum sulphate, aluminum chloride, aluminum nitrate, sulfuric acid, hydrochloric acid, and nitric acid, wherein at least one of one of the basic or acidic precursors comprises aluminum, to obtain a boehmite suspension, wherein a) is operated at a temperature of between 5 and 35° C., and wherein the amount of the basic precursor is chosen in order to obtain a pH of end of precipitation in the reaction medium of between 7.5 and 9.5,
b) filtering and washing the boehmite precipitate obtained in a),
c) contacting the precipitate obtained in b) with at least one lithium source,
d) filtering the suspension obtained in c) to obtain a paste,
e) drying the paste obtained at the end of d) at a temperature of between 20 and 80° C.,
f) shaping the basic extrusion-mixed dough in which the dried dough resulting from e) is mixed in the presence of an amount of a base between 0.5 and 3% by weight relative to the dry matter, wherein the base is selected from the group consisting of inorganic bases and organic bases in solution, and in which the dough is then subjected to an extrusion, and
g) hydrothermally treating the dried shaped material obtained at the end of step f), at a temperature of between 50 and 200° C.,
thereby providing a crystallized solid material of formula LiX x 2Al(OH) 3 ,nH 2 O, wherein n is between 0.01 and 10, and x is equal to 1 when X is an anion selected from the group consisting of chloride, hydroxide and nitrate anions, and x is 0.5 when X is an anion selected from the group consisting of sulfate and carbonate anions.

2. Method according to claim 1 , wherein the basic precursor is sodium hydroxide (NaOH).

3. Method according to claim 1 , wherein the acidic precursor is aluminum trichloride (AlCl 3 ).

4. Method according to claim 1 , wherein a) is carried out at a temperature between 10 and 25° C.

5. Method according to claim 1 , wherein the amount of the basic precursor is selected in order to obtain a precipitation end pH of a) in the reaction medium of between 7.7 and 8.8.

6. Method according to claim 1 , wherein the source(s) of lithium is/are selected from the group consisting of lithium chloride (LiCl), lithium hydroxide (LiOH) nitrate Lithium (LiNO 3 ), lithium sulphate (Li 2 SO 4 ) and lithium carbonate (Li 2 CO 3 ), alone or as a mixture.

7. Method according to claim 6 , wherein the lithium source is lithium chloride (LiCl).

8. Method according to claim 1 , wherein the shaping during f) is carried out in the presence of ammonia.

9. Method according to claim 8 , wherein the dried paste is mixed in the presence of an amount of base of between 0.5 and 2.5% by weight relative to the dry matter, wherein the dry matter is the weight of the paste of e), dried in an oven at 200° C. for 6 h in the shaping f).

10. The method according to claim 1 , wherein the dry matter of dried dough is defined as the dough resulting from e) dried in an oven at 200° C. for 6 h.

Assignees

• Eramet
• Ifp Energies Now

Inventors

• Boualleg Malika
• Burdet Fabien André Pierre
• Gohin Morgan Julien Florian

Classifications

• C01F7/782

  containing carbonate ions, e.g. dawsonite · CPC title

• C01F7/78

  Compounds containing aluminium, with or without oxygen or hydrogen, and containing two or more other elements (aluminates C01F7/02; compounds containing aluminium, fluorine and alkali or alkaline earth metals C01F7/54; nitrates containing other cations besides aluminium C01F7/66; sulfides, sulfites or sulfates containing other cations besides aluminium C01F7/70 - C01F7/74) · CPC title

• C01D15/00

  Lithium compounds · CPC title

• C01F7/025

  Granulation or agglomeration · CPC title

• C01F7/02

  Aluminium oxide; Aluminium hydroxide; Aluminates · CPC title