EP4304773A1 - Product comprising a lithium adsorbent - Google Patents
Product comprising a lithium adsorbentInfo
- Publication number
- EP4304773A1 EP4304773A1 EP22713968.0A EP22713968A EP4304773A1 EP 4304773 A1 EP4304773 A1 EP 4304773A1 EP 22713968 A EP22713968 A EP 22713968A EP 4304773 A1 EP4304773 A1 EP 4304773A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lithium
- doped
- optionally hydrated
- product
- mixtures
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 179
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 179
- 239000003463 adsorbent Substances 0.000 title claims abstract description 86
- 239000000203 mixture Substances 0.000 claims abstract description 63
- 150000001768 cations Chemical class 0.000 claims abstract description 60
- 150000004676 glycans Chemical class 0.000 claims abstract description 51
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 49
- 239000005017 polysaccharide Substances 0.000 claims abstract description 49
- 239000002245 particle Substances 0.000 claims abstract description 27
- 239000011230 binding agent Substances 0.000 claims abstract description 19
- 238000000605 extraction Methods 0.000 claims abstract description 11
- 239000012267 brine Substances 0.000 claims abstract description 10
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 25
- 239000003349 gelling agent Substances 0.000 claims description 24
- 229910052596 spinel Inorganic materials 0.000 claims description 24
- 239000011029 spinel Substances 0.000 claims description 24
- 239000011575 calcium Substances 0.000 claims description 22
- 229910001680 bayerite Inorganic materials 0.000 claims description 21
- 235000010443 alginic acid Nutrition 0.000 claims description 20
- 229920000615 alginic acid Polymers 0.000 claims description 20
- 239000011572 manganese Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims description 19
- 229940072056 alginate Drugs 0.000 claims description 18
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 229910052748 manganese Inorganic materials 0.000 claims description 16
- 229910052791 calcium Inorganic materials 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 13
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 229910052788 barium Inorganic materials 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000007493 shaping process Methods 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- 150000007942 carboxylates Chemical group 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000001814 pectin Substances 0.000 claims description 6
- 235000010987 pectin Nutrition 0.000 claims description 6
- 229920001277 pectin Polymers 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 238000001879 gelation Methods 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000010955 niobium Substances 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 description 60
- 239000000243 solution Substances 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 14
- 239000002904 solvent Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- -1 cesium ions Chemical class 0.000 description 10
- 238000002336 sorption--desorption measurement Methods 0.000 description 9
- 239000004014 plasticizer Substances 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 239000000314 lubricant Substances 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 235000010407 ammonium alginate Nutrition 0.000 description 5
- 229910001593 boehmite Inorganic materials 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 5
- 238000003795 desorption Methods 0.000 description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 5
- 230000003252 repetitive effect Effects 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 239000000728 ammonium alginate Substances 0.000 description 4
- KPGABFJTMYCRHJ-YZOKENDUSA-N ammonium alginate Chemical compound [NH4+].[NH4+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O KPGABFJTMYCRHJ-YZOKENDUSA-N 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- MVLVMROFTAUDAG-UHFFFAOYSA-N ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC MVLVMROFTAUDAG-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 150000004804 polysaccharides Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000002285 radioactive effect Effects 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000010345 tape casting Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 1
- 238000002270 exclusion chromatography Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910001679 gibbsite Inorganic materials 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 1
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000015927 pasta Nutrition 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- 235000010408 potassium alginate Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/046—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing halogens, e.g. halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3007—Moulding, shaping or extruding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3071—Washing or leaching
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/10—Oxides or hydroxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- TITLE Product comprising a lithium adsorbent Technical area
- the present invention relates to a product comprising a lithium adsorbent and to a method of manufacturing products comprising a lithium adsorbent.
- Brines are sources of lithium, for which an extraction of said lithium is necessary.
- This extraction, or capture can be carried out using columns filled with an active material, which selectively and reversibly captures the lithium when the brine comes into contact with it.
- the lithium is then recovered by passing slightly saline and acidified water through these columns. This results in a concentrated lithium solution which will be purified before a precipitation step, generally in the form of lithium carbonate.
- Lithium adsorbents are materials advantageously used as an active material allowing the production of the concentrated lithium solution within the extraction columns.
- Application KR20190078350 describes various lithium adsorbent materials in a lithium capture application.
- Application WO2018002336 describes a material for capturing lithium of formula (LiCI) x .2AI(OH) 3 , nhhO with x between 0.4 and 1 and n between 0.01 and 10.
- Application CN103212388 describes a process for the selective and irreversible extraction of radioactive rubidium and cesium ions in a brine containing such ions, in particular from radioactive nuclear waste, from a solution comprising a hydrosol of sodium alginate and of a powder of potassium tetraphenylborate.
- Lithium uptake is accompanied by an increase in volume of the lithium adsorbent material located in the extraction column. Then, when the lithium is subsequently recovered by passing slightly saline and acidified water through said columns, the volume of the lithium adsorbent material decreases. Said material thus undergoes repeated cycles of increase and decrease in volume which can lead to a degradation of its shape and therefore to a decrease in the efficiency of lithium capture.
- An object of the invention is to respond, at least partially, to this need. Disclosure of Invention
- this object is achieved by means of a product advantageously allowing the facilitated extraction of lithium, said product comprising particles bound by a binder, said binder comprising a gelled polysaccharide comprising a group establishing an ionic bond with a cation divalent, a trivalent cation and mixtures thereof, said particles being essentially, preferably being, particles of a lithium adsorbent.
- the binder consists of said gelled polysaccharide.
- the gelled polysaccharide comprises a group establishing an ionic bond with an alkaline-earth cation, preferably chosen from the cations of Ca, Sr, Ba and their mixtures, preferably with a Ca cation.
- the group is chosen from carboxylate groups (-COO-) or sulphonate groups (-SO 3 ), more preferably said group is a carboxylate group.
- the gelled polysaccharide is an alginate gelled under the action of a divalent cation, a trivalent cation and mixtures thereof, preferably under the action of a divalent cation, more preferably under the action of a cation of calcium.
- the gelled polysaccharide is a pectin gelled under the action of a divalent cation, a trivalent cation and mixtures thereof, preferably under the action of a divalent cation, more preferably under the action of a cation of calcium
- the lithium adsorbent is chosen from:
- lithiated bayerite preferably a material of formula (LiCI) x .2AI(OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10;
- lithium aluminate optionally hydrated and/or doped, said lithium aluminate preferably corresponding to the formula UAIO2, optionally hydrated and/or doped;
- manganese and lithium spinel being preferably chosen from a manganese and lithium spinel of formula Li (i+X) Mn (2 -y ) M'y0 4 with -0.20 ⁇ x ⁇ 0.4 and 0 ⁇ y ⁇ 1, the element M' being chosen from aluminum, cobalt, nickel, chromium, iron, magnesium, titanium, vanadium, copper, zinc, gallium, calcium, niobium, yttrium, barium, silicon, boron, zirconium, lithium and mixtures thereof, the electroneutrality of said lithium manganate being ensured by the content of oxygen;
- a cobalt and lithium spinel optionally hydrated and/or doped, said cobalt and lithium spinel preferably having the formula UCO2O4, optionally hydrated and/or doped;
- lithium titanate optionally hydrated and/or doped, said lithium titanate being preferably chosen from a lithium titanate corresponding to the formula LiTi0 2 , LhTiOs, LÎ2TÎ307, LÎ4TÎ50i2, and mixtures thereof, optionally hydrated and/or or doped(s), preferably LhTiCb, optionally hydrated and/or doped;
- the lithium adsorbent is chosen from:
- lithiated bayerite preferably a material of formula (LiCI) x .2AI(OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10;
- lithium titanate optionally hydrated and/or doped
- said lithium titanate preferably being chosen from a lithium titanate corresponding to the formula LiTiC>2, Li 2 TiC> 3 , Li 2 Ti 3 07, Li 4 Ti 0i 2 , and mixtures thereof, optionally hydrated and/or doped, preferably LhTiCb, optionally hydrated and/or doped ;
- the lithium adsorbent is a lithiated bayerite, preferably a material of formula (LiCI) x .2AI(OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10.
- mass quantity of particles of a lithium adsorbent, after drying at 100°C for 12 hours, is greater than or equal to 95% and less than 99.9%, based on the mass of said product after drying at 100°C for 12 hours.
- the product is in the form of cylinders, polylobes, rings, or spheres, preferably, the largest dimension of which is less than 100 mm, preferably less than 80 mm, preferably less than 50 mm and the small dimension, in a plane perpendicular to the direction of the largest dimension, is greater than 1 ⁇ m.
- Products comprising a lithium adsorbent described above, in particular put in the form of macroscopic objects, have improved resistance to repetitive cycling adsorption-desorption of lithium in particular in lithium extraction columns described above.
- the invention also relates to a process for manufacturing a product comprising a lithium adsorbent, in particular a product as described above, comprising at least the following steps: a) mixing raw materials to form a starting charge, said charge of starting comprising a powder of a lithium adsorbent, and a polysaccharide which can be gelled under the action of a gelling agent, the mass ratio of the quantity of said polysaccharide to the total quantity of said polysaccharide and of the powder of a lithium adsorbent being preferably greater than or equal to 0.1% and preferably less than or equal to 10%, more preferably less than or equal to 5%, b) shaping of said starting charge, so as to obtain a preform, c ) bringing said preform into contact with said gelling agent and gelling said polysaccharide so as to obtain said product comprising a lithium adsorbent, d) optionally, drying said product comprising u n adsorbing lithium.
- the lithium adsorbent is a lithiated bayerite, preferably a material of formula (LiCI) x .2AI(OH ) 3 , nH 2 0, with x between 0.4 and 1 and n between 0.01 and 10.
- the polysaccharide is an alginate or a pectin, preferably an alginate.
- the gelling agent is chosen from Ca, Sr, Ba and mixtures thereof, preferably the gelling agent is Ca.
- the invention also relates to a product capable of being obtained by the method as described above.
- the invention finally relates to a lithium capture device, in particular an extraction column, comprising a product according to the invention or a product obtained or capable of being obtained by the method according to the invention as described previously.
- lithium adsorbent refers to any material capable of retaining lithium in its structure by adsorption, in particular chemical or physical, and/or by exchange between an ion of its structure with an Li+ ion.
- a lithiated bayerite in particular a material of formula (LiCI) x .2AI(OH) 3 , nhhO with x between 0.4 and 1 and n between 0.01 and 10, is an example of a lithium adsorbent material.
- lithium bayerite The compound of formula LiCI.2AI(0H) 3 .nH 2 0 as indicated in the ICDD PDF 00-031-0700 sheet, but also by extension, is called "lithium bayerite".
- compounds having a ratio of molar amounts of lithium and aluminum, Li/Al different from 0.5 In some modes, it may be less than 0.5. According to other modes, it may be greater than 0.5.
- polysaccharides refers to polymers composed of sequences of saccharide units linked by glycosidic bonds.
- gellable polysaccharide under the action of a gelling agent means a polysaccharide capable of forming a gel under the action of said gelling agent.
- alginate has the formula (O Q HZO Q ) ⁇
- Alginate is a polyosidic chain comprising carboxylate groups (COO- ).
- Calcium Ca 2+ ions (gelling agent) react with two strands of alginate, that is to say with the carboxylate groups COO , leading to the polymerization of the alginate chains and the bonding of the molecules between them. The reaction thus allows the creation of a gel.
- the starting charge comprises at least one powder of a lithium adsorbent.
- the lithium adsorbent powder(s) may or may be provided in a dry form, but also in a wet form, for example in the form of a suspension and /or a paste.
- the starting charge contains a lithiated bayerite powder, preferably a powder of a material of formula (LiCI) x .2AI(OH) 3 , nhhO, with x between 0.4 and 1.0 and n between 0.01 and 10, said powder is supplied in a wet form, preferably in the form of a suspension and/or a paste.
- a lithiated bayerite powder preferably a powder of a material of formula (LiCI) x .2AI(OH) 3 , nhhO, with x between 0.4 and 1.0 and n between 0.01 and 10
- said powder is supplied in a wet form, preferably in the form of a suspension and/or a paste.
- the starting charge comprises at least two powders of a lithium adsorbent, preferably at least two of said powders of a lithium adsorbent are made of a different lithium adsorbent.
- the starting charge comprises a single powder of a lithium adsorbent.
- the lithium adsorbent is chosen from: a lithiated bayerite, preferably a material of formula (LiCI) x .2Al(OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10; a lithium aluminate, optionally hydrated and/or doped, said lithium aluminate preferably corresponding to the formula UAIO 2 , optionally hydrated and/or doped; a manganese and lithium spinel, optionally doped, said manganese and lithium spinel being preferably chosen from a manganese and lithium spinel of formula Li (i+X) Mn (2 -y ) M'y0 4 with - 0.20 ⁇ x ⁇ 0.4 and 0 ⁇ y ⁇ 1, the element M' being chosen from aluminum, cobalt, nickel, chromium, iron, magnesium, titanium, vanadium, copper, zinc, gallium, calcium, niobium, yttrium, bar
- a lithiated magnesium oxide, optionally hydrated and/or doped said lithiated magnesium oxide preferably having the formula LiMg0 2 , optionally hydrated and/or doped;
- a cobalt and lithium spinel optionally hydrated and/or doped, said cobalt and lithium spinel preferably having the formula UC0 2 O 4 , optionally hydrated and/or doped;
- a lithium titanate optionally hydrated and/or doped, said lithium titanate preferably being chosen from a lithium titanate corresponding to the formula LiTi0 2 , LhTiOs, LÎ2TÎ307, Li 4 Ti 5 0i2, and mixtures thereof, optionally hydrated(s ) and/or doped, preferably LhTiCb, optionally hydrated and/or doped; hhTiCb, optionally hydrated and/or doped;
- H2T13O7 optionally hydrated and/or doped
- H4T15O12 optionally hydrated and/or doped
- the lithium adsorbent is chosen from: a lithiated bayerite, preferably a material of formula (LiCI) x .2Al(OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10; a manganese and lithium spinel, optionally doped; a lithium titanate, optionally hydrated and/or doped, said lithium titanate being preferably chosen from a lithium titanate corresponding to the formula LiTi0 2 , L TiOs , Li 2 Ti 3 0 7 , Li 4 Ti 0i 2 , and their mixtures, optionally hydrated and/or doped, preferably Li 2 Ti0 3 , optionally hydrated and/or doped ;
- H2T1O3 optionally hydrated and/or spiked; and their mixtures.
- the lithium adsorbent is a lithiated bayerite, preferably a material of formula (LiCI) x .2AI(OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10
- the median size of the lithium adsorbent powder is greater than 0.1 ⁇ m and/or less than 100 ⁇ m.
- the starting charge contains a polysaccharide comprising a group capable of forming an ionic bond with a gelling agent chosen from divalent cations, trivalent cations (for example an Fe or Al cation) and mixtures thereof for the formation of a gelled polysaccharide, in particular in an amount such that the mass ratio of the amount of said polysaccharide to the total amount of said polysaccharide and lithium adsorbent powder is greater than or equal to 0.1% and preferably less than or equal to 10%, preferably still less than 5%.
- a gelling agent chosen from divalent cations, trivalent cations (for example an Fe or Al cation) and mixtures thereof for the formation of a gelled polysaccharide, in particular in an amount such that the mass ratio of the amount of said polysaccharide to the total amount of said polysaccharide and lithium adsorbent powder is greater than or equal to 0.1% and preferably less than or equal to 10%, preferably still less than 5%.
- said mass ratio is greater than or equal to 0.2%, preferably greater than or equal to 0.3% and preferably less than or equal to 4%, preferably less than or equal to 3%, preferably less than or equal at 2%, preferably less than or equal to 1%.
- the polysaccharide group capable of forming an ionic bond with a gelling agent chosen from divalent cations, trivalent cations and mixtures thereof is chosen from a carboxylate group COO or a sulphonate group SO 3 , more preferably said group is a COO- carboxylate group.
- the polysaccharide comprises a group capable of forming an ionic bond with a gelling agent chosen from alkaline-earth cations, preferably chosen from Ca, Sr, Ba cations and mixtures thereof.
- a gelling agent chosen from alkaline-earth cations, preferably chosen from Ca, Sr, Ba cations and mixtures thereof.
- the polysaccharide comprises a group capable of forming an ionic bond with a Ca cation.
- the polysaccharide comprising a group capable of forming an ionic bond with a gelling agent is chosen from alginates and pectins.
- the polysaccharide comprising a group capable of forming an ionic bond with a gelling agent is chosen from alginates, preferably from sodium alginates, potassium alginates, ammonium alginates, and mixtures thereof.
- the alginate is an ammonium alginate.
- the starting charge contains a powder of a lithium adsorbent and a polysaccharide comprising a group capable of forming an ionic bond with a gelling agent chosen from divalent cations, trivalent cations and mixtures thereof.
- a gelling agent chosen from divalent cations, trivalent cations and mixtures thereof.
- the polysaccharide comprising a group capable of forming an ionic bond with a gelling agent chosen from divalent cations, trivalent cations and mixtures thereof, preferably alginate, can be provided in the form of a solution.
- the starting charge may comprise, in addition to the adsorbent powder(s), lithium and polysaccharide comprising a group capable of forming an ionic bond with a gelation chosen from divalent cations, trivalent cations and mixtures thereof, a solvent and/or an organic binder and/or a plasticizer and/or a lubricant and/or pore-forming particles, the natures and quantities of which are adapted to the method formatting step b).
- the solvent is water.
- the amount of solvent is adapted to the shaping process implemented in step b) as well as to the presence of polysaccharide comprising a group capable of forming an ionic bond with a gelling agent chosen from divalent cations, trivalent cations and their mixtures in the starting charge.
- a step of removing part of the solvent can be carried out, before step b).
- the starting charge optionally contains an organic binder facilitating the constitution of the preform, preferably in a content of between 0.1% and 10%, preferably between 0.2% and 2% by mass based on the mass of the lithium adsorbent powder(s) of the starting charge.
- All the organic binders conventionally used for the manufacture of porous ceramic products can be used, for example polyvinyl alcohol (PVA) or polyethylene glycol (PEG), methylstearate, ethylstearate, waxes, polyolefins, polyolefin oxides, glycerin, propionic acid, maleic acid, benzyl alcohol, isopropanol, butyl alcohol, paraffin and polyethylene dispersion, and mixtures thereof.
- PVA polyvinyl alcohol
- PEG polyethylene glycol
- methylstearate methylstearate
- ethylstearate waxes
- polyolefins polyolefin oxides
- glycerin glycerin
- propionic acid maleic acid
- benzyl alcohol isopropanol
- butyl alcohol paraffin and polyethylene dispersion, and mixtures thereof.
- the starting charge optionally contains a plasticizer, also facilitating the constitution of the preform.
- the content of plasticizer is between 0.1% and 10%, preferably between 0.5% and 5%, by mass based on the mass of the lithium adsorbent powder(s). of the starting load.
- the plasticizer can constitute a binder.
- the plasticizers conventionally used for the manufacture of porous ceramic products can be used, for example polyethylene glycol, polyolefin oxides, hydrogenated oils, alcohols, in particular glycerol and glycol, esters, and mixtures thereof.
- the starting charge optionally contains a lubricant, also facilitating the constitution of the preform.
- the lubricant content is between 0.1% and 10%, preferably between 0.5% and 5% by weight of the lithium adsorbent powder(s) of the starting charge.
- lubricants conventionally used for the manufacture of porous ceramic products can be used, for example petroleum jelly and/or glycerin and/or waxes.
- the starting charge optionally contains pore-forming particles, well known to those skilled in the art, which are intended to be eliminated during the process according to the invention, thus leaving room for pores.
- pore-forming particles well known to those skilled in the art, which are intended to be eliminated during the process according to the invention, thus leaving room for pores.
- Their quantity and their dimensions are chosen so as in particular to adjust the pore volume in the lithium adsorbent-based product obtained at the end of step b) or at the end of step c).
- said pore-forming particles are made of a material soluble in the solvent.
- binder and/or the lubricant and/or the plasticizer depend in particular on the shaping technique used in step b).
- the starting charge does not contain any constituents other than the lithium adsorbent powder(s), the polysaccharide, a solvent, an organic binder, a plasticizer, a lubricant and particles porogens.
- the polysaccharide, preferably the alginate, the solvent, preferably the water are mixed in such a way as to obtain an intimate mixture.
- the other constituents of the starting charge in particular the lithium adsorbent powder(s), the optional binder, lubricant, plasticizer and blowing particles are added with stirring.
- the quantity of solvent preferably water
- the quantity of solvent can be added in several times, in a quantity determined according to the technique chosen for shaping.
- the solvent preferably water, is provided, at least in part, by said suspension and/or said paste .
- the mixing of the various constituents can be carried out according to any technique known to those skilled in the art, for example in a mixer, preferably in a high-intensity mixer or in a Z-arm mixer, in a turbulat, in a jar mill with balls, preferably alumina balls.
- the mixing is carried out in a high intensity mixer or in a Z-arm mixer.
- the total mixing time is preferably greater than 5 minutes, and preferably less than 30 minutes, preferably less than 20 minutes.
- Step b) can be preceded by a step of removing at least part of the solvent, so as to adapt the amount of solvent, preferably water, to the shaping technique. considered in step b).
- All the known techniques for at least partially eliminating a solvent, preferably water, can be used, preferably drying, preferably in air, at atmospheric pressure.
- the maximum temperature reached during said drying is greater than 20°C, and preferably less than 100°C, preferably less than 80°C, preferably less than 60°C.
- the drying cycle has a plateau at said maximum temperature reached.
- the holding time at the level is preferably greater than 1 hour, and preferably less than 20 hours, preferably less than 15 hours.
- step b) the starting charge is shaped so as to obtain a preform.
- the shaping can be carried out using any technique known to those skilled in the art, for example extrusion, granulation, pressing, casting, atomization, serigraphy (or “screen printing” in English), tape casting (or “tape casting” in English), or drop by drop gelation (or “drip casting” in English).
- the preforms obtained can be in the form of cylinders, polylobes, rings, or spheres.
- step c) the preform is brought into contact with a solution comprising a gelling agent chosen from divalent cations, trivalent cations and mixtures thereof, capable of causing the polysaccharide to gel, so as to obtain the product based on a lithium adsorbent.
- a gelling agent chosen from divalent cations, trivalent cations and mixtures thereof, capable of causing the polysaccharide to gel, so as to obtain the product based on a lithium adsorbent.
- the solution comprising a gelling agent chosen from divalent cations, trivalent cations and mixtures thereof, capable of causing the polysaccharide to gel, is well known to those skilled in the art.
- the gelling agent is preferably chosen from alkaline-earth cations, preferably chosen from Ca, Sr, Ba cations and mixtures thereof.
- the gelling agent is a Ca cation.
- the solution containing the gelling agent chosen from divalent cations, trivalent cations and mixtures thereof is preferably chosen from a solution comprising a divalent cation salt, a solution comprising a trivalent cation salt, or the source of lithium from from which the lithium is extracted, preferably brine, in particular when it contains such a cation.
- the solution comprising a divalent cation salt or a trivalent cation salt is chosen from an iodide solution of said cation and/or a chloride solution of said cation.
- the gelling solution is a solution comprising an alkaline-earth cation iodide and/or an alkaline-earth cation chloride. More preferably, the gelation solution is a solution comprising an alkaline earth cation chloride, preferably a solution comprising calcium chloride.
- the gelling solution is the source of lithium from which the lithium is extracted, preferably the brine from which the lithium must be collected, in particular when the latter comprises a divalent and/or trivalent cation.
- the gelling solution is a calcium chloride solution, the calcium chloride concentration of which is preferably greater than 1 mol/l, preferably greater than 2 mol/l of solution.
- the bringing into contact can for example be carried out by immersing the preform in a bath of gelling solution or by spraying the preform with the gelling solution.
- step b) and step c) are combined, in particular when the preform is implemented by dropwise gelling.
- a product based on lithium adsorbent is obtained.
- Said lithium adsorbent-based product may be in the form of cylinders, polylobes, rings, or spheres.
- the preform is shaped so that the largest dimension of the product based on lithium adsorbent is less than 100 mm, preferably less than 80 mm, preferably less than 50 mm, preferably less than 30 mm, or even less than 10 mm and/or that the smallest dimension of the lithium adsorbent-based product in a plane perpendicular to the direction of the largest dimension is greater than 1 ⁇ m, or even greater than 10 ⁇ m (micrometers).
- step d) optional, the product based on a lithium adsorbent is dried.
- the maximum temperature reached during said drying is greater than 20°C, and preferably less than 140°C, preferably less than 100°C, preferably less than 80°C.
- the drying cycle has a plateau at said maximum temperature reached.
- the holding time at the plateau is preferably greater than 1 hour, preferably greater than 2 hours, preferably greater than 5 hours and preferably less than 20 hours, preferably less than 15 hours. Drying is preferably carried out in air, at atmospheric pressure.
- step d a dry product based on lithium adsorbent is obtained.
- the invention also relates to a product comprising particles bound by a binder, said binder comprising, preferably consisting of, a gelled polysaccharide comprising a group establishing an ionic bond with a divalent cation, a trivalent cation and mixtures thereof, preferably a gelled alginate, said particles being essentially particles of a lithium adsorbent.
- a binder comprising, preferably consisting of, a gelled polysaccharide comprising a group establishing an ionic bond with a divalent cation, a trivalent cation and mixtures thereof, preferably a gelled alginate, said particles being essentially particles of a lithium adsorbent.
- the binder of the product comprising a lithium adsorbent according to the invention comprises, preferably consists essentially of, a gelled polysaccharide comprising a group establishing an ionic bond with a divalent cation, a trivalent cation and their mixtures, preferably with an alkaline-earth cation, preferably chosen from Ca, Sr, Ba cations and mixtures thereof, preferably a Ca cation.
- said gelled polysaccharide a gelled alginate or a gelled pectin, preferably a gelled alginate.
- the gelled polysaccharide, in particular the gelled alginate, contained in the binder can for example be demonstrated by steric exclusion chromatography.
- the product comprising a lithium adsorbent according to the invention consists essentially, after drying at 100° C. for 12 hours, of particles of a lithium adsorbent, bound by a binder consisting essentially of a gelled alginate.
- the particles of a lithium adsorbent of the product comprising a lithium adsorbent according to the invention are particles of a lithium adsorbent chosen from: a lithiated bayerite, preferably a material of formula (LiCI) x .2AI (OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10; a lithium aluminate, optionally hydrated and/or doped, said lithium aluminate preferably corresponding to the formula UAIO2, optionally hydrated and/or doped; a manganese and lithium spinel, optionally doped, said manganese and lithium spinel being preferably chosen from a manganese and lithium spinel of formula Li (i+X) Mn (2 -y ) M'y0 4 with - 0.20 ⁇ x ⁇ 0.4 and 0 £ y £ 1 , the element M' being chosen from aluminum, cobalt, nickel, chromium, iron, magnesium,
- a lithiated magnesium oxide, optionally hydrated and/or doped said lithiated magnesium oxide preferably having the formula LiMg0 2 , optionally hydrated and/or doped;
- H2T13O7 optionally hydrated and/or doped
- H4T15O12 optionally hydrated and/or doped
- the lithium adsorbent is chosen from: a lithiated bayerite, preferably a material of formula (LiCI) x .2Al(OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10; a manganese and lithium spinel, optionally doped; a lithium titanate, optionally hydrated and/or doped, said lithium titanate preferably being chosen from a lithium titanate corresponding to the formula LiTi0 2 , Li 2 Ti03 , Li 2 Ti 3 07 , Li 4 Ti 0i 2 , and their mixtures, optionally hydrated and/or doped, preferably Li 2 TiO3, optionally hydrated and/or doped ;
- H2T1O3 optionally hydrated and/or spiked; and their mixtures.
- the lithium adsorbent is a lithiated bayerite, preferably a material of formula (LiCI) x .2AI(OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10 .
- the product comprising a lithium adsorbent according to the invention comprises a mixture of at least two populations of particles of a lithium adsorbent, at least two of said populations of particles of a lithium adsorbent are into a different lithium adsorbent.
- the mass ratio of the quantity of gelled polysaccharide to the total quantity of said gelled polysaccharide and of the particles of a lithium adsorbent is greater than or equal to 0.1% , preferably greater than or equal to 0.2%, preferably greater than or equal to 0.3% and preferably less than or equal to 10%, more preferably less than or equal to 5%, preferably less than or equal to 4% , preferably less than or equal to 3%, preferably less than or equal to 2%, preferably less than or equal to 1%.
- the quantity of lithium adsorbent particles in the product is greater for the same volume.
- the mass quantity of particles of a lithium adsorbent, after drying at 100° C. for 12 hours is greater than or equal to 90%, preferably greater than 95%, preferably greater than or equal to 96%, preferably greater than or equal to 97%, preferably greater than or equal to 98%, and less than 99.9%, preferably less than 99.8%, preferably less than 99.7%, based on the mass of the product comprising a lithium adsorbent according to the invention , after drying at 100°C for 12 hours.
- the product comprising a lithium adsorbent according to the invention can be in the form of cylinders, polylobes, rings, or spheres.
- the largest dimension of the product according to the invention (or the macroscopic object according to the invention) comprising a lithium adsorbent according to the invention is less than 100 mm, preferably less than 80 mm, preferably less than 50 mm, preferably less than 30 mm, or even less than 10 mm.
- the smallest dimension of the product according to the invention (or the macroscopic object according to the invention) comprising a lithium adsorbent, in a plane perpendicular to the direction of the largest dimension is greater than 1 ⁇ m, or even greater than 10 pm.
- the invention also relates to a product comprising a lithium adsorbent obtained or capable of being obtained by the process according to the invention.
- This product is remarkable for its ability to retain its physical integrity during repetitive lithium adsorption-desorption cycling. This property moreover constitutes a signature of the method according to the invention.
- the water content of a dough is determined as being the loss of mass, expressed as a percentage, after drying in air at 200°C for 16 hours.
- the pastes of the examples are previously air-dried for 170 hours at 25°C.
- the acquisitions are carried out using an X'Pert type device from Panalytical, equipped with a copper anode, over an angular range 2Q between 5° and 80°, with a pitch of 0.017°, and a counting time of 300 s/step.
- the front optic has a fixed 0.25° divergence slit, a 0.02 rad Soller slit, a 10 mm mask and a fixed 0.5° anti-scatter slit.
- the sample is rotating on itself.
- the rear optic has a fixed anti-scattering slit of 0.25°, a Soller slit of 0.02 rad and a nickel filter.
- the diffraction patterns are then qualitatively analyzed using EVA software and the ICDD2016 database.
- the PDF data sheet 00-031-0700 of the ICDD2016 database is used to identify the phase (UCI).2AI(OH) 3 , xH 2 0.
- the crystallized phase of lithiated bayerite highlighted may present a slight angular offset of the peaks compared to said data sheet, a consequence in particular of the quantity of Li inserted into the structure of the lithiated bayerite.
- the content of elements other than H and O, partly Li, Cl and Al, is determined on pasta dried at 200°C for 16 hours in air, by inductively coupled plasma spectrometry, using a 5800 ICP device -OES from Agilent.
- Aluminum trichloride hexahydrate AICl 3.6H 2 0 of purity greater than 99% by mass, marketed by the company Merck, for example 1,
- Oxalic acid of purity greater than 99% by mass, marketed by the company Merck, for example 1,
- Lithium hydroxide monohydrate LiOH, H 2 0
- LiOH, H 2 0 Lithium hydroxide monohydrate
- Lithium chloride LiCI of purity greater than 99.5%% by mass, for examples 1 and 2,
- Hydrochloric acid HCl of purity greater than 99% by mass, in aqueous solution at 16M, for example 2,
- Example 1 The product of Example 1 (comparative) was obtained as follows:
- Boehmite precipitation is carried out in the following manner. 2500 g of aluminum trichloride hexahydrate (AICl 3.6H 2 0 ) are added to 3950 g of demineralized water, the whole being kept under stirring in a 30 liter stainless steel jacketed reactor. Then, still with stirring, a solution of 1200 g of sodium hydroxide (NaOH) and 3 liters of demineralized water are added gradually, so as to adjust the pH. The pH reached at the end of the synthesis is equal to 8. The temperature is maintained at 20° C. for the duration of the boehmite precipitation step. Then the boehmite precipitate is washed and filtered using a filter press.
- Al 3.6H 2 0 aluminum trichloride hexahydrate
- the water content of the boehmite precipitate at the end of this step is 85% by mass. Then, 2500 g of said boehmite precipitate are replumped in 1600 g of demineralised water at ambient temperature, then a solution containing 170 g of LiCl and 16.7 liters of demineralised water is added (which corresponds to a Li/ AI equal to 0.39), the mixture being stirred and heated at 80° C. for 1 hour.
- the mixture thus obtained is cooled to 60° C., then filtered in a filter press so as to obtain a paste.
- the paste thus obtained has the characteristics shown in Table 1 below.
- Said paste is then dried at 50°C in air until it has a water content equal to 50%. Then, 120 g of said dried paste, still at a temperature equal to 50° C., are introduced into a Z-arm mixer. Then 2.38 g of a 10 g/l oxalic acid solution are added to said dough under stirring. A homogeneous mixture is obtained, which is spread on a metal grid with a thickness equal to 1 mm and perforated with circular holes with a diameter equal to 1.5 mm, then scraped with a spatula on each side of the grid. so that said mixture fills the holes of said grid. The grid is then said to be “loaded”.
- the grid is placed under a circulation of hot air at 60°C, which makes it possible to “unload” said grid, the objects formed falling into a container placed under the grid.
- Said objects obtained are in the form of cylinders with an average length equal to 0.8 mm and an average diameter equal to 1.4 mm.
- Example 2 The product of Example 2 (according to the invention) was obtained as follows:
- LiCI is added, so that the molar ratio between the Cl provided by LiCI and GAI present initially in the mixture is equal to 1, the whole is mixed for a time equal to 5 minutes, the temperature being maintained at 25°C.
- the Li/Al molar ratio is equal to 1.5.
- the mixture is then heated using a hot plate, to a temperature equal to 60°C, the time during which said mixture is at a temperature greater than or equal to 50°C being equal to 15 minutes.
- the mixture is then maintained at a temperature equal to 60° C. for a time equal to 45 minutes.
- HCl is added to the mixture, so that the pH of the mixture is lowered to a value equal to 3, the value of the Cl/Al molar ratio in the mixture after addition of HCl being equal to 1.6, the duration of mixing being equal to 15 minutes, and the temperature being maintained equal to 60°C.
- the mixture thus obtained is filtered through a Buchner filter, at ambient temperature (below 50° C.), with filter papers of permeability equal to 2 ⁇ m so as to obtain a paste.
- the time during which the mixture is at a temperature greater than or equal to 50° C. is equal to 5 minutes.
- the paste obtained consists for more than 99% by mass of water, lithiated bayerite, and LiCI.
- a starting charge in accordance with the object of the present invention was produced, formed from a mixture of said paste obtained after filtration and ammonium alginate, the content of said alginate being equal to 1% by mass based on the mass of the starting batch, after drying at 200°C for 16 hours.
- Said paste containing lithiated bayerite and ammonium alginate was mixed in a planetary mixer under hot air created by a heat gun set on a temperature equal to 100° C., for 120 minutes so as to obtain a homogeneous starting charge and having a water content compatible with the shaping technique.
- the starting charge was then spread on a metal grid of thickness equal to 1 mm and perforated with circular holes of diameter equal to 1.5 mm, then scraped using a spatula on each side of the grid of so that said starting charge fills the holes of said grid.
- the grid is then said to be “loaded”.
- the grid is placed under a circulation of hot air at 60° C., which makes it possible to “unload” said grid, the objects formed falling into a container placed under the grid.
- Said objects obtained are in the form of cylinders with an average length equal to 0.8 mm and an average diameter equal to 1.4 mm.
- the desorption step followed by the adsorption step corresponds to a simulation of a lithium adsorption-desorption cycle.
- the product undergoes a total of 10 lithium adsorption-desorption cycles.
- the product of Example 2 does not generate this phenomenon, even after 10 adsorption-desorption cycles of lithium: the aqueous solution of lithium chloride and the brine remain perfectly clear at the end of the desorption stage and at the end of the adsorption stage, respectively.
- the product of Example 2 according to the invention therefore has better resistance to repetitive cycling of adsorption-desorption of lithium than the product of example 1, comparative.
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Abstract
The present invention relates to a product for the extraction of lithium from a brine, said product comprising particles bound by a binder, said binder comprising a gelled polysaccharide comprising a group establishing an ionic bond with a divalent cation, a trivalent cation and mixtures thereof, and preferably consisting of said gelled polysaccharide, said particles being essentially particles of a lithium adsorbent.
Description
DESCRIPTION DESCRIPTION
TITRE : Produit comprenant un adsorbant du lithium Domaine technique TITLE: Product comprising a lithium adsorbent Technical area
La présente invention se rapporte à un produit comprenant un adsorbant du lithium et à un procédé de fabrication de produits comprenant un adsorbant du lithium. The present invention relates to a product comprising a lithium adsorbent and to a method of manufacturing products comprising a lithium adsorbent.
Technique antérieure Prior technique
L’utilisation du lithium, notamment dans les batteries, est en constante augmentation. The use of lithium, particularly in batteries, is constantly increasing.
Les saumures sont des sources de lithium, pour lesquelles une extraction dudit lithium est nécessaire. Brines are sources of lithium, for which an extraction of said lithium is necessary.
Cette extraction, ou captation, peut s’effectuer à l’aide de colonnes remplies d’un matériau actif, qui capte sélectivement et réversiblement le lithium lorsque la saumure est à son contact. Le lithium est ensuite récupéré en faisant passer de l’eau légèrement saline et acidifiée dans ces colonnes. Il en résulte une solution concentrée en lithium qui sera purifiée avant une étape de précipitation, généralement sous la forme de carbonate de lithium. This extraction, or capture, can be carried out using columns filled with an active material, which selectively and reversibly captures the lithium when the brine comes into contact with it. The lithium is then recovered by passing slightly saline and acidified water through these columns. This results in a concentrated lithium solution which will be purified before a precipitation step, generally in the form of lithium carbonate.
Les adsorbants du lithium sont des matériaux avantageusement utilisés en tant que matériau actif permettant l’obtention de la solution concentrée en lithium au sein des colonnes d’extraction. Lithium adsorbents are materials advantageously used as an active material allowing the production of the concentrated lithium solution within the extraction columns.
La demande KR20190078350 décrit différents matériaux adsorbant du lithium dans une application de captation du lithium. Application KR20190078350 describes various lithium adsorbent materials in a lithium capture application.
La demande WO2018002336 décrit un matériau pour la captation du lithium de formule (LiCI)x.2AI(OH)3, nhhO avec x compris entre 0,4 et 1 et n compris entre 0,01 et 10. Application WO2018002336 describes a material for capturing lithium of formula (LiCI) x .2AI(OH) 3 , nhhO with x between 0.4 and 1 and n between 0.01 and 10.
La demande CN103212388 décrit un procédé d’extraction sélectif et irréversible des ions radioactifs de rubidium et de césium dans une saumure contenant de tels ions, notamment issue de déchets nucléaires radioactifs, à partir d’une solution comprenant un hydrosol d’alginate de sodium et d’une poudre de tétraphénylborate de potassium. Application CN103212388 describes a process for the selective and irreversible extraction of radioactive rubidium and cesium ions in a brine containing such ions, in particular from radioactive nuclear waste, from a solution comprising a hydrosol of sodium alginate and of a powder of potassium tetraphenylborate.
La captation du lithium s’accompagne d’une augmentation de volume du matériau adsorbant du lithium localisé dans la colonne d’extraction. Puis, lorsque le lithium est ensuite récupéré en faisant passer de l’eau légèrement saline et acidifiée dans lesdites colonnes, le volume du matériau adsorbant du lithium diminue. Ledit matériau subit ainsi des cycles répétés d’augmentation et de diminution de volume pouvant conduire à une dégradation de sa forme et donc à une diminution de l’efficacité de la captation du lithium. Lithium uptake is accompanied by an increase in volume of the lithium adsorbent material located in the extraction column. Then, when the lithium is subsequently recovered by passing slightly saline and acidified water through said columns, the volume of the lithium adsorbent material decreases. Said material thus undergoes repeated cycles of increase and decrease in volume which can lead to a degradation of its shape and therefore to a decrease in the efficiency of lithium capture.
Il existe un besoin pour des produits à base d’un adsorbant du lithium, obtenus par mise en forme d’une poudre, éventuellement humidifiée, lesdits produits présentant une bonne résistance aux cyclages répétitifs d’adsorption-désorption de lithium dans l’application. There is a need for products based on a lithium adsorbent, obtained by shaping a powder, optionally moistened, said products having good resistance to repetitive lithium adsorption-desorption cycling in the application.
Un but de l’invention est de répondre, au moins partiellement, à ce besoin.
Exposé de l’invention An object of the invention is to respond, at least partially, to this need. Disclosure of Invention
Selon l’invention, on atteint ce but au moyen d’un produit permettant avantageusement l’extraction facilitée du lithium, ledit produit comprenant des particules liées par un liant, ledit liant comprenant un polysaccharide gélifié comprenant un groupement établissant une liaison ionique avec un cation divalent, un cation trivalent et leurs mélanges, lesdites particules étant essentiellement, de préférence étant, des particules d’un adsorbant du lithium. De préférence le liant est constitué par ledit polysaccharide gélifié. According to the invention, this object is achieved by means of a product advantageously allowing the facilitated extraction of lithium, said product comprising particles bound by a binder, said binder comprising a gelled polysaccharide comprising a group establishing an ionic bond with a cation divalent, a trivalent cation and mixtures thereof, said particles being essentially, preferably being, particles of a lithium adsorbent. Preferably the binder consists of said gelled polysaccharide.
Selon des modes de réalisation préférés mais non limitatifs de la présente invention, qui peuvent, le cas échéant, être combinés entre eux : le polysaccharide gélifié comprend un groupement établissant une liaison ionique avec un cation alcalino-terreux, de préférence choisi parmi les cations de Ca, Sr, Ba et leurs mélanges, de préférence avec un cation de Ca. le groupement est choisi parmi les groupements carboxylates (-COO-) ou les groupements sulfonates (-SO3 ), de préférence encore ledit groupement est un groupement carboxylate. le polysaccharide gélifié est un alginate gélifié sous l’action d’un cation divalent, d’un cation trivalent et leurs mélanges, de préférence sous l’action d’un cation divalent, de préférence encore sous l’action d’un cation de calcium. le polysaccharide gélifié est une pectine gélifiée sous l’action d’un cation divalent, d’un cation trivalent et leurs mélanges, de préférence sous l’action d’un cation divalent, de préférence encore sous l’action d’un cation de calcium l’adsorbant du lithium est choisi parmi : According to preferred but non-limiting embodiments of the present invention, which can, where appropriate, be combined with each other: the gelled polysaccharide comprises a group establishing an ionic bond with an alkaline-earth cation, preferably chosen from the cations of Ca, Sr, Ba and their mixtures, preferably with a Ca cation. the group is chosen from carboxylate groups (-COO-) or sulphonate groups (-SO 3 ), more preferably said group is a carboxylate group. the gelled polysaccharide is an alginate gelled under the action of a divalent cation, a trivalent cation and mixtures thereof, preferably under the action of a divalent cation, more preferably under the action of a cation of calcium. the gelled polysaccharide is a pectin gelled under the action of a divalent cation, a trivalent cation and mixtures thereof, preferably under the action of a divalent cation, more preferably under the action of a cation of calcium the lithium adsorbent is chosen from:
- une bayérite lithiée, de préférence un matériau de formule (LiCI)x.2AI(OH)3, nhhO, avec x compris entre 0,4 et 1 et n compris entre 0,01 et 10 ; - a lithiated bayerite, preferably a material of formula (LiCI) x .2AI(OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10;
- un aluminate de lithium, optionnellement hydraté et/ou dopé, ledit aluminate de lithium répondant de préférence à la formule UAIO2, optionnellement hydraté et/ou dopé ;- a lithium aluminate, optionally hydrated and/or doped, said lithium aluminate preferably corresponding to the formula UAIO2, optionally hydrated and/or doped;
- un spinelle de manganèse et de lithium, optionnellement dopé, ledit spinelle de manganèse et de lithium étant de préférence choisi parmi un spinelle de manganèse et de lithium de formule Li(i+X)Mn(2-y)M’y04 avec -0,20 < x < 0,4 et 0 < y < 1, l’élément M’ étant choisi parmi l’aluminium, le cobalt, le nickel, le chrome, le fer, le magnésium, le titane, le vanadium, le cuivre, le zinc, le gallium, le calcium, le niobium, l’yttrium, le baryum, le silicium, le bore, le zirconium, le lithium et leurs mélanges, l’électroneutralité dudit manganate de lithium étant assurée par la teneur en oxygène ;- a manganese and lithium spinel, optionally doped, said manganese and lithium spinel being preferably chosen from a manganese and lithium spinel of formula Li (i+X) Mn (2 -y ) M'y0 4 with -0.20 <x <0.4 and 0 <y <1, the element M' being chosen from aluminum, cobalt, nickel, chromium, iron, magnesium, titanium, vanadium, copper, zinc, gallium, calcium, niobium, yttrium, barium, silicon, boron, zirconium, lithium and mixtures thereof, the electroneutrality of said lithium manganate being ensured by the content of oxygen;
- un oxyde de fer lithié, optionnellement hydraté et/ou dopé, ledit oxyde de fer lithié répondant de préférence à la formule LiFe02, optionnellement hydraté et/ou dopé ;
- Un oxyde de magnésium lithié, optionnellement hydraté et/ou dopé, ledit oxyde de magnésium lithié répondant de préférence à la formule LiMg02, optionnellement hydraté et/ou dopé ; - A lithiated iron oxide, optionally hydrated and/or doped, said lithiated iron oxide preferably having the formula LiFe0 2 , optionally hydrated and/or doped; - A lithiated magnesium oxide, optionally hydrated and/or doped, said lithiated magnesium oxide preferably having the formula LiMg0 2 , optionally hydrated and/or doped;
- Un spinelle de cobalt et de lithium, optionnellement hydraté et/ou dopé, ledit spinelle de cobalt et de lithium répondant de préférence à la formule UC02O4, optionnellement hydraté et/ou dopé ; - A cobalt and lithium spinel, optionally hydrated and/or doped, said cobalt and lithium spinel preferably having the formula UCO2O4, optionally hydrated and/or doped;
- Un titanate de lithium, optionnellement hydraté et/ou dopé, ledit titanate de lithium étant de préférence choisi parmi un titanate de lithium répondant à la formule LiTi02, LhTiOs, LÎ2TÎ307, LÎ4TÎ50i2, et leurs mélanges, optionnellement hydraté(s) et/ou dopé(s), de préférence LhTiCb, optionnellement hydraté et/ou dopé ; - A lithium titanate, optionally hydrated and/or doped, said lithium titanate being preferably chosen from a lithium titanate corresponding to the formula LiTi0 2 , LhTiOs, LÎ2TÎ307, LÎ4TÎ50i2, and mixtures thereof, optionally hydrated and/or or doped(s), preferably LhTiCb, optionally hydrated and/or doped;
- H2T1O3, optionnellement hydraté et/ou dopé ; - H2T1O3, optionally hydrated and/or doped;
- H2T13O7, optionnellement hydraté et/ou dopé ; - H2T13O7, optionally hydrated and/or doped;
- H4T15O12, optionnellement hydraté et/ou dopé ; - H4T15O12, optionally hydrated and/or doped;
- et leurs mélanges. - and mixtures thereof.
- l’adsorbant du lithium est choisi parmi : - the lithium adsorbent is chosen from:
- une bayérite lithiée, de préférence un matériau de formule (LiCI)x.2AI(OH)3, nhhO, avec x compris entre 0,4 et 1 et n compris entre 0,01 et 10 ; - a lithiated bayerite, preferably a material of formula (LiCI) x .2AI(OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10;
- un spinelle de manganèse et de lithium, optionnellement dopé ; - a manganese and lithium spinel, optionally doped;
- un titanate de lithium, optionnellement hydraté et/ou dopé, ledit titanate de lithium étant de préférence choisi parmi un titanate de lithium répondant à la formule LiTiC>2, Li2TiC>3, Li2Ti307, Li4Ti 0i2, et leurs mélanges, optionnellement hydraté(s) et/ou dopé(s), de préférence LhTiCb, optionnellement hydraté et/ou dopé; - a lithium titanate, optionally hydrated and/or doped, said lithium titanate preferably being chosen from a lithium titanate corresponding to the formula LiTiC>2, Li 2 TiC> 3 , Li 2 Ti 3 07, Li 4 Ti 0i 2 , and mixtures thereof, optionally hydrated and/or doped, preferably LhTiCb, optionally hydrated and/or doped ;
- H2T1O3, optionnellement hydraté et/ou dopé ; - H2T1O3, optionally hydrated and/or doped;
- et leurs mélanges. - and mixtures thereof.
- l’adsorbant du lithium est une bayérite lithiée, de préférence un matériau de formule (LiCI)x.2AI(OH)3, nhhO, avec x compris entre 0,4 et 1 et n compris entre 0,01 et 10. la quantité massique de particules d’un adsorbant du lithium, après séchage à 100°C pendant 12 heures, est supérieure ou égale à 95% et inférieure à 99,9%, sur la base de la masse dudit produit après séchage à 100°C pendant 12 heures. - the lithium adsorbent is a lithiated bayerite, preferably a material of formula (LiCI) x .2AI(OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10. mass quantity of particles of a lithium adsorbent, after drying at 100°C for 12 hours, is greater than or equal to 95% and less than 99.9%, based on the mass of said product after drying at 100°C for 12 hours.
Le produit se présente sous la forme de cylindres, de polylobés, d’anneaux, ou de sphères, de préférence, dont plus grande dimension est inférieure à 100 mm, de préférence inférieure à 80 mm, de préférence inférieure à 50 mm et la plus petite dimension, dans un plan perpendiculaire à la direction de la plus grande dimension, est supérieure à 1 pm. The product is in the form of cylinders, polylobes, rings, or spheres, preferably, the largest dimension of which is less than 100 mm, preferably less than 80 mm, preferably less than 50 mm and the small dimension, in a plane perpendicular to the direction of the largest dimension, is greater than 1 µm.
Les produits comprenant un adsorbant du lithium décrit précédemment, en particulier mis sous forme d’objets macroscopiques présentent une résistance améliorée aux cyclages répétitifs
d’adsorption-désorption de lithium notamment dans des colonnes d’extraction du lithium décrites précédemment. Products comprising a lithium adsorbent described above, in particular put in the form of macroscopic objects, have improved resistance to repetitive cycling adsorption-desorption of lithium in particular in lithium extraction columns described above.
L’invention concerne également un procédé de fabrication d’un produit comprenant un adsorbant du lithium, notamment un produit tel que décrit précédemment, comprenant au moins les étapes suivantes : a) mélange de matières premières pour former une charge de départ, ladite charge de départ comportant une poudre d’un adsorbant du lithium, et un polysaccharide gélifiable sous l’action d’un agent de gélification, le rapport massique de la quantité dudit polysaccharide sur la quantité totale dudit polysaccharide et de la poudre d’un adsorbant du lithium étant de préférence supérieur ou égal à 0,1% et de préférence inférieur ou égal à 10%, de préférence encore inférieur ou égal à 5%, b) mise en forme de ladite charge de départ, de manière à obtenir une préforme, c) mise en contact de ladite préforme avec ledit agent de gélification et gélification dudit polysaccharide de manière à obtenir ledit produit comprenant un adsorbant du lithium, d) optionnellement, séchage dudit produit comprenant un adsorbant du lithium. The invention also relates to a process for manufacturing a product comprising a lithium adsorbent, in particular a product as described above, comprising at least the following steps: a) mixing raw materials to form a starting charge, said charge of starting comprising a powder of a lithium adsorbent, and a polysaccharide which can be gelled under the action of a gelling agent, the mass ratio of the quantity of said polysaccharide to the total quantity of said polysaccharide and of the powder of a lithium adsorbent being preferably greater than or equal to 0.1% and preferably less than or equal to 10%, more preferably less than or equal to 5%, b) shaping of said starting charge, so as to obtain a preform, c ) bringing said preform into contact with said gelling agent and gelling said polysaccharide so as to obtain said product comprising a lithium adsorbent, d) optionally, drying said product comprising u n adsorbing lithium.
Selon des modes de réalisation préférés mais non limitatifs de la présente invention, qui peuvent, le cas échéant, être combinés entre eux : l’adsorbant du lithium est une bayérite lithiée, de préférence un matériau de formule (LiCI)x.2AI(OH)3, nH20, avec x compris entre 0,4 et 1 et n compris entre 0,01 et 10. le polysaccharide est un alginate ou une pectine, de préférence un alginate. l’agent gélifiant est choisi parmi Ca, Sr, Ba et leurs mélanges, de préférence l’agent gélifiant est Ca. According to preferred but non-limiting embodiments of the present invention, which can, where appropriate, be combined with one another: the lithium adsorbent is a lithiated bayerite, preferably a material of formula (LiCI) x .2AI(OH ) 3 , nH 2 0, with x between 0.4 and 1 and n between 0.01 and 10. the polysaccharide is an alginate or a pectin, preferably an alginate. the gelling agent is chosen from Ca, Sr, Ba and mixtures thereof, preferably the gelling agent is Ca.
L’invention concerne également un produit susceptible d’être obtenu par le procédé tel que décrit précédemment. The invention also relates to a product capable of being obtained by the method as described above.
L’invention concerne enfin un dispositif de captation du lithium, en particulier une colonne d’extraction, comportant un produit selon l’invention ou un produit obtenu ou susceptible d’être obtenu par le procédé selon l’invention tels que décrits précédemment. The invention finally relates to a lithium capture device, in particular an extraction column, comprising a product according to the invention or a product obtained or capable of being obtained by the method according to the invention as described previously.
Définitions Definitions
- On appelle « adsorbant du lithium » tout matériau capable de retenir du lithium dans sa structure par adsorption, en particulier chimique ou physique, et/ou par échange entre un ion de sa structure avec un ion Li+. Une bayérite lithiée, en particulier un matériau de formule (LiCI)x.2AI(OH)3, nhhO avec x compris entre 0,4 et 1 et n compris entre 0,01 et 10, est un exemple de matériau adsorbant du lithium. - The term “lithium adsorbent” refers to any material capable of retaining lithium in its structure by adsorption, in particular chemical or physical, and/or by exchange between an ion of its structure with an Li+ ion. A lithiated bayerite, in particular a material of formula (LiCI) x .2AI(OH) 3 , nhhO with x between 0.4 and 1 and n between 0.01 and 10, is an example of a lithium adsorbent material.
- On appelle notamment « bayérite lithiée » le composé de formule LiCI.2AI(0H)3.nH20 tel qu’indiqué dans la fiche ICDD PDF 00-031-0700, mais également par extension, des
composés présentant un rapport des quantités molaires du lithium et de l’aluminium, Li/AI différent de 0,5. Dans certains modes, il peut être inférieur à 0,5. Selon d’autres modes, il peut être supérieur à 0,5. - The compound of formula LiCI.2AI(0H) 3 .nH 2 0 as indicated in the ICDD PDF 00-031-0700 sheet, but also by extension, is called "lithium bayerite". compounds having a ratio of molar amounts of lithium and aluminum, Li/Al different from 0.5. In some modes, it may be less than 0.5. According to other modes, it may be greater than 0.5.
- On appelle « polysaccharides », selon la définition classique, des polymères composés d’enchaînements d’unités osidiques reliées par des liaisons glycosidiques. - The term "polysaccharides", according to the classic definition, refers to polymers composed of sequences of saccharide units linked by glycosidic bonds.
- 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. - The term “gellable polysaccharide” under the action of a gelling agent means a polysaccharide capable of forming a gel under the action of said gelling agent.
- 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 (OQHZOQ )^ 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. - A gelled polysaccharide results from the association of polysaccharide chains under the action of a gelling agent. By way of example, alginate has the formula (O Q HZO Q )^ Alginate is a polyosidic chain comprising carboxylate groups (COO- ). Calcium Ca 2+ ions (gelling agent) react with two strands of alginate, that is to say with the carboxylate groups COO , leading to the polymerization of the alginate chains and the bonding of the molecules between them. The reaction thus allows the creation of a gel.
Tous les pourcentages de la présente description sont des pourcentages en masse, sauf indication contraire. All percentages herein are percentages by weight, unless otherwise indicated.
Les verbes « contenir », « comprendre » et « présenter » doivent être interprétés de manière large, non limitative, sauf indication contraire. The verbs “contain”, “understand” and “present” must be interpreted in a broad, non-limiting way, unless otherwise indicated.
Description détaillée detailed description
Un procédé de fabrication d’un produit selon l’invention va maintenant être détaillé. A method of manufacturing a product according to the invention will now be detailed.
A l’étape a), la charge de départ comporte au moins une poudre d’un adsorbant du lithium. Dans le procédé selon l’invention, la ou les poudre(s) d’adsorbant du lithium peut ou peuvent être apportée(s) sous une forme sèche, mais également sous une forme humide, par exemple sous la forme d’une suspension et/ou d’une pâte. In step a), the starting charge comprises at least one powder of a lithium adsorbent. In the method according to the invention, the lithium adsorbent powder(s) may or may be provided in a dry form, but also in a wet form, for example in the form of a suspension and /or a paste.
Dans un mode de réalisation, notamment lorsque la charge de départ contient une poudre de bayérite lithiée, de préférence une poudre d’un matériau de formule (LiCI)x.2AI(OH)3, nhhO, avec x compris entre 0,4 et 1,0 et n compris entre 0,01 et 10, ladite poudre est apportée sous une forme humide, de préférence sous la forme d’une suspension et/ou d’une pâte. In one embodiment, in particular when the starting charge contains a lithiated bayerite powder, preferably a powder of a material of formula (LiCI) x .2AI(OH) 3 , nhhO, with x between 0.4 and 1.0 and n between 0.01 and 10, said powder is supplied in a wet form, preferably in the form of a suspension and/or a paste.
Dans un mode de réalisation, la charge de départ comporte au moins deux poudres d’un adsorbant du lithium, de préférence au moins deux desdites poudres d’un adsorbant du lithium sont en un adsorbant du lithium différent. In one embodiment, the starting charge comprises at least two powders of a lithium adsorbent, preferably at least two of said powders of a lithium adsorbent are made of a different lithium adsorbent.
Dans un mode de réalisation préféré, la charge de départ comporte une seule poudre d’un adsorbant du lithium. In a preferred embodiment, the starting charge comprises a single powder of a lithium adsorbent.
De préférence, l’adsorbant du lithium est choisi parmi :
une bayérite lithiée, de préférence un matériau de formule (LiCI)x.2AI(OH)3, nhhO, avec x compris entre 0,4 et 1 et n compris entre 0,01 et 10 ; un aluminate de lithium, optionnellement hydraté et/ou dopé, ledit aluminate de lithium répondant de préférence à la formule UAIO2, optionnellement hydraté et/ou dopé ; un spinelle de manganèse et de lithium, optionnellement dopé, ledit spinelle de manganèse et de lithium étant de préférence choisi parmi un spinelle de manganèse et de lithium de formule Li(i+X)Mn(2-y)M’y04 avec -0,20 < x < 0,4 et 0 < y < 1, l’élément M’ étant choisi parmi l’aluminium, le cobalt, le nickel, le chrome, le fer, le magnésium, le titane, le vanadium, le cuivre, le zinc, le gallium, le calcium, le niobium, l’yttrium, le baryum, le silicium, le bore, le zirconium, le lithium et leurs mélanges, l’électroneutralité dudit manganate de lithium étant assurée par la teneur en oxygène ; un oxyde de fer lithié, optionnellement hydraté et/ou dopé, ledit oxyde de fer lithié répondant de préférence à la formule LiFe02, optionnellement hydraté et/ou dopé ;Preferably, the lithium adsorbent is chosen from: a lithiated bayerite, preferably a material of formula (LiCI) x .2Al(OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10; a lithium aluminate, optionally hydrated and/or doped, said lithium aluminate preferably corresponding to the formula UAIO 2 , optionally hydrated and/or doped; a manganese and lithium spinel, optionally doped, said manganese and lithium spinel being preferably chosen from a manganese and lithium spinel of formula Li (i+X) Mn (2 -y ) M'y0 4 with - 0.20 < x < 0.4 and 0 < y < 1, the element M' being chosen from aluminum, cobalt, nickel, chromium, iron, magnesium, titanium, vanadium, copper, zinc, gallium, calcium, niobium, yttrium, barium, silicon, boron, zirconium, lithium and mixtures thereof, the electroneutrality of said lithium manganate being ensured by the oxygen content ; a lithiated iron oxide, optionally hydrated and/or doped, said lithiated iron oxide preferably having the formula LiFe0 2 , optionally hydrated and/or doped;
Un oxyde de magnésium lithié, optionnellement hydraté et/ou dopé, ledit oxyde de magnésium lithié répondant de préférence à la formule LiMg02, optionnellement hydraté et/ou dopé ; A lithiated magnesium oxide, optionally hydrated and/or doped, said lithiated magnesium oxide preferably having the formula LiMg0 2 , optionally hydrated and/or doped;
Un spinelle de cobalt et de lithium, optionnellement hydraté et/ou dopé, ledit spinelle de cobalt et de lithium répondant de préférence à la formule UC02O4, optionnellement hydraté et/ou dopé ; A cobalt and lithium spinel, optionally hydrated and/or doped, said cobalt and lithium spinel preferably having the formula UC0 2 O 4 , optionally hydrated and/or doped;
Un titanate de lithium, optionnellement hydraté et/ou dopé, ledit titanate de lithium étant de préférence choisi parmi un titanate de lithium répondant à la formule LiTi02, LhTiOs, LÎ2TÎ307, Li4Ti50i2, et leurs mélanges, optionnellement hydraté(s) et/ou dopé(s), de préférence LhTiCb, optionnellement hydraté et/ou dopé ; hhTiCb, optionnellement hydraté et/ou dopé ; A lithium titanate, optionally hydrated and/or doped, said lithium titanate preferably being chosen from a lithium titanate corresponding to the formula LiTi0 2 , LhTiOs, LÎ2TÎ307, Li 4 Ti 5 0i2, and mixtures thereof, optionally hydrated(s ) and/or doped, preferably LhTiCb, optionally hydrated and/or doped; hhTiCb, optionally hydrated and/or doped;
H2T13O7, optionnellement hydraté et/ou dopé ; H2T13O7, optionally hydrated and/or doped;
H4T15O12, optionnellement hydraté et/ou dopé ; H4T15O12, optionally hydrated and/or doped;
Et leurs mélanges. And their mixtures.
De préférence l’adsorbant du lithium est choisi parmi : une bayérite lithiée, de préférence un matériau de formule (LiCI)x.2AI(OH)3, nhhO, avec x compris entre 0,4 et 1 et n compris entre 0,01 et 10 ; un spinelle de manganèse et de lithium, optionnellement dopé ; un titanate de lithium, optionnellement hydraté et/ou dopé, ledit titanate de lithium étant de préférence choisi parmi un titanate de lithium répondant à la formule LiTi02, L TiOs, Li2Ti307, Li4Ti 0i2, et leurs mélanges, optionnellement hydraté(s) et/ou dopé(s), de préférence Li2Ti03, optionnellement hydraté et/ou dopé ; Preferably, the lithium adsorbent is chosen from: a lithiated bayerite, preferably a material of formula (LiCI) x .2Al(OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10; a manganese and lithium spinel, optionally doped; a lithium titanate, optionally hydrated and/or doped, said lithium titanate being preferably chosen from a lithium titanate corresponding to the formula LiTi0 2 , L TiOs , Li 2 Ti 3 0 7 , Li 4 Ti 0i 2 , and their mixtures, optionally hydrated and/or doped, preferably Li 2 Ti0 3 , optionally hydrated and/or doped ;
H2T1O3, optionnellement hydraté et/ou dopé ;
et leurs mélanges. H2T1O3, optionally hydrated and/or spiked; and their mixtures.
De préférence, l’adsorbant du lithium est une bayérite lithiée, de préférence un matériau de formule (LiCI)x.2AI(OH)3, nhhO, avec x compris entre 0,4 et 1 et n compris entre 0,01 et 10. De préférence, la taille médiane de la poudre d’adsorbant du lithium est supérieure à 0,1 pm et/ou inférieure à 100 pm. Preferably, the lithium adsorbent is a lithiated bayerite, preferably a material of formula (LiCI) x .2AI(OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10 Preferably, the median size of the lithium adsorbent powder is greater than 0.1 μm and/or less than 100 μm.
La charge de départ contient un polysaccharide comprenant un groupement apte former une liaison ionique avec un agent de gélification choisi parmi les cations divalents, les cations trivalents (par exemple un cation de Fe ou d’AI) et leurs mélanges pour la formation d’un polysaccharide gélifié, notamment en une quantité telle que le rapport massique de la quantité dudit polysaccharide sur la quantité totale dudit polysaccharide et de poudre d’adsorbant du lithium est supérieur ou égal à 0,1% et de préférence inférieur ou égal à 10%, de préférence encore inférieur à 5%. De préférence, ledit rapport massique est supérieur ou égal à 0,2%, de préférence supérieure ou égale à 0,3% et de préférence inférieur ou égal à 4%, de préférence inférieur ou égal à 3%, de préférence inférieur ou égal à 2%, de préférence inférieur ou égal à 1%. The starting charge contains a polysaccharide comprising a group capable of forming an ionic bond with a gelling agent chosen from divalent cations, trivalent cations (for example an Fe or Al cation) and mixtures thereof for the formation of a gelled polysaccharide, in particular in an amount such that the mass ratio of the amount of said polysaccharide to the total amount of said polysaccharide and lithium adsorbent powder is greater than or equal to 0.1% and preferably less than or equal to 10%, preferably still less than 5%. 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 at 2%, preferably less than or equal to 1%.
De préférence, le groupement du polysaccharide apte former une liaison ionique avec un agent de gélification choisi parmi les cations divalents, les cations trivalents et leurs mélanges, est choisi parmi un groupement carboxylate COO ou un groupement sulfonate SO3 , de préférence encore ledit groupement est un groupement carboxylate COO-. Preferably, the polysaccharide group capable of forming an ionic bond with a gelling agent chosen from divalent cations, trivalent cations and mixtures thereof, is chosen from a carboxylate group COO or a sulphonate group SO 3 , more preferably said group is a COO- carboxylate group.
De préférence, le polysaccharide comprend un groupement apte former une liaison ionique avec un agent de gélification choisi parmi les cations alcalino-terreux, de préférence choisi parmi les cations de Ca, Sr, Ba et leurs mélanges. De préférence, le polysaccharide comprend un groupement apte former une liaison ionique avec un cation de Ca. Preferably, the polysaccharide comprises a group capable of forming an ionic bond with a gelling agent chosen from alkaline-earth cations, preferably chosen from Ca, Sr, Ba cations and mixtures thereof. Preferably, the polysaccharide comprises a group capable of forming an ionic bond with a Ca cation.
De préférence, le polysaccharide comprenant un groupement apte former une liaison ionique avec un agent de gélification est choisi parmi les alginates et les pectines. Preferably, the polysaccharide comprising a group capable of forming an ionic bond with a gelling agent is chosen from alginates and pectins.
De préférence le polysaccharide comprenant un groupement apte former une liaison ionique avec un agent de gélification est choisi parmi les alginates, de préférence parmi les alginates de sodium, les alginates de potassium, les alginates d’ammonium, et leurs mélanges. De préférence l’alginate est un alginate d’ammonium. 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, and mixtures thereof. Preferably the alginate is an ammonium alginate.
De préférence, la charge de départ contient une poudre d’un adsorbant du lithium et un polysaccharide comprenant un groupement apte former une liaison ionique avec un agent de gélification choisi parmi les cations divalents, les cations trivalents et leurs mélanges. Preferably, the starting charge contains a powder of a lithium adsorbent and a polysaccharide comprising a group capable of forming an ionic bond with a gelling agent chosen from divalent cations, trivalent cations and mixtures thereof.
Dans le procédé selon l’invention, le polysaccharide comprenant un groupement apte former une liaison ionique avec un agent de gélification choisi parmi les cations divalents, les cations trivalents et leurs mélanges, de préférence l’alginate peut être apporté sous la forme d’une solution.
Comme cela est bien connu de l’homme du métier, la charge de départ peut comporter, en plus de la ou des poudre(s) d’adsorbant du lithium et du polysaccharide comprenant un groupement apte à former une liaison ionique avec un agent de gélification choisi parmi les cations divalents, les cations trivalents et leurs mélanges, un solvant et/ou un liant organique et/ou un plastifiant et/ou un lubrifiant et/ou des particules porogènes, dont les natures et les quantités sont adaptées à la méthode de mise en forme de l’étape b). In the process according to the invention, the polysaccharide comprising a group capable of forming an ionic bond with a gelling agent chosen from divalent cations, trivalent cations and mixtures thereof, preferably alginate, can be provided in the form of a solution. As is well known to those skilled in the art, the starting charge may comprise, in addition to the adsorbent powder(s), lithium and polysaccharide comprising a group capable of forming an ionic bond with a gelation chosen from divalent cations, trivalent cations and mixtures thereof, a solvent and/or an organic binder and/or a plasticizer and/or a lubricant and/or pore-forming particles, the natures and quantities of which are adapted to the method formatting step b).
De préférence le solvant est l’eau. La quantité de solvant est adaptée au procédé de mise en forme mis en œuvre de l’étape b) ainsi qu’à la présence de polysaccharide comprenant un groupement apte à former une liaison ionique avec un agent de gélification choisi parmi les cations divalents, les cations trivalents et leurs mélanges dans la charge de départ. Preferably the solvent is water. The amount of solvent is adapted to the shaping process implemented in step b) as well as to the presence of polysaccharide comprising a group capable of forming an ionic bond with a gelling agent chosen from divalent cations, trivalent cations and their mixtures in the starting charge.
Dans un mode de réalisation, en particulier lorsque la charge de départ contient une quantité de solvant, de préférence d’eau, trop importante vis-à-vis du procédé de mise en forme envisagé à l’étape b), en particulier lorsque la poudre d’adsorbant du lithium est apportée sous une forme humide, une étape d’élimination d’une partie du solvant peut être effectuée, avant l’étape b). In one embodiment, in particular when the starting charge contains a quantity of solvent, preferably water, that is too large with respect to the shaping process envisaged in step b), in particular when the lithium adsorbent powder is provided in a wet form, a step of removing part of the solvent can be carried out, before step b).
La charge de départ contient optionnellement un liant organique facilitant la constitution de la préforme, de préférence en une teneur comprise entre 0, 1 % et 10%, de préférence entre 0,2% et 2% en masse sur la base de la masse de la ou des poudre(s) d’adsorbant du lithium de la charge de départ. The starting charge optionally contains an organic binder facilitating the constitution of the preform, preferably in a content of between 0.1% and 10%, preferably between 0.2% and 2% by mass based on the mass of the lithium adsorbent powder(s) of the starting charge.
Tous les liants organiques classiquement utilisés pour la fabrication de produits poreux céramiques peuvent être mis en œuvre, par exemple l’alcool polyvinylique (PVA) ou les polyéthylènes glycol (PEG), le méthylstéarate, l’éthylstéarate, les cires, les polyoléfines, les oxydes de polyoléfines, la glycérine, l’acide propionique, l’acide maléique, l’alcool benzylique, l’isopropanol, l’alcool butylique, une dispersion de paraffine et de polyéthylène, et leurs mélanges. All the organic binders conventionally used for the manufacture of porous ceramic products can be used, for example polyvinyl alcohol (PVA) or polyethylene glycol (PEG), methylstearate, ethylstearate, waxes, polyolefins, polyolefin oxides, glycerin, propionic acid, maleic acid, benzyl alcohol, isopropanol, butyl alcohol, paraffin and polyethylene dispersion, and mixtures thereof.
La charge de départ contient optionnellement un plastifiant, facilitant également la constitution de la préforme. The starting charge optionally contains a plasticizer, also facilitating the constitution of the preform.
De préférence, la teneur en plastifiant est comprise entre 0,1% et 10%, de préférence entre 0,5% et 5%, en masse sur la base de la masse de la ou des poudre(s) d’adsorbant du lithium de la charge de départ. Le plastifiant peut constituer un liant. Preferably, the content of plasticizer is between 0.1% and 10%, preferably between 0.5% and 5%, by mass based on the mass of the lithium adsorbent powder(s). of the starting load. The plasticizer can constitute a binder.
Tous les plastifiants classiquement utilisés pour la fabrication de produits poreux céramiques peuvent être mis en œuvre, par exemple le polyéthylène glycol, les oxydes de polyoléfines, les huiles hydrogénées, les alcools, notamment le glycérol et le glycol, les esters, et leurs mélanges.
La charge de départ contient optionnellement un lubrifiant, facilitant également la constitution de la préforme. De préférence, la teneur en lubrifiant est comprise entre 0,1% et 10%, de préférence entre 0,5% et 5% en masse de la ou des poudre(s) d’adsorbant du lithium de la charge de départ. All the plasticizers conventionally used for the manufacture of porous ceramic products can be used, for example polyethylene glycol, polyolefin oxides, hydrogenated oils, alcohols, in particular glycerol and glycol, esters, and mixtures thereof. The starting charge optionally contains a lubricant, also facilitating the constitution of the preform. Preferably, the lubricant content is between 0.1% and 10%, preferably between 0.5% and 5% by weight of the lithium adsorbent powder(s) of the starting charge.
Tous les lubrifiants classiquement utilisés pour la fabrication de produits poreux céramiques peuvent être mis en œuvre, par exemple la vaseline et/ou la glycérine et/ou des cires. All the lubricants conventionally used for the manufacture of porous ceramic products can be used, for example petroleum jelly and/or glycerin and/or waxes.
La charge de départ contient optionnellement des particules porogènes, bien connues de l’homme du métier, qui sont destinées à être éliminés lors du procédé selon l’invention, laissant ainsi la place à des pores. Leur quantité et leurs dimensions sont choisies de manière à notamment ajuster le volume poreux dans le produit à base d’adsorbant du lithium obtenu en fin d’étape b) ou en fin d’étape c). De préférence, lesdites particules porogènes sont en un matériau soluble dans le solvant. The starting charge optionally contains pore-forming particles, well known to those skilled in the art, which are intended to be eliminated during the process according to the invention, thus leaving room for pores. Their quantity and their dimensions are chosen so as in particular to adjust the pore volume in the lithium adsorbent-based product obtained at the end of step b) or at the end of step c). Preferably, said pore-forming particles are made of a material soluble in the solvent.
La présence et la nature du liant et/ou du lubrifiant et/ou du plastifiant sont notamment fonction de la technique de mise en forme utilisée à l’étape b). The presence and nature of the binder and/or the lubricant and/or the plasticizer depend in particular on the shaping technique used in step b).
Dans un mode de réalisation préféré, la charge de départ ne contient pas d’autres constituants que la ou les poudre(s) d’adsorbant du lithium, le polysaccharide, un solvant, un liant organique, un plastifiant, un lubrifiant et des particules porogènes. In a preferred embodiment, the starting charge does not contain any constituents other than the lithium adsorbent powder(s), the polysaccharide, a solvent, an organic binder, a plasticizer, a lubricant and particles porogens.
De préférence, le polysaccharide, de préférence l’alginate, le solvant, de préférence l’eau sont mélangés de manière à obtenir un mélange intime. Puis les autres constituants de la charge de départ, en particulier la ou les poudre(s) d’adsorbant du lithium, les liant, lubrifiant, plastifiant et particules porogènes optionnels sont ajoutés sous agitation. Preferably, the polysaccharide, preferably the alginate, the solvent, preferably the water are mixed in such a way as to obtain an intimate mixture. Then the other constituents of the starting charge, in particular the lithium adsorbent powder(s), the optional binder, lubricant, plasticizer and blowing particles are added with stirring.
Dans un mode de réalisation, la quantité de solvant, de préférence de l’eau, peut être ajoutée en plusieurs fois, en une quantité déterminée en fonction de la technique choisie pour la mise en forme. In one embodiment, the quantity of solvent, preferably water, can be added in several times, in a quantity determined according to the technique chosen for shaping.
Dans un mode de réalisation, lorsque la poudre d’adsorbant du lithium est apportée par une suspension et/ou une pâte, le solvant, de préférence l’eau, est apporté, au moins en partie, par ladite suspension et/ou ladite pâte. In one embodiment, when the lithium adsorbent powder is provided by a suspension and/or a paste, the solvent, preferably water, is provided, at least in part, by said suspension and/or said paste .
Le mélange des différents constituants peut être effectué suivant toute technique connue de l’homme du métier, par exemple en mélangeur, de préférence en mélangeur à haute intensité ou en mélangeur à bras en Z, en turbulat, en broyeur à jarre avec des billes, de préférence des billes en alumine. De préférence, le mélange est effectué dans un mélangeur à haute intensité ou dans un mélangeur à bras en Z. The mixing of the various constituents can be carried out according to any technique known to those skilled in the art, for example in a mixer, preferably in a high-intensity mixer or in a Z-arm mixer, in a turbulat, in a jar mill with balls, preferably alumina balls. Preferably, the mixing is carried out in a high intensity mixer or in a Z-arm mixer.
Le temps total de mélange est de préférence supérieur à 5 minutes, et de préférence inférieur à 30 minutes, de préférence inférieur à 20 minutes. The total mixing time is preferably greater than 5 minutes, and preferably less than 30 minutes, preferably less than 20 minutes.
L’étape b) peut être précédée d’une étape d’élimination d’au moins une partie du solvant, de manière à adapter la quantité de solvant, de préférence l’eau, à la technique de mise en forme
envisagée à l’étape b). Toutes les techniques connues pour éliminer au moins en partie un solvant, de préférence l’eau peuvent être utilisées, de préférence un séchage, de préférence sous air, à la pression atmosphérique. De préférence, la température maximale atteinte lors dudit séchage est supérieure à 20°C, et de préférence inférieure à 100°C, de préférence inférieure à 80°C, de préférence inférieure à 60°C. Step b) can be preceded by a step of removing at least part of the solvent, so as to adapt the amount of solvent, preferably water, to the shaping technique. considered in step b). All the known techniques for at least partially eliminating a solvent, preferably water, can be used, preferably drying, preferably in air, at atmospheric pressure. 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.
De préférence encore, le cycle de séchage présente un palier à ladite température maximale atteinte. Le temps de maintien au palier est de préférence supérieur à 1 heure, et de préférence inférieur à 20 heures, de préférence inférieure à 15 heures. Preferably again, the drying cycle has a plateau at said maximum temperature reached. The holding time at the level is preferably greater than 1 hour, and preferably less than 20 hours, preferably less than 15 hours.
A l’étape b), la charge de départ est mise en forme de manière à obtenir une préforme.In step b), the starting charge is shaped so as to obtain a preform.
La mise en forme peut être 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). The shaping can be carried out using any technique known to those skilled in the art, for example extrusion, granulation, pressing, casting, atomization, serigraphy (or "screen printing" in English), tape casting (or "tape casting" in English), or drop by drop gelation (or "drip casting" in English).
Les préformes obtenues peuvent se présenter sous la forme de cylindres, de polylobés, d’anneaux, ou de sphères. The preforms obtained can be in the form of cylinders, polylobes, rings, or spheres.
A l’étape c), la préforme est mise en contact avec une solution comprenant un agent de gélification choisi parmi les cations divalents, les cations trivalents et leurs mélanges, apte à faire gélifier le polysaccharide, de manière à obtenir le produit à base d’un adsorbant du lithium. In step c), the preform is brought into contact with a solution comprising a gelling agent chosen from divalent cations, trivalent cations and mixtures thereof, capable of causing the polysaccharide to gel, so as to obtain the product based on a lithium adsorbent.
La solution comprenant un agent de gélification choisi parmi les cations divalents, les cations trivalents et leurs mélanges, apte à faire gélifier le polysaccharide est bien connue de l’homme du métier. The solution comprising a gelling agent chosen from divalent cations, trivalent cations and mixtures thereof, capable of causing the polysaccharide to gel, is well known to those skilled in the art.
L’agent de gélification est de préférence choisi parmi les cations alcalino-terreux, de préférence choisi parmi les cations de Ca, Sr, Ba et leurs mélanges. De préférence l’agent de gélification est un cation de Ca. The gelling agent is preferably chosen from alkaline-earth cations, preferably chosen from Ca, Sr, Ba cations and mixtures thereof. Preferably the gelling agent is a Ca cation.
La solution contenant l’agent de gélification choisi parmi les cations divalents, les cations trivalents et leurs mélanges est de préférence choisie parmi une solution comportant un sel de cation divalent, une solution comportant un sel de cation trivalent, ou la source de lithium à partir de laquelle le lithium est extrait, de préférence la saumure, en particulier lorsqu’elle contient un tel cation. The solution containing the gelling agent chosen from divalent cations, trivalent cations and mixtures thereof is preferably chosen from a solution comprising a divalent cation salt, a solution comprising a trivalent cation salt, or the source of lithium from from which the lithium is extracted, preferably brine, in particular when it contains such a cation.
De préférence la solution comportant un sel de cation divalent ou un sel de cation trivalent, est choisie parmi une solution d’iodure dudit cation et/ou une solution de chlorure dudit cation. De préférence la solution de gélification est une solution comportant un iodure de cation alcalino-terreux et/ou un chlorure de cation alcalino-terreux. De préférence encore, la solution de gélification est une solution comportant un chlorure de cation alcalino-terreux, de préférence une solution comportant du chlorure de calcium.
Dans un mode de réalisation préféré, la solution de gélification est la source de lithium à partir de laquelle le lithium est extrait, de préférence la saumure dont le lithium doit être capté, notamment lorsque celle-ci comprend un cation divalent et/ou trivalent. 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 gelation 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 source of lithium from which the lithium is extracted, preferably the brine from which the lithium must be collected, in particular when the latter comprises a divalent and/or trivalent cation.
Dans un autre mode de réalisation possible, la solution gélifiante est une solution de chlorure de calcium, dont la concentration en chlorure de calcium est de préférence supérieure à 1 mol/l, de préférence supérieure à 2 mol/l de solution. 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.
La mise en contact 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. The bringing into contact can for example be carried out by immersing the preform in a bath of gelling solution or by spraying the preform with the gelling solution.
Dans un mode de réalisation, l’étape b) et l’étape c) sont confondues, notamment lorsque la préforme est mise en œuvre par gélification en goutte à goutte. In one embodiment, step b) and step c) are combined, in particular when the preform is implemented by dropwise gelling.
A l’issue de l’étape c), on obtient un produit à base d’adsorbant du lithium. Ledit produit à base d’adsorbant du lithium peut se présenter sous la forme de cylindres, de polylobés, d’anneaux, ou de sphères. At the end of step c), a product based on lithium adsorbent is obtained. Said lithium adsorbent-based product may be in the form of cylinders, polylobes, rings, or spheres.
De préférence, la préforme est conformée de manière que la plus grande dimension du produit à base d’adsorbant du lithium soit 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 que la plus petite dimension du produit à base d’adsorbant du lithium dans un plan perpendiculaire à la direction de la plus grande dimension soit supérieure à 1 pm, voire supérieure à 10 pm (micromètres). Preferably, the preform is shaped so that the largest dimension of the product based on lithium adsorbent is less than 100 mm, preferably less than 80 mm, preferably less than 50 mm, preferably less than 30 mm, or even less than 10 mm and/or that the smallest dimension of the lithium adsorbent-based product in a plane perpendicular to the direction of the largest dimension is greater than 1 μm, or even greater than 10 μm (micrometers).
A l’étape d), optionnelle, le produit à base d’un adsorbant du lithium est séché. In step d), optional, the product based on a lithium adsorbent is dried.
De préférence, la température maximale atteinte lors dudit séchage est supérieure à 20°C, et de préférence inférieure à 140°C, de préférence inférieure à 100°C, de préférence inférieure à 80°C. Preferably, the maximum temperature reached during said drying is greater than 20°C, and preferably less than 140°C, preferably less than 100°C, preferably less than 80°C.
De préférence encore, le cycle de séchage présente un palier à ladite température maximale atteinte. Le temps de maintien au palier est de préférence supérieur à 1 heure, de préférence supérieur à 2 heures, de préférence supérieur à 5 heures et de préférence inférieur à 20 heures, de préférence inférieur à 15 heures. Le séchage s’effectue de préférence sous air, à la pression atmosphérique. Preferably again, the drying cycle has a plateau at said maximum temperature reached. The holding time at the plateau is preferably greater than 1 hour, preferably greater than 2 hours, preferably greater than 5 hours and preferably less than 20 hours, preferably less than 15 hours. Drying is preferably carried out in air, at atmospheric pressure.
A l’issue de l’étape d), on obtient un produit sec à base d’adsorbant du lithium. At the end of step d), a dry product based on lithium adsorbent is obtained.
L’invention concerne également un produit comprenant des particules liées par un liant, ledit liant comprenant, de préférence étant constitué par, un polysaccharide gélifié comprenant un groupement établissant une liaison ionique avec un cation divalent, un cation trivalent et leurs mélanges, de préférence un alginate gélifié, lesdites particules étant essentiellement des particules d’un adsorbant du lithium.
Un tel produit est notamment issu d’un procédé tel que précédemment décrit. The invention also relates to a product comprising particles bound by a binder, said binder comprising, preferably consisting of, a gelled polysaccharide comprising a group establishing an ionic bond with a divalent cation, a trivalent cation and mixtures thereof, preferably a gelled alginate, said particles being essentially particles of a lithium adsorbent. Such a product is in particular derived from a process as described above.
De préférence, le liant du produit comprenant un adsorbant du lithium selon l’invention comprend, de préférence est constitué essentiellement par, un polysaccharide gélifié comprenant un groupement établissant une liaison ionique avec un cation divalent, un cation trivalent et leurs mélanges, de préférence avec un cation alcalino-terreux, de préférence choisi parmi les cations de Ca, Sr, Ba et leurs mélanges, de préférence un cation de Ca. Preferably, the binder of the product comprising a lithium adsorbent according to the invention comprises, preferably consists essentially of, a gelled polysaccharide comprising a group establishing an ionic bond with a divalent cation, a trivalent cation and their mixtures, preferably with an alkaline-earth cation, preferably chosen from Ca, Sr, Ba cations and mixtures thereof, preferably a Ca cation.
De préférence ledit polysaccharide gélifié un alginate gélifié ou une pectine gélifiée, de préférence un alginate gélifié. Preferably said gelled polysaccharide a gelled alginate or a gelled pectin, preferably a gelled alginate.
Dans le produit (ou objet macroscopique) comprenant un adsorbant du lithium selon l’invention, le polysaccharide gélifié, notamment l’alginate gélifié, contenu dans le liant peut être par exemple mis en évidence par chromatographie d’exclusion stérique. In the product (or macroscopic object) comprising a lithium adsorbent according to the invention, the gelled polysaccharide, in particular the gelled alginate, contained in the binder can for example be demonstrated by steric exclusion chromatography.
De préférence, le produit comprenant un adsorbant du lithium selon l’invention est constitué essentiellement, après séchage à 100°C pendant 12 heures, par des particules d’un adsorbant du lithium, liées par un liant consistant essentiellement en un alginate gélifié.Preferably, the product comprising a lithium adsorbent according to the invention consists essentially, after drying at 100° C. for 12 hours, of particles of a lithium adsorbent, bound by a binder consisting essentially of a gelled alginate.
De préférence, les particules d’un adsorbant du lithium du produit comprenant un adsorbant du lithium selon l’invention sont des particules d’un adsorbant du lithium choisies parmi : une bayérite lithiée, de préférence un matériau de formule (LiCI)x.2AI(OH)3, nhhO, avec x compris entre 0,4 et 1 et n compris entre 0,01 et 10 ; un aluminate de lithium, optionnellement hydraté et/ou dopé, ledit aluminate de lithium répondant de préférence à la formule UAIO2, optionnellement hydraté et/ou dopé ; un spinelle de manganèse et de lithium, optionnellement dopé, ledit spinelle de manganèse et de lithium étant de préférence choisi parmi un spinelle de manganèse et de lithium de formule Li(i+X)Mn(2-y)M’y04 avec -0,20 < x < 0,4 et 0 £ y £ 1 , l’élément M’ étant choisi parmi l’aluminium, le cobalt, le nickel, le chrome, le fer, le magnésium, le titane, le vanadium, le cuivre, le zinc, le gallium, le calcium, le niobium, l’yttrium, le baryum, le silicium, le bore, le zirconium, le lithium et leurs mélanges, l’électroneutralité dudit manganate de lithium étant assurée par la teneur en oxygène ; un oxyde de fer lithié, optionnellement hydraté et/ou dopé, ledit oxyde de fer lithié répondant de préférence à la formule LiFe02, optionnellement hydraté et/ou dopé ;Preferably, the particles of a lithium adsorbent of the product comprising a lithium adsorbent according to the invention are particles of a lithium adsorbent chosen from: a lithiated bayerite, preferably a material of formula (LiCI) x .2AI (OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10; a lithium aluminate, optionally hydrated and/or doped, said lithium aluminate preferably corresponding to the formula UAIO2, optionally hydrated and/or doped; a manganese and lithium spinel, optionally doped, said manganese and lithium spinel being preferably chosen from a manganese and lithium spinel of formula Li (i+X) Mn (2 -y ) M'y0 4 with - 0.20 < x < 0.4 and 0 £ y £ 1 , the element M' being chosen from aluminum, cobalt, nickel, chromium, iron, magnesium, titanium, vanadium, copper, zinc, gallium, calcium, niobium, yttrium, barium, silicon, boron, zirconium, lithium and mixtures thereof, the electroneutrality of said lithium manganate being ensured by the oxygen content ; a lithiated iron oxide, optionally hydrated and/or doped, said lithiated iron oxide preferably having the formula LiFe0 2 , optionally hydrated and/or doped;
Un oxyde de magnésium lithié, optionnellement hydraté et/ou dopé, ledit oxyde de magnésium lithié répondant de préférence à la formule LiMg02, optionnellement hydraté et/ou dopé ; A lithiated magnesium oxide, optionally hydrated and/or doped, said lithiated magnesium oxide preferably having the formula LiMg0 2 , optionally hydrated and/or doped;
Un spinelle de cobalt et de lithium, optionnellement hydraté et/ou dopé, ledit spinelle de cobalt et de lithium répondant de préférence à la formule UC02O4, optionnellement hydraté et/ou dopé ;
Un titanate de lithium, optionnellement hydraté et/ou dopé, ledit titanate de lithium étant de préférence choisi parmi un titanate de lithium répondant à la formule LiTi02, LhTiOs, LhThO?, LUTisO^, et leurs mélanges, optionnellement hydraté(s) et/ou dopé(s), de préférence LhTiCb, optionnellement hydraté et/ou dopé ; hhTiCb, optionnellement hydraté et/ou dopé ; A cobalt and lithium spinel, optionally hydrated and/or doped, said cobalt and lithium spinel preferably having the formula UC0 2 O 4 , optionally hydrated and/or doped; A lithium titanate, optionally hydrated and/or doped, said lithium titanate being preferably chosen from a lithium titanate corresponding to the formula LiTi0 2 , LhTiOs, LhThO 2 , LUTisO 3 , and mixtures thereof, optionally hydrated and / or doped (s), preferably LhTiCb, optionally hydrated and / or doped; hhTiCb, optionally hydrated and/or doped;
H2T13O7, optionnellement hydraté et/ou dopé ; H2T13O7, optionally hydrated and/or doped;
H4T15O12, optionnellement hydraté et/ou dopé ; H4T15O12, optionally hydrated and/or doped;
Et leurs mélanges. And their mixtures.
De préférence l’adsorbant du lithium est choisi parmi : une bayérite lithiée, de préférence un matériau de formule (LiCI)x.2AI(OH)3, nhhO, avec x compris entre 0,4 et 1 et n compris entre 0,01 et 10 ; un spinelle de manganèse et de lithium, optionnellement dopé ; un titanate de lithium, optionnellement hydraté et/ou dopé, ledit titanate de lithium étant de préférence choisi parmi un titanate de lithium répondant à la formule LiTi02, Li2Ti03, Li2Ti307, Li4Ti 0i2, et leurs mélanges, optionnellement hydraté(s) et/ou dopé(s), de préférence Li2Ti03, optionnellement hydraté et/ou dopé ; Preferably, the lithium adsorbent is chosen from: a lithiated bayerite, preferably a material of formula (LiCI) x .2Al(OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10; a manganese and lithium spinel, optionally doped; a lithium titanate, optionally hydrated and/or doped, said lithium titanate preferably being chosen from a lithium titanate corresponding to the formula LiTi0 2 , Li 2 Ti03 , Li 2 Ti 3 07 , Li 4 Ti 0i 2 , and their mixtures, optionally hydrated and/or doped, preferably Li 2 TiO3, optionally hydrated and/or doped ;
H2T1O3, optionnellement hydraté et/ou dopé ; et leurs mélanges. H2T1O3, optionally hydrated and/or spiked; and their mixtures.
De préférence, l’adsorbant du lithium est une bayérite lithiée, de préférence un matériau de formule (LiCI)x.2AI(OH)3, nhhO, avec x compris entre 0,4 et 1 et n compris entre 0,01 et 10.Preferably, the lithium adsorbent is a lithiated bayerite, preferably a material of formula (LiCI) x .2AI(OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10 .
Dans un mode de réalisation, lorsque le produit comprenant un adsorbant du lithium selon l’invention comporte un mélange d’au moins deux populations de particules d’un adsorbant du lithium, au moins deux desdites populations de particules d’un adsorbant du lithium sont en un adsorbant du lithium différent. In one embodiment, when the product comprising a lithium adsorbent according to the invention comprises a mixture of at least two populations of particles of a lithium adsorbent, at least two of said populations of particles of a lithium adsorbent are into a different lithium adsorbent.
De préférence, dans le produit comprenant un adsorbant du lithium selon l’invention, le rapport massique de la quantité du polysaccharide gélifié sur la quantité totale dudit polysaccharide gélifié et des particules d’un adsorbant du lithium est supérieur ou égal à 0,1%, de préférence supérieur ou égal à 0,2%, de préférence supérieur ou égal à 0,3% et de préférence inférieur ou égal à 10%, de préférence encore inférieur ou égal à 5%, de préférence inférieur ou égal à 4%, de préférence inférieur ou égal à 3%, de préférence inférieur ou égal à 2%, de préférence inférieur ou égal à 1%. Avantageusement, la quantité de particules d’adsorbant du lithium dans le produit est plus importante pour un même volume. Preferably, in the product comprising a lithium adsorbent according to the invention, the mass ratio of the quantity of gelled polysaccharide to the total quantity of said gelled polysaccharide and of the particles of a lithium adsorbent is greater than or equal to 0.1% , preferably greater than or equal to 0.2%, preferably greater than or equal to 0.3% and preferably less than or equal to 10%, more preferably less than or equal to 5%, preferably less than or equal to 4% , preferably less than or equal to 3%, preferably less than or equal to 2%, preferably less than or equal to 1%. Advantageously, the quantity of lithium adsorbent particles in the product is greater for the same volume.
De préférence, dans le produit comprenant un adsorbant du lithium selon l’invention, la quantité massique de particules d’un adsorbant du lithium, après séchage à 100°C pendant 12 heures, est supérieure ou égale à 90%, de préférence supérieure à 95%, de préférence supérieure ou égale à 96%, de préférence supérieure ou égale à 97%, de préférence
supérieure ou égale à 98%, et inférieure à 99,9%, de préférence inférieure à 99,8%, de préférence inférieure à 99,7%, sur la base de la masse du produit comprenant un adsorbant du lithium selon l’invention, après séchage à 100°C pendant 12 heures. Preferably, in the product comprising a lithium adsorbent according to the invention, the mass quantity of particles of a lithium adsorbent, after drying at 100° C. for 12 hours, is greater than or equal to 90%, preferably greater than 95%, preferably greater than or equal to 96%, preferably greater than or equal to 97%, preferably greater than or equal to 98%, and less than 99.9%, preferably less than 99.8%, preferably less than 99.7%, based on the mass of the product comprising a lithium adsorbent according to the invention , after drying at 100°C for 12 hours.
Le produit comprenant un adsorbant du lithium selon l’invention peut se présenter sous la forme de cylindres, de polylobés, d’anneaux, ou de sphères. The product comprising a lithium adsorbent according to the invention can be in the form of cylinders, polylobes, rings, or spheres.
De préférence, la plus grande dimension du produit selon l’invention (ou l’objet macroscopique selon l’invention) comprenant un adsorbant du lithium selon l’invention est 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. De préférence encore, la plus petite dimension du produit selon l’invention (ou l’objet macroscopique selon l’invention) comprenant un adsorbant du lithium, dans un plan perpendiculaire à la direction de la plus grande dimension, est supérieure à 1 pm, voire supérieure à 10 pm. Preferably, the largest dimension of the product according to the invention (or the macroscopic object according to the invention) comprising a lithium adsorbent according to the invention is less than 100 mm, preferably less than 80 mm, preferably less than 50 mm, preferably less than 30 mm, or even less than 10 mm. Preferably again, the smallest dimension of the product according to the invention (or the macroscopic object according to the invention) comprising a lithium adsorbent, in a plane perpendicular to the direction of the largest dimension, is greater than 1 μm, or even greater than 10 pm.
L’invention concerne aussi un produit comprenant un adsorbant du lithium obtenu ou susceptible d’être obtenu par le procédé selon l’invention. Ce produit est remarquable de par sa capacité à conserver son intégrité physique lors d’un cyclage répétitif d’adsorption- désorption de lithium. Cette propriété constitue d’ailleurs une signature du procédé selon l’invention. The invention also relates to a product comprising a lithium adsorbent obtained or capable of being obtained by the process according to the invention. This product is remarkable for its ability to retain its physical integrity during repetitive lithium adsorption-desorption cycling. This property moreover constitutes a signature of the method according to the invention.
Exemples Examples
Les exemples non limitatifs suivants sont donnés dans le but d'illustrer l'invention. The following non-limiting examples are given for the purpose of illustrating the invention.
Protocole de mesure Measurement protocol
La teneur en eau d’une pâte est déterminée comme étant la perte de masse, exprimée en pourcentage, après séchage sous air à 200°C pendant 16 heures The water content of a dough is determined as being the loss of mass, expressed as a percentage, after drying in air at 200°C for 16 hours.
La nature des phases cristallisées des pâtes fabriquées dans le cadre des exemples est déterminée par la méthode classique suivante : The nature of the crystallized phases of the pastes manufactured within the framework of the examples is determined by the following conventional method:
Les pâtes des exemples sont préalablement séchées à l’air pendant 170 heures à 25°C.The pastes of the examples are previously air-dried for 170 hours at 25°C.
Les acquisitions sont réalisées au moyen d’un appareil du type X’Pert de la société Panalytical, équipé d’une anode en cuivre, sur un domaine angulaire 2Q compris entre 5° et 80°, avec un pas de 0,017°, et un temps de comptage de 300 s/pas. L’optique avant comporte une fente de divergence fixe de 0,25°, une fente de Soller de 0,02 rad, un masque de 10 mm et une fente anti-diffusion fixe de 0,5°. L’échantillon est en rotation sur lui-même. L’optique arrière comporte une fente anti-diffusion fixe de 0,25°, une fente de Soller de 0,02 rad et un filtre nickel. The acquisitions are carried out using an X'Pert type device from Panalytical, equipped with a copper anode, over an angular range 2Q between 5° and 80°, with a pitch of 0.017°, and a counting time of 300 s/step. The front optic has a fixed 0.25° divergence slit, a 0.02 rad Soller slit, a 10 mm mask and a fixed 0.5° anti-scatter slit. The sample is rotating on itself. The rear optic has a fixed anti-scattering slit of 0.25°, a Soller slit of 0.02 rad and a nickel filter.
Les diagrammes de diffraction sont ensuite analysés qualitativement à l’aide du logiciel EVA et de la base de données ICDD2016.
La fiche de données PDF 00-031-0700 de la base de données ICDD2016 permet d’identifier la phase (UCI).2AI(OH)3, xH20. The diffraction patterns are then qualitatively analyzed using EVA software and the ICDD2016 database. The PDF data sheet 00-031-0700 of the ICDD2016 database is used to identify the phase (UCI).2AI(OH) 3 , xH 2 0.
La phase cristallisée de bayérite lithiée mise en évidence peut présenter un léger décalage angulaire des pics par rapport à ladite fiche de données, conséquence notamment de la quantité de Li inséré dans la structure de la bayérite lithiée. The crystallized phase of lithiated bayerite highlighted may present a slight angular offset of the peaks compared to said data sheet, a consequence in particular of the quantity of Li inserted into the structure of the lithiated bayerite.
La teneur en les éléments autres que H et O, en partie en Li, Cl et Al, est déterminée sur les pâtes séchées à 200°C pendant 16 heures sous air, par spectrométrie à plasma à couplage inductif, en utilisant un appareil 5800 ICP-OES de la marque Agilent. The content of elements other than H and O, partly Li, Cl and Al, is determined on pasta dried at 200°C for 16 hours in air, by inductively coupled plasma spectrometry, using a 5800 ICP device -OES from Agilent.
Protocole de fabrication : Manufacturing protocol:
Les matières premières suivantes ont été utilisées pour les exemples : The following raw materials were used for the examples:
Du trichlorure d’aluminium hexahydraté AICl3,6H20, de pureté supérieure à 99% en masse, commercialisé par la société Merck, pour l’exemple 1, Aluminum trichloride hexahydrate AICl 3.6H 2 0 , of purity greater than 99% by mass, marketed by the company Merck, for example 1,
Une poudre d’hydroxyde de sodium NaOH, de pureté supérieure à 99% en masse, commercialisée par la société Merck, pour l’exemple 1 , A powder of sodium hydroxide NaOH, of purity greater than 99% by mass, marketed by the company Merck, for example 1,
De l’acide oxalique, de pureté supérieure à 99% en masse, commercialisé par la société Merck, pour l’exemple 1, Oxalic acid, of purity greater than 99% by mass, marketed by the company Merck, for example 1,
Une poudre de gibbsite AI(OH)3, présentant une taille médiane égale à 1 ,6 pm, de pureté supérieure à 99,5% en masse et une surface spécifique égale à 5 m2/g, pour l’exemple 2, A powder of gibbsite AI(OH)3, having a median size equal to 1.6 μm, of purity greater than 99.5% by mass and a specific surface area equal to 5 m 2 /g, for Example 2,
De l’hydroxyde de lithium monohydraté (LiOH,H20), de pureté supérieure à 99,5% en masse, pour l’exemple 2, Lithium hydroxide monohydrate (LiOH, H 2 0), of purity greater than 99.5% by mass, for Example 2,
Du chlorure de lithium LiCI, de pureté supérieure à 99,5%% en masse, pour les exemples 1 et 2, Lithium chloride LiCI, of purity greater than 99.5%% by mass, for examples 1 and 2,
De l’acide chlorhydrique HCl, de pureté supérieure à 99% en masse, en solution aqueuse à 16M, pour l’exemple 2, Hydrochloric acid HCl, of purity greater than 99% by mass, in aqueous solution at 16M, for example 2,
Un alginate d’ammonium de pureté supérieur à 99% en masse, pour l’exemple 2. An ammonium alginate with a purity greater than 99% by mass, for Example 2.
Le produit de l’exemple 1 (comparatif) a été obtenu de la manière suivante : The product of Example 1 (comparative) was obtained as follows:
Une précipitation de boehmite est réalisée de la manière suivante. 2500 g de trichlorure d’aluminium hexahydraté (AICl3,6H20) sont ajoutés à 3950 g d’eau déminéralisée, le tout étant maintenu sous agitation dans un réacteur de 30 litres double enveloppe en acier inoxydable. Ensuite, toujours sous agitation, une solution de 1200 g d’hydroxyde de sodium (NaOH) et 3 litres d’eau déminéralisée sont ajoutés progressivement, de manière à ajuster le pH. Le pH atteint en fin de synthèse est égal à 8. La température est maintenue à 20°C pendant toute à durée de l'étape de précipitation de la boehmite. Puis le précipité de boehmite est lavé et filtré à l’aide d’un filtre presse. La teneur en eau du précipité de boehmite à la fin de cette étape est de 85% en masse.
Puis, 2500 g dudit précipité de boehmite sont repulpés dans 1600 g d’eau déminéralisée à température ambiante, puis une solution contenant 170 g de LiCI et 16,7 litres d’eau déminéralisée est ajoutée (ce qui correspond à un rapport molaire Li/AI égal à 0,39), le mélange étant agité et chauffé à 80°C pendant 1 heure. Boehmite precipitation is carried out in the following manner. 2500 g of aluminum trichloride hexahydrate (AICl 3.6H 2 0 ) are added to 3950 g of demineralized water, the whole being kept under stirring in a 30 liter stainless steel jacketed reactor. Then, still with stirring, a solution of 1200 g of sodium hydroxide (NaOH) and 3 liters of demineralized water are added gradually, so as to adjust the pH. The pH reached at the end of the synthesis is equal to 8. The temperature is maintained at 20° C. for the duration of the boehmite precipitation step. Then the boehmite precipitate is washed and filtered using a filter press. The water content of the boehmite precipitate at the end of this step is 85% by mass. Then, 2500 g of said boehmite precipitate are replumped in 1600 g of demineralised water at ambient temperature, then a solution containing 170 g of LiCl and 16.7 liters of demineralised water is added (which corresponds to a Li/ AI equal to 0.39), the mixture being stirred and heated at 80° C. for 1 hour.
Le mélange ainsi obtenu est refroidi à 60°C, puis filtré dans un filtre presse de manière à obtenir une pâte. La pâte ainsi obtenue présente les caractéristiques figurant dans le tableau 1 suivant. The mixture thus obtained is cooled to 60° C., then filtered in a filter press so as to obtain a paste. The paste thus obtained has the characteristics shown in Table 1 below.
[Tableau 1]
[Table 1]
Ladite pâte est ensuite séchée à 50°C sous air jusqu’à présenter une teneur en eau égale à 50%. Puis, 120 g de ladite pâte séchée, encore à une température égale à 50°C sont introduits dans un mélangeur à bras en Z. Puis 2,38 g d’une solution d’acide oxalique à 10 g/l sont ajoutés à ladite pâte sous agitation. Un mélange homogène est obtenu, qui est étalé sur une grille métallique d’épaisseur égale à 1 mm et perforée de trous circulaires de diamètre égal à 1,5 mm, puis raclé à l’aide d’une spatule de chaque côté de la grille de manière à ce que ledit mélange remplisse les trous de ladite grille. La grille est alors dite « chargée ». Une fois que la grille est chargée, elle est placée sous une circulation d’air chaud à 60°C, ce qui permet de « décharger » ladite grille, les objets formés tombant dans un récipient disposé sous la grille. Lesdits objets obtenus se présentent sous la forme de cylindres de longueur moyenne égale à 0,8 mm et de diamètre moyen égal à 1,4 mm. Said paste is then dried at 50°C in air until it has a water content equal to 50%. Then, 120 g of said dried paste, still at a temperature equal to 50° C., are introduced into a Z-arm mixer. Then 2.38 g of a 10 g/l oxalic acid solution are added to said dough under stirring. A homogeneous mixture is obtained, which is spread on a metal grid with a thickness equal to 1 mm and perforated with circular holes with a diameter equal to 1.5 mm, then scraped with a spatula on each side of the grid. so that said mixture fills the holes of said grid. The grid is then said to be “loaded”. 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 equal to 0.8 mm and an average diameter equal to 1.4 mm.
Le produit de l’exemple 2 (selon l’invention) a été obtenu de la manière suivante : The product of Example 2 (according to the invention) was obtained as follows:
500 g d’hydroxyde d’aluminium sont ajoutés à 2000 g d’eau, à une température égale à 25°C, dans un broyeur LabStar commercialisé par la société Netzsch et broyés pendant 75 minutes. A la fin de cette étape, l’hydroxyde d’aluminium en suspension dans l’eau présente une taille médiane égale à 0,55 pm. Puis on ajoute 134,15 g de (LiOH, H2O) de manière que le rapport molaire entre le OH apporté par (LiOH, H2O) et l’AI présent initialement dans le mélange soit
égal à 0,5. L’ensemble est mélangé pendant une durée égale à 5 minutes, la température étant maintenue à 25°C. Puis, on ajoute LiCI, de manière à ce que le rapport molaire entre le Cl apporté par LiCI et GAI présent initialement dans le mélange soit égal à 1, l’ensemble est mélangé pendant une durée égale à 5 minutes, la température étant maintenue à 25°C. Le rapport molaire Li/AI est égal à 1 ,5. 500 g of aluminum hydroxide are added to 2000 g of water, at a temperature equal to 25° C., in a LabStar grinder marketed by the company Netzsch and ground for 75 minutes. At the end of this stage, the aluminum hydroxide in suspension in water has a median size equal to 0.55 μm. Then 134.15 g of (LiOH, H2O) are added so that the molar ratio between the OH provided by (LiOH, H2O) and the Al initially present in the mixture is equal to 0.5. The whole is mixed for a time equal to 5 minutes, the temperature being maintained at 25°C. Then, LiCI is added, so that the molar ratio between the Cl provided by LiCI and GAI present initially in the mixture is equal to 1, the whole is mixed for a time equal to 5 minutes, the temperature being maintained at 25°C. The Li/Al molar ratio is equal to 1.5.
Le mélange est ensuite chauffé à l’aide d’une plaque chauffante, à une température égale à 60°C, le temps pendant lequel ledit mélange est à une température supérieure ou égale à 50°C étant égal à 15 minutes. Puis le mélange est maintenu à une température égale à 60°C pendant une durée égale à 45 minutes. Puis, HCl est ajouté dans le mélange, de manière que le pH du mélange soit abaissé à une valeur égale à 3, la valeur du rapport molaire Cl/Al dans le mélange après ajout de HCl étant égal à 1 ,6, la durée de mélange étant égale à 15 minutes, et la température étant maintenue égale à 60°C. Enfin, le mélange ainsi obtenu est filtré sur Büchner, à température ambiante (inférieure à 50°C), avec des papiers filtres de perméabilité égale à 2 pm de manière à obtenir une pâte. Lors de la filtration, le temps pendant lequel le mélange est à une température supérieure ou égale à 50°C est égal à 5 minutes. The mixture is then heated using a hot plate, to a temperature equal to 60°C, the time during which said mixture is at a temperature greater than or equal to 50°C being equal to 15 minutes. The mixture is then maintained at a temperature equal to 60° C. for a time equal to 45 minutes. Then, HCl is added to the mixture, so that the pH of the mixture is lowered to a value equal to 3, the value of the Cl/Al molar ratio in the mixture after addition of HCl being equal to 1.6, the duration of mixing being equal to 15 minutes, and the temperature being maintained equal to 60°C. Finally, the mixture thus obtained is filtered through a Buchner filter, at ambient temperature (below 50° C.), with filter papers of permeability equal to 2 μm so as to obtain a paste. During filtration, the time during which the mixture is at a temperature greater than or equal to 50° C. is equal to 5 minutes.
La pâte ainsi obtenue présente les caractéristiques figurant dans le tableau 2 suivant. [Tableau 2]
The paste thus obtained has the characteristics shown in Table 2 below. [Table 2]
La pâte obtenue est constituée pour plus de 99% en masse d’eau, de bayérite lithiée, et de LiCI. The paste obtained consists for more than 99% by mass of water, lithiated bayerite, and LiCI.
Puis, une charge de départ conforme à l’objet de la présente invention a été réalisée, formée d’un mélange de ladite pâte obtenue après filtration et d’alginate d’ammonium, la teneur en ledit alginate étant égale à 1% en masse sur la base de la masse de la charge de départ, après un séchage à 200°C pendant 16 heures. Then, a starting charge in accordance with the object of the present invention was produced, formed from a mixture of said paste obtained after filtration and ammonium alginate, the content of said alginate being equal to 1% by mass based on the mass of the starting batch, after drying at 200°C for 16 hours.
Ladite pâte contenant la bayérite lithiée et l’alginate d’ammonium ont été mélangés dans un batteur mélangeur planétaire sous air chaud créé par un décapeur thermique réglé sur une
température égale à 100°C, pendant 120 minutes de manière à obtenir une charge de départ homogène et présentant une teneur en eau compatible avec la technique de mise en forme. La charge de départ a ensuite été étalée sur une grille métallique d’épaisseur égale à 1 mm et perforée de trous circulaires de diamètre égal à 1,5 mm, puis raclée à l’aide d’une spatule de chaque côté de la grille de manière à ce que ladite charge de départ remplisse les trous de ladite grille. La grille est alors dite « chargée ». Une fois que la grille est chargée, elle est placée sous une circulation d’air chaud à 60°C, ce qui permet de « décharger » ladite grille, les objets formés tombant dans un récipient disposé sous la grille. Lesdits objets obtenus se présentent sous la forme de cylindres de longueur moyenne égale à 0,8 mm et de diamètre moyen égal à 1,4 mm. Said paste containing lithiated bayerite and ammonium alginate was mixed in a planetary mixer under hot air created by a heat gun set on a temperature equal to 100° C., for 120 minutes so as to obtain a homogeneous starting charge and having a water content compatible with the shaping technique. The starting charge was then spread on a metal grid of thickness equal to 1 mm and perforated with circular holes of diameter equal to 1.5 mm, then scraped using a spatula on each side of the grid of so that said starting charge fills the holes of said grid. The grid is then said to be “loaded”. 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 equal to 0.8 mm and an average diameter equal to 1.4 mm.
La résistance aux cyclages répétitifs d’adsorption-désorption de lithium des objets des exemples 1 et 2 a ensuite été déterminée selon le protocole suivant. The resistance to repetitive lithium adsorption-desorption cycling of the objects of examples 1 and 2 was then determined according to the following protocol.
Pour chaque exemple, 5 g de produit sont introduits dans un bêcher, puis 20 ml d’une solution aqueuse de chlorure de lithium de concentration égale à 0,02 mol/l sont versés dans ledit bêcher. Les produits de l’exemple sont laissés 3 heures au contact de ladite solution aqueuse de chlorure de lithium. Cette mise en contact correspond à une étape de désorption du lithium. Puis les produits sont séparés de ladite solution aqueuse de chlorure de lithium, après avoir été brièvement mis en agitation, ce qui permet de constater la présence éventuelle d’un voile blanchâtre. Après séparation, lesdits produits sont ensuite mis en contact pendant 3 heures avec 20 ml d’une saumure présentant une concentration en lithium égale à 0,06 mol/l. Cette mise en contact correspond à une étape d’adsorption du lithium. Puis, les produits sont séparés de ladite saumure, après avoir été brièvement mis en agitation, ce qui permet de constater la présence éventuelle d’un voile blanchâtre. L’étape de désorption suivie de l’étape d’adsorption correspond à une simulation d’un cycle d’adsorption-désorption de lithium.For each example, 5 g of product are introduced into a beaker, then 20 ml of an aqueous solution of lithium chloride with a concentration equal to 0.02 mol/l are poured into said beaker. The products of the example are left for 3 hours in contact with said aqueous solution of lithium chloride. This contacting corresponds to a lithium desorption step. Then the products are separated from the said aqueous solution of lithium chloride, after having been briefly stirred, which makes it possible to observe the possible presence of a whitish veil. After separation, said products are then brought into contact for 3 hours with 20 ml of a brine having a lithium concentration equal to 0.06 mol/l. This contacting corresponds to a lithium adsorption step. Then, the products are separated from the said brine, after having been briefly stirred, which makes it possible to note the possible presence of a whitish veil. The desorption step followed by the adsorption step corresponds to a simulation of a lithium adsorption-desorption cycle.
Le produit subit au total 10 cycles d’adsorption-désorption de lithium. The product undergoes a total of 10 lithium adsorption-desorption cycles.
Il est vérifié lors du premier cycle que les produits de l’exemple 1 et de l’exemple 2 libèrent du lithium lors de l’étape de désorption et adsorbent du lithium lors de l’étape d’adsorption. It is verified during the first cycle that the products of example 1 and example 2 release lithium during the desorption step and adsorb lithium during the adsorption step.
Pour le produit de l’exemple 1 , comparatif, on constate lors de chaque cycle, l’apparition d’un voile blanchâtre qui trouble la solution aqueuse de chlorure de lithium et la saumure en fin de l’étape de désorption et en fin de l’étape d’adsorption, respectivement. Ce voile est le signe de la dégradation du produit de l’exemple 1 lors de chaque cycle d’adsorption-désorption de lithium. For the product of example 1, comparative, one notes during each cycle, the appearance of a whitish veil which clouds the aqueous solution of lithium chloride and the brine at the end of the desorption stage and at the end of the adsorption step, respectively. This haze is the sign of the degradation of the product of Example 1 during each lithium adsorption-desorption cycle.
Au contraire du produit de l’exemple 1 , le produit de l’exemple 2, selon l’invention, ne génère pas ce phénomène, même au bout de 10 cycles d’adsorption-désorption de lithium : la solution aqueuse de chlorure de lithium et la saumure restent parfaitement claires en fin de l’étape de désorption et en fin de l’étape d’adsorption, respectivement. Le produit de l’exemple 2 selon
l’invention présente donc une meilleure résistance aux cyclages répétitifs d’adsorption- désorption de lithium que le produit de l’exemple 1, comparatif. Unlike the product of Example 1, the product of Example 2, according to the invention, does not generate this phenomenon, even after 10 adsorption-desorption cycles of lithium: the aqueous solution of lithium chloride and the brine remain perfectly clear at the end of the desorption stage and at the end of the adsorption stage, respectively. The product of Example 2 according to the invention therefore has better resistance to repetitive cycling of adsorption-desorption of lithium than the product of example 1, comparative.
Bien entendu, l'invention n'est pas limitée aux modes de réalisation décrits, fournis seulement à des fins d'illustration.
Of course, the invention is not limited to the embodiments described, provided for illustration purposes only.
Claims
1. Produit pour l’extraction du lithium présent dans une saumure, ledit produit comprenant des particules liées par un liant, ledit liant comprenant un polysaccharide gélifié comprenant un groupement établissant une liaison ionique avec un cation divalent, un cation trivalent et leurs mélanges, et de préférence étant constitué par ledit polysaccharide gélifié, lesdites particules étant des particules d’un adsorbant du lithium. 1. Product for the extraction of lithium present in a brine, said product comprising particles bound by a binder, said binder comprising a gelled polysaccharide comprising a group establishing an ionic bond with a divalent cation, a trivalent cation and mixtures thereof, and preferably consisting of said gelled polysaccharide, said particles being particles of a lithium adsorbent.
2. Produit selon la revendication 1, dans lequel le polysaccharide gélifié comprend un groupement établissant une liaison ionique avec un cation alcalino-terreux. 2. Product according to claim 1, in which the gelled polysaccharide comprises a group establishing an ionic bond with an alkaline-earth cation.
3. Produit selon la revendication précédente, dans lequel le polysaccharide gélifié comprend un groupement établissant une liaison ionique avec les cations de Ca, Sr, Ba et leurs mélanges, de préférence avec un cation de Ca. 3. Product according to the preceding claim, in which the gelled polysaccharide comprises a group establishing an ionic bond with the cations of Ca, Sr, Ba and their mixtures, preferably with a cation of Ca.
4. Produit selon l’une des revendications 2 ou 3, dans lequel ledit groupement est choisi parmi les groupements carboxylates ou les groupements sulfonates. 4. Product according to one of Claims 2 or 3, in which the said group is chosen from carboxylate groups or sulphonate groups.
5. Produit selon l’une des revendications précédentes, dans lequel le polysaccharide gélifié est un alginate gélifié sous l’action d’un cation divalent, d’un cation trivalent et leurs mélanges. 5. Product according to one of the preceding claims, in which the gelled polysaccharide is an alginate gelled under the action of a divalent cation, a trivalent cation and mixtures thereof.
6. Produit selon l’une des revendications 1 à 4, dans lequel le polysaccharide gélifié est une pectine gélifiée sous l’action d’un cation divalent, d’un cation trivalent et leurs mélanges. 6. Product according to one of claims 1 to 4, in which the gelled polysaccharide is a pectin gelled under the action of a divalent cation, a trivalent cation and mixtures thereof.
7. Produit selon l’une des revendications précédentes, dans lequel l’adsorbant du lithium est choisi parmi : 7. Product according to one of the preceding claims, in which the lithium adsorbent is chosen from:
- une bayérite lithiée, de préférence un matériau de formule (LiCI)x.2AI(OH)3, nH20, avec x compris entre 0,4 et 1 et n compris entre 0,01 et 10 ; - a lithiated bayerite, preferably a material of formula (LiCI) x .2AI(OH) 3 , nH 2 0, with x between 0.4 and 1 and n between 0.01 and 10;
- un aluminate de lithium, optionnellement hydraté et/ou dopé, ledit aluminate de lithium répondant de préférence à la formule UAIO2, optionnellement hydraté et/ou dopé ;- a lithium aluminate, optionally hydrated and/or doped, said lithium aluminate preferably corresponding to the formula UAIO2, optionally hydrated and/or doped;
- un spinelle de manganèse et de lithium, optionnellement dopé, ledit spinelle de manganèse et de lithium étant de préférence choisi parmi un spinelle de manganèse et de lithium de formule Li(i+X)Mn(2-y)M’y04 avec -0,20 < x < 0,4 et 0 < y < 1, l’élément M’ étant choisi parmi l’aluminium, le cobalt, le nickel, le chrome, le fer, le magnésium, le titane, le vanadium, le cuivre, le zinc, le gallium, le calcium, le niobium, l’yttrium, le baryum, le silicium, le bore, le zirconium, le lithium et leurs mélanges, l’électroneutralité dudit manganate de lithium étant assurée par la teneur en oxygène ;- a manganese and lithium spinel, optionally doped, said manganese and lithium spinel being preferably chosen from a manganese and lithium spinel of formula Li (i+X) Mn (2 -y ) M'y0 4 with -0.20 <x <0.4 and 0 <y <1, the element M' being chosen from aluminum, cobalt, nickel, chromium, iron, magnesium, titanium, vanadium, copper, zinc, gallium, calcium, niobium, yttrium, barium, silicon, boron, zirconium, lithium and mixtures thereof, the electroneutrality of said lithium manganate being ensured by the content of oxygen;
- un oxyde de fer lithié, optionnellement hydraté et/ou dopé, ledit oxyde de fer lithié répondant de préférence à la formule LiFe02, optionnellement hydraté et/ou dopé ;- A lithiated iron oxide, optionally hydrated and/or doped, said lithiated iron oxide preferably having the formula LiFe0 2 , optionally hydrated and/or doped;
- Un oxyde de magnésium lithié, optionnellement hydraté et/ou dopé, ledit oxyde de magnésium lithié répondant de préférence à la formule LiMg02, optionnellement hydraté et/ou dopé ;
- Un spinelle de cobalt et de lithium, optionnellement hydraté et/ou dopé, ledit spinelle de cobalt et de lithium répondant de préférence à la formule UC02O4, optionnellement hydraté et/ou dopé ; - A lithiated magnesium oxide, optionally hydrated and/or doped, said lithiated magnesium oxide preferably having the formula LiMg0 2 , optionally hydrated and/or doped; - A cobalt and lithium spinel, optionally hydrated and/or doped, said cobalt and lithium spinel preferably having the formula UC0 2 O 4 , optionally hydrated and/or doped;
- Un titanate de lithium, optionnellement hydraté et/ou dopé, ledit titanate de lithium étant de préférence choisi parmi un titanate de lithium répondant à la formule LiTi02, LhTiOs, LÎ2TÎ307, LÎ4TÎ50i2, et leurs mélanges, optionnellement hydraté(s) et/ou dopé(s), de préférence LhTiCb, optionnellement hydraté et/ou dopé ; - A lithium titanate, optionally hydrated and/or doped, said lithium titanate being preferably chosen from a lithium titanate corresponding to the formula LiTi0 2 , LhTiOs, LÎ2TÎ307, LÎ4TÎ50i2, and mixtures thereof, optionally hydrated and/or or doped(s), preferably LhTiCb, optionally hydrated and/or doped;
- H2T1O3, optionnellement hydraté et/ou dopé ; - H2T1O3, optionally hydrated and/or doped;
- H2T13O7, optionnellement hydraté et/ou dopé ; - H2T13O7, optionally hydrated and/or doped;
- H4T15O12, optionnellement hydraté et/ou dopé ; - H4T15O12, optionally hydrated and/or doped;
- et leurs mélanges. - and mixtures thereof.
8. Produit selon la revendication précédente, dans lequel l’adsorbant du lithium est choisi parmi : 8. Product according to the preceding claim, in which the lithium adsorbent is chosen from:
- une bayérite lithiée, de préférence un matériau de formule (LiCI)x.2AI(OH)3, nhhO, avec x compris entre 0,4 et 1 et n compris entre 0,01 et 10 ; - a lithiated bayerite, preferably a material of formula (LiCI) x .2AI(OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10;
- un spinelle de manganèse et de lithium, optionnellement dopé ; - a manganese and lithium spinel, optionally doped;
- un titanate de lithium, optionnellement hydraté et/ou dopé, ledit titanate de lithium étant de préférence choisi parmi un titanate de lithium répondant à la formule LiTiC>2, Li2TiC>3, Li2Ti307, Li4Ti 0i2, et leurs mélanges, optionnellement hydraté(s) et/ou dopé(s), de préférence Li2TiC>3, optionnellement hydraté et/ou dopé; - a lithium titanate, optionally hydrated and/or doped, said lithium titanate preferably being chosen from a lithium titanate corresponding to the formula LiTiC>2, Li 2 TiC> 3 , Li 2 Ti 3 07, Li 4 Ti 0i 2 , and mixtures thereof, optionally hydrated and/or doped, preferably Li 2 TiC>3, optionally hydrated and/or doped ;
- H2T1O3, optionnellement hydraté et/ou dopé ; - H2T1O3, optionally hydrated and/or doped;
- et leurs mélanges. - and mixtures thereof.
9. Produit selon la revendication précédente, dans lequel l’adsorbant du lithium est une bayérite lithiée, de préférence un matériau de formule (LiCI)x.2AI(OH)3, nhhO, avec x compris entre 0,4 et 1 et n compris entre 0,01 et 10. 9. Product according to the preceding claim, in which the lithium adsorbent is a lithiated bayerite, preferably a material of formula (LiCI) x .2AI (OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10.
10. Produit selon l’une des revendications précédentes, dans lequel la proportion massique de particules de l’adsorbant du lithium, après séchage à 100°C pendant 12 heures, est supérieure ou égale à 95% et inférieure à 99,9% de la masse totale dudit produit. 10. Product according to one of the preceding claims, in which the mass proportion of particles of the lithium adsorbent, after drying at 100° C. for 12 hours, is greater than or equal to 95% and less than 99.9% of the total mass of said product.
11. Produit selon l’une des revendications précédentes, se présentant sous la forme de cylindres, de polylobés, d’anneaux, ou de sphères, de préférence, dont plus grande dimension est inférieure à 100 mm, et la plus petite dimension, dans un plan perpendiculaire à la direction de la plus grande dimension, est supérieure à 1 pm. 11. Product according to one of the preceding claims, in the form of cylinders, polylobes, rings, or spheres, preferably, the largest dimension of which is less than 100 mm, and the smallest dimension, in a plane perpendicular to the direction of the largest dimension, is greater than 1 µm.
12. Procédé de fabrication d’un produit comprenant un adsorbant du lithium, en particulier d’un produit selon l’une des revendications 1 à 11 comprenant au moins les étapes suivantes : a) mélange de matières premières pour former une charge de départ, ladite charge de départ comportant une poudre d’un adsorbant du lithium, et un polysaccharide
gélifiable sous l’action d’un agent de gélification, le rapport massique de la quantité dudit polysaccharide sur la quantité totale dudit polysaccharide et de la poudre d’un adsorbant du lithium étant de préférence supérieur ou égal à 0,1% et de préférence inférieur ou égal à 10%, de préférence encore inférieure ou égal à 5%, b) mise en forme de ladite charge de départ, de manière à obtenir une préforme, c) mise en contact de ladite préforme avec ledit agent de gélification, pour la gélification dudit polysaccharide, de manière à obtenir ledit produit comprenant un adsorbant du lithium, d) optionnellement, séchage du produit comprenant un adsorbant du lithium. 12. A method of manufacturing a product comprising a lithium adsorbent, in particular a product according to one of claims 1 to 11 comprising at least the following steps: a) mixing raw materials to form a starting charge, said starting charge comprising a powder of a lithium adsorbent, and a polysaccharide gelable under the action of a gelling agent, the mass ratio of the quantity of said polysaccharide to the total quantity of said polysaccharide and of the powder of a lithium adsorbent preferably being greater than or equal to 0.1% and preferably less than or equal to 10%, more preferably still less than or equal to 5%, b) shaping said starting charge, so as to obtain a preform, c) bringing said preform into contact with said gelling agent, for gelation of said polysaccharide, so as to obtain said product comprising a lithium adsorbent, d) optionally, drying of the product comprising a lithium adsorbent.
13. Procédé de fabrication selon la revendication précédente, dans lequel l’adsorbant du lithium est une bayérite lithiée, de préférence un matériau de formule (LiCI)x.2AI(OH)3, nhhO, avec x compris entre 0,4 et 1 et n compris entre 0,01 et 10. 13. Manufacturing process according to the preceding claim, in which the lithium adsorbent is a lithiated bayerite, preferably a material of formula (LiCI) x .2AI (OH) 3 , nhhO, with x between 0.4 and 1 and n between 0.01 and 10.
14. Procédé de fabrication selon l’une des deux revendications précédentes, dans lequel le polysaccharide est un alginate ou une pectine, de préférence un alginate. 14. Manufacturing process according to one of the two preceding claims, in which the polysaccharide is an alginate or a pectin, preferably an alginate.
15. Procédé de fabrication selon l’une des trois revendications précédentes, dans lequel l’agent gélifiant est choisi parmi Ca, Sr, Ba et leurs mélanges, de préférence Ca. 15. Manufacturing process according to one of the three preceding claims, in which the gelling agent is chosen from Ca, Sr, Ba and their mixtures, preferably Ca.
16. Dispositif de captation du lithium, en particulier une colonne d’extraction, comportant un produit selon l’une des revendications 1 à 11 ou un produit obtenu ou susceptible d’être obtenu par le procédé selon l’une des revendications 12 à 15.
16. Device for capturing lithium, in particular an extraction column, comprising a product according to one of claims 1 to 11 or a product obtained or capable of being obtained by the process according to one of claims 12 to 15 .
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR2102483A FR3120548A1 (en) | 2021-03-12 | 2021-03-12 | Product comprising a lithium adsorbent |
| PCT/FR2022/050403 WO2022189743A1 (en) | 2021-03-12 | 2022-03-07 | Product comprising a lithium adsorbent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4304773A1 true EP4304773A1 (en) | 2024-01-17 |
Family
ID=88471707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP22713968.0A Pending EP4304773A1 (en) | 2021-03-12 | 2022-03-07 | Product comprising a lithium adsorbent |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US20240165580A1 (en) |
| EP (1) | EP4304773A1 (en) |
| CN (1) | CN116981510A (en) |
-
2022
- 2022-03-07 US US18/550,174 patent/US20240165580A1/en active Pending
- 2022-03-07 CN CN202280020990.8A patent/CN116981510A/en active Pending
- 2022-03-07 EP EP22713968.0A patent/EP4304773A1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| US20240165580A1 (en) | 2024-05-23 |
| CN116981510A (en) | 2023-10-31 |
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