CN115869898B - Lithium adsorbent, preparation method thereof and extraction method of lithium ions - Google Patents
Lithium adsorbent, preparation method thereof and extraction method of lithium ions Download PDFInfo
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- CN115869898B CN115869898B CN202210838498.3A CN202210838498A CN115869898B CN 115869898 B CN115869898 B CN 115869898B CN 202210838498 A CN202210838498 A CN 202210838498A CN 115869898 B CN115869898 B CN 115869898B
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 129
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 239000003463 adsorbent Substances 0.000 title claims abstract description 113
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000000605 extraction Methods 0.000 title abstract description 8
- 238000001179 sorption measurement Methods 0.000 claims abstract description 79
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000003795 desorption Methods 0.000 claims abstract description 28
- 150000002500 ions Chemical class 0.000 claims abstract description 27
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000001556 precipitation Methods 0.000 claims abstract description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001424 calcium ion Inorganic materials 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000002594 sorbent Substances 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 9
- -1 boron anions Chemical class 0.000 abstract description 7
- 230000008929 regeneration Effects 0.000 abstract description 4
- 238000011069 regeneration method Methods 0.000 abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 229910052796 boron Inorganic materials 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 44
- 238000000034 method Methods 0.000 description 39
- 238000005086 pumping Methods 0.000 description 24
- 239000000843 powder Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 19
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 230000002572 peristaltic effect Effects 0.000 description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 8
- 239000001099 ammonium carbonate Substances 0.000 description 8
- 239000012267 brine Substances 0.000 description 8
- 235000010410 calcium alginate Nutrition 0.000 description 8
- 239000000648 calcium alginate Substances 0.000 description 8
- 229960002681 calcium alginate Drugs 0.000 description 8
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 8
- 238000011068 loading method Methods 0.000 description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 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 2
- 229910007052 Li—Ti—O Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- DBDNZCBRIPTLJF-UHFFFAOYSA-N boron(1-) monohydride Chemical compound [BH-] DBDNZCBRIPTLJF-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000002431 foraging effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- UPSTZHREJLEJFW-UHFFFAOYSA-M lithium;hydroxy carbonate Chemical compound [Li+].OOC([O-])=O UPSTZHREJLEJFW-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000136 polysorbate Polymers 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- HSEYYGFJBLWFGD-UHFFFAOYSA-N 4-methylsulfanyl-2-[(2-methylsulfanylpyridine-3-carbonyl)amino]butanoic acid Chemical compound CSCCC(C(O)=O)NC(=O)C1=CC=CN=C1SC HSEYYGFJBLWFGD-UHFFFAOYSA-N 0.000 description 1
- 229910018626 Al(OH) Inorganic materials 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical group [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910008090 Li-Mn-O Inorganic materials 0.000 description 1
- 229910006369 Li—Mn—O Inorganic materials 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- 229910003176 Mn-O Inorganic materials 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229940118662 aluminum carbonate Drugs 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- XHFVDZNDZCNTLT-UHFFFAOYSA-H chromium(3+);tricarbonate Chemical group [Cr+3].[Cr+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O XHFVDZNDZCNTLT-UHFFFAOYSA-H 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910000154 gallium phosphate Inorganic materials 0.000 description 1
- LWFNJDOYCSNXDO-UHFFFAOYSA-K gallium;phosphate Chemical group [Ga+3].[O-]P([O-])([O-])=O LWFNJDOYCSNXDO-UHFFFAOYSA-K 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical group [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 229940067606 lecithin Drugs 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
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229950008882 polysorbate Drugs 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
-
- 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
Abstract
The invention discloses a lithium adsorbent, a preparation method thereof and a lithium ion extraction method. The lithium adsorbent comprises hydroxycarbonate with a chemical formula of MXCO 3 (OH) 2 M is selected from NH 4 + 、Na + And K + X is selected from Al 3+ 、Fe 3+ 、Cr 3+ And Ga 3+ Any one of them. The preparation method comprises the following steps: constructing a reaction system comprising M ions, X ions and carbonate and/or bicarbonate ions; and carrying out precipitation reaction to obtain the lithium adsorbent. The lithium adsorbent does not need a lithium source for preparation, and raw materials required for preparation are easy to obtain and low in cost; the prepared lithium adsorbent has low solution loss, long cycle life, high selectivity (no adsorption of boron anions) and higher adsorption capacity; when the lithium adsorbent is used for extracting lithium ions, the adsorption and desorption rate is high, acid-base regeneration is not needed, and the lithium adsorbent is environment-friendly and has good economic benefit.
Description
Technical Field
The invention relates to the technical field of adsorption materials, in particular to a lithium adsorbent, a preparation method thereof and a lithium ion extraction method.
Background
Lithium and its compounds are widely used in nuclear fusion, ceramic glass, cement, aircraft products, and especially in the lithium ion battery industry. Most of the lithium is extracted from terrestrial minerals. However, the availability of land-based lithium-containing minerals is limited and there is a need to develop alternative lithium sources, such as lithium ions in liquids.
Primary liquid lithium resources are, for example, sea water and salt lake brine, which are practically inexhaustible, estimated to amount to about 2300 hundred million tons. Therefore, development of a method for efficiently extracting lithium from liquid resources is urgent.
Seawater and salt lake brine have many anions and cations coexisting, such as Li + 、Na + 、K + 、Mg 2+ 、Ca 2+ 、Cl - 、Borate，SO 4 2- And plasma anions and cations. In the process of extracting lithium resources, other ions in the salt lake can interfere with the separation of lithium, so that the difficulty of extracting lithium resources is increased. In recent years, many different methods have been explored for extracting lithium ions from seawater and salt lake brine, such as electrodialysis, coprecipitation, solvent extraction, membrane separation, and adsorption methods, among which adsorption has proven to be a particularly useful treatment method.
For example, the currently studied adsorbents are Li/Al-LDHs, li-Mn-O and Li-Ti-O, wherein the advantages of the adsorption capacity and the like of the Li-Mn-O and Li-Ti-O adsorbents are obvious, but the adsorbents cannot be applied on a large scale because the adsorbents are adsorbed in an alkaline environment and desorbed in an acidic environment, and have the problems of high dissolution loss and the like. While the Li/Al-LDHs adsorbent has been industrialized, the problems of low adsorption capacity, high solution loss, boron anion co-adsorption, lithium source synthesis, cost promotion and the like exist.
For example, in some prior art, the aluminum-based lithium adsorbent Li/Al-LDHs is prepared and synthesized in a neutral normal temperature environment or under a reagent heating condition (45-180 ℃) such as urea according to Li/al=1:3-4:1 by using lithium chloride, lithium carbonate, lithium sulfate, lithium nitrate, lithium hydroxide as a lithium source, aluminum chloride, aluminum sulfate, aluminum carbonate, aluminum hydroxide, amorphous aluminum oxide and the like as an aluminum source, and aging, filtering and drying after more than 2-12 hours to obtain a white solid powder lithium adsorbent. The prepared lithium adsorbent also needs to desorb lithium to form a compound with lithium deficiency, so that the adsorbent can be recycled. LiAl-LDHs has low adsorption capacity, high dissolution loss, weak anti-ion (especially boron anions) interference performance, structural change during adsorbent regeneration, high dissolution loss rate and adsorption capacity attenuation.
Therefore, the current situation needs a novel adsorbent with low cost, low dissolution loss, environmental protection, no lithium source preparation and no acid-base desorption.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a lithium adsorbent, a preparation method thereof and a lithium ion extraction method.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
in a first aspect, the present invention provides a lithium adsorbent comprising a hydroxycarbonate having the formula MXCO 3 (OH) 2 Wherein M is selected from NH 4 + 、Na + And K + X is selected from Al 3+ 、Fe 3+ 、Cr 3+ And Ga 3+ Any one of the following.
In a second aspect, the present invention also provides a method for preparing a lithium adsorbent, comprising:
constructing a reaction system comprising M ions, X ions and carbonate ions and/or bicarbonate ions, wherein the M ions comprise NH 4 + 、Na + And K + Any one or more than two of the above, X ions comprise Al 3+ 、Cr 3+ 、Fe 3+ And Ga 3+ Any one or a combination of two or more of them;
and (3) carrying out precipitation reaction on the reaction system to obtain the lithium adsorbent.
In a third aspect, the present invention also provides a method for extracting lithium ions, including:
providing the above lithium adsorbent;
contacting a solution to be extracted containing lithium ions with the lithium adsorbent so that the lithium ions in the solution to be extracted are adsorbed by the lithium adsorbent;
and enabling desorption liquid to be in contact with the lithium adsorbent so as to enable lithium ions adsorbed in the lithium adsorbent to be desorbed into the desorption liquid.
In a fourth aspect, the invention also provides the use of the hydroxycarbonate as a lithium adsorbent.
Further, the application may involve adsorption and desorption processes, and in some special application scenarios, such as removal of lithium impurities in a solution system, etc., may involve only adsorption processes and not desorption processes.
Based on the technical scheme, compared with the prior art, the invention has the beneficial effects that:
the preparation method of the lithium adsorbent provided by the invention has the advantages of no lithium source preparation, readily available raw materials and low cost; the prepared lithium adsorbent has low solution loss, long cycle life, strong ion interference resistance and higher adsorption capacity; meanwhile, when the lithium adsorbent provided by the invention is used for extracting lithium ions, water is used for desorption, so that the lithium adsorbent is green and environment-friendly and has good economic benefit.
The above description is only an overview of the technical solutions of the present invention, and in order to enable those skilled in the art to more clearly understand the technical means of the present application, the present invention may be implemented according to the content of the specification, the following description is given of the preferred embodiments of the present invention with reference to the accompanying drawings.
Drawings
FIG. 1 is an XRD pattern of a lithium adsorbent according to an exemplary embodiment of the invention;
FIG. 2 is a surface topography electron micrograph of a lithium adsorbent provided in accordance with another exemplary embodiment of the present invention;
fig. 3 is a graph showing the elemental content of a lithium adsorbent according to another exemplary embodiment of the present invention.
Detailed Description
The hydroxycarbonate is a layered compound, can reversibly intercalate and deintercalate lithium ions while maintaining a framework due to a special structure thereof, has the advantages of high stability, high capacity, low dissolution loss, stable structure and the like, and is a promising lithium adsorbent material. The technical scheme, the implementation process, the principle and the like are further explained as follows.
It is first noted that in the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as described herein, and therefore the scope of the present invention is not limited to the specific embodiments disclosed below.
Moreover, relational terms such as "first" and "second", and the like, may be used solely to distinguish one from another component or method step having the same name, without necessarily requiring or implying any actual such relationship or order between such components or method steps.
The embodiment of the invention provides a lithium adsorbent, which comprises hydroxycarbonate, wherein the chemical formula of the hydroxycarbonate is MXCO 3 (OH) 2 Wherein M is selected from NH 4 + 、Na + And K + X is selected from Al 3+ 、Fe 3+ 、Cr 3+ And Ga 3+ Any one of the following.
In some embodiments, the hydroxycarbonate may include: NH (NH) 4 AlCO 3 (OH) 2 、NaAlCO 3 (OH) 2 、KAlCO 3 (OH) 2 、NH 4 CrCO 3 (OH) 2 、NaCrCO 3 (OH) 2 、KCrCO 3 (OH) 2 、NH 4 FeCO 3 (OH) 2 、NaFeCO 3 (OH) 2 、KFeCO 3 (OH) 2 、NH 4 GaCO 3 (OH) 2 、NaGaCO 3 (OH) 2 KGaCO 3 (OH) 2 Any one or a combination of two or more of them.
In some embodiments, the lithium adsorbent may further include a carrier, and the hydroxycarbonate is dispersed on the carrier and pelletized.
In some embodiments, the amount of adsorption of lithium ions by the lithium adsorbent may be 7-15mg/g.
The embodiment of the invention also provides a preparation method of the lithium adsorbent, which comprises the following steps:
constructing a reaction system comprising M ions, X ions and carbonate ions and/or bicarbonate ions, wherein the M ions comprise NH 4 + 、Na + And K + Any one or more than two of the above, X ions comprise Al 3+ 、Fe 3+ 、Cr 3+ And Ga 3+ Any one or a combination of two or more of them.
The novel hydroxycarbonate lithium adsorbent provided by the technical scheme can be prepared by adopting a one-step method, does not need a lithium source, does not need to be applied after eluting lithium, has the advantages of pure water desorption and regeneration, and is low in dissolution loss and high in structural stability. The hydroxycarbonate has the advantages of high structural strength, low solution loss, no need of lithium source and repeated cyclic utilization. The synthesis process is simple, the price is low, the pollution to the environment is avoided, and the inorganic salts (aluminum, iron, chromium-based and other salts) of the main carrier used in the synthesis are all common inorganic salts. The conditions used for synthesis are mild, and the method is suitable for large-scale production.
And (3) carrying out precipitation reaction on the reaction system to obtain the lithium adsorbent.
In some embodiments, the concentration of M ions in the reaction system may be in the range of 0.1 to 14mol/L.
In some embodiments, the concentration of X ions in the reaction system may be in the range of 0.1 to 14mol/L.
In some embodiments, the total concentration of carbonate ions and bicarbonate ions in the reaction system may be from 0.1 to 14mol/L. The concentration of the ions is not a definite fixed value, and therefore, the concentration of the ions in the invention refers to the equivalent concentration of the ions calculated according to the assumption of complete dissociation of the fed compound; the total concentration means that when both carbonate ions and bicarbonate ions are present, the total concentration is the sum of the concentrations of both, and when only one of them is present, the total concentration is the concentration of one of them.
Moreover, the above concentration ranges are preferred partial concentration ranges of the equilibrium preparation time cost and the solution cost of the present invention, and in some embodiments, the ion concentration may be significantly lower than the above concentration ranges, and a lithium adsorbent having lithium adsorption activity may also be prepared. Therefore, the above preferred concentration ranges are not limiting to the scope of the present invention, and lithium adsorbents equivalent obtained by those skilled in the art based on other concentrations that are possible to replace the technical idea of the present invention are also included in the scope of the present invention.
In some embodiments, the reaction system further comprises a carbonate ion and a bicarbonate ion including a surfactant and/or ammonia and/or urea.
In some embodiments, the concentration of surfactant in the reaction system may be in the range of 0.01 to 4mol/L.
In some embodiments, the total concentration of ammonia and urea in the reaction system may be 0.1 to 10mol/L.
In some embodiments, the precipitation reaction may be at a temperature of 25-180 ℃, for a time of 2-24 hours, and at a ph of 9-10.5.
Likewise, the above concentrations and pH selections are also preferred partial parameter ranges for the balance of time cost and solution cost of the present invention, and in some embodiments may be outside of these ranges, for example, in some embodiments a pH value other than 9-10.5 may be used to obtain a lithium adsorbent having adsorption activity. The present invention focuses on creatively exploring the application of the above hydroxycarbonates in the field of lithium adsorption, while the preferred parameters in the preparation of lithium adsorbents are obviously not limiting the scope of protection of the present invention.
In some embodiments, the method of making may further comprise: and drying, grinding and granulating the lithium adsorbent obtained by the precipitation reaction.
In some embodiments, the lithium adsorbent is granulated by dispersing in a carrier solution and cross-linking with calcium ions. Concretely, sodium alginate is adopted to drop CaCl 2 Solution rapid prototyping granulation, ca 2+ The presence of (c) helps to maintain strength. This is just a rapid spherical granulation process. It should be noted that the above granulation forming method is only a preferred granulation method according to the embodiments of the present invention, and the technical effects of the present invention may also be achieved by using other granulation forming methods commonly used for various adsorbents in the prior art, and equivalent replacement of the granulation method should be within the protection scope of the present invention.
Based on the above outlined exemplary embodiments, some of the more preferred embodiments may be implemented using the following steps:
and synthesizing the hydroxycarbonate lithium adsorbent by adopting a conventional stirring method or a hydrothermal method. 1.5-7mol/L Al is configured 2 (SO 4 ) 3 ·18H 2 O (which may be replaced with iron sulfate, potassium carbonate, chromium carbonate, gallium phosphate, iron hydroxide, chloride such as iron chloride, aluminum chloride, etc., carbonic acid, sulfuric acid, carbonic acid, etc., and the like), 2 to 20mmol of urea (which may be replaced with ammonia water, etc.), and 0.6 to 1.2mol of a surfactant (which may be selected from the range of, for example, 1. Anionic surfactant;, for example, stearic acid, sodium dodecyl benzene sulfonate, etc., 2. Cationic surfactant: quaternary ammonium compound, etc., 3. Zwitterionic surfactant: lecithin, amino acid type, betaine type, etc., 4. Nonionic surfactant: alkyl glucoside (APG), fatty acid glyceride, fatty acid sorbitan (span), polysorbate (Tween), 5.PEO, PEG, etc.) are dissolved in 30 to 65mL of water, stirred uniformly, and then placed in a solution of dropwise added 0.5 to 3mol/L of ammonium bicarbonate or ammonium carbonate, stirred or transferred to a 50 to 1000mL of a hydrothermal reaction kettle at room temperature to 95 ℃ continuously, after the reaction is completed, cooled to a pH of the reaction kettle is cooled until the reaction is completed, and the reaction layer is washed until the deionized water is nearly the same. After washing, the wet powder is dried in an oven at 50-80 ℃. Finally, a powder product is obtained, which can be used as a lithium adsorbent. The product can be further ground and then sealed and stored for standby. The powder product may be, for example: NH (NH) 4 AlCO 3 (OH) 2 、NaAlCO 3 (OH) 2 、KAlCO 3 (OH) 2 、NH 4 CrCO 3 (OH) 2 、NaCrCO 3 (OH) 2 、KCrCO 3 (OH) 2 、NH 4 FeCO 3 (OH) 2 、NaFeCO 3 (OH) 2 、KFeCO 3 (OH) 2 、NH 4 GaCO 3 (OH) 2 、NaGaCO 3 (OH) 2 KGaCO 3 (OH) 2 Any one of the above or a compound salt of a plurality of hydroxycarbonates is prepared by compounding a plurality of ions during the preparation.
In the technical scheme, the surfactant acts as a pore-forming agent and a morphology regulator, and the mesopores and macropores obviously increase the adsorption capacity of the adsorbent. .
The embodiment of the invention also provides a lithium ion extraction method, which comprises the following steps:
the lithium adsorbent provided in the above examples or the lithium adsorbent prepared by the preparation method provided in the above examples is provided.
And contacting the liquid to be extracted containing lithium ions with the lithium adsorbent so that the lithium ions in the liquid to be extracted are adsorbed by the lithium adsorbent.
And enabling desorption liquid to be in contact with the lithium adsorbent so as to enable lithium ions adsorbed in the lithium adsorbent to be desorbed into the desorption liquid.
In some embodiments, the desorption liquid may comprise water. Pure water can be used as desorption liquid, and the water possibly contains some unavoidable impurities, so that the desorption effect is not affected, and of course, an aqueous solution can also be used as desorption liquid, wherein some components assisting in desorption can be dissolved.
Based on the above outlined exemplary embodiments, some of the more preferred embodiments may be implemented using the following steps:
adsorption process
According to the packing height, the inner diameter and the packing particle size of an adsorption column, a proper pump speed is selected, the lithium adsorbent is transferred into the adsorption column, the mode of lower inlet and upper outlet is adopted, the concentration of lithium ions in effluent liquid is detected, dynamic adsorption is stopped when the lithium ions in extracting solution just penetrate through the adsorption column, and the adsorption capacity is 7-15mg/g.
Desorption process
And selecting proper pump speed according to the packing height, the inner diameter and the packing particle size of the adsorption column, pumping eluent (water) into the adsorption column from bottom to top, collecting the eluent, detecting the concentration of lithium ions in the effluent, stopping pumping the eluent when the concentration of the lithium ions in the effluent is reduced to zero, repeating the operation described in the step 2, and repeatedly adsorbing and desorbing to finish the extraction of the lithium ions.
Of course, the above is merely an example of a preferred embodiment, and the present invention focuses on providing an adsorbent, and as to how to use the adsorbent to perform extraction of lithium ions, there are various common methods in the art, for example, an alternative method of standing and soaking to perform adsorption and so on, which will not be described herein.
Based on the above exemplary technical scheme, the embodiment of the invention designs and provides a synthesis method of a hydroxycarbonate lithium adsorbent and a process route applied to lithium adsorption, wherein the adsorbent has the characteristics of low solution loss, high selectivity, high anti-interference, especially strong anti-boron anion interference, no need of lithium source preparation, and the process route for extracting lithium ions has the advantages of low cost, simple process flow and no pollution.
The technical scheme of the invention is further described in detail below through a plurality of embodiments and with reference to the accompanying drawings. However, the examples are chosen to illustrate the invention only and are not intended to limit the scope of the invention.
Example 1
This example illustrates the synthesis of a hydroxycarbonate lithium adsorbent and its lithium adsorption application.
Preparing 1.5mol/L ammonium bicarbonate solution with deionized water at room temperature, regulating pH to about 10 with ammonia water, and adding 0.5mol/L Al 2 (SO 4 ) 3 The solution was added dropwise to the ammonium bicarbonate solution (wherein NH 4 HCO 3 /Al 2 (SO 4 ) 3 Molar ratio of 3/1), at 55℃for 8h.
Finally, white sediment is obtained, the prepared white sediment is kept stand for aging, washed by deionized water and dried to obtain a sample. Finally obtain white powder product of NH 4 AlCO 3 (OH) 2 See XRD test for its structure shown in figure 1.
Then granulating by calcium alginate method (the calcium alginate granulating step comprises mixing 10g of the white powder product NH 4 AlCO 3 (OH) 2 Dispersing in 2g/100ml sodium alginate solution, and then dripping 4% CaCl 2 Granulation in solution), the estimated lithium sorbent loading was 80%. Loading the granulated adsorbent into an adsorption column with the inner diameter of 3cm, pumping 500mg/L lithium chloride solution from the lower end of the adsorption column by a peristaltic pump, and carrying out dynamic adsorption at the pumping speed of 55mL/h.
And stopping dynamic adsorption when the outflow of lithium ions is detected.
And then pumping deionized water at a flow rate of 3mL/min until no lithium ions flow out, and completing the desorption of the lithium ions.
In this example, the adsorption capacity of the above-mentioned lithium adsorbent was 7.79mg/g. The adsorption capacity was calculated for the total mass of lithium adsorbent formed by the combination of the hydroxycarbonate and the support in this example and the following examples.
Example 2
This example illustrates the synthesis of a lithium hydroxy acid salt adsorbent and its lithium adsorption application.
1.2 mol.L -1 654ml of aluminum nitrate solution is slowly added into 1170ml of 2mol/L ammonium carbonate solution in a dropwise manner, and the mixture solution is continuously stirred, the temperature of the mixture solution is controlled between 55 ℃ and 65 ℃, the pH value is between 7 and 8, and the mixture solution is subjected to 10 hours.
After the reaction was completed, cooled to room temperature, aged for 10 hours, filtered, and continuously washed with deionized water until the pH of the supernatant water was approximately 7. After washing, the wet white powder was dried in an oven at 60 ℃. Finally obtain white powder product NH 4 AlCO 3 (OH) 2 The product is further ground and then sealed and stored for standby.
Then granulating by calcium alginate method, loading the granulated adsorbent into an adsorption column with an inner diameter of 3em, pumping 1000mg/L lithium chloride solution from the lower end of the adsorption column by peristaltic pump, and pumping at a speed of 50mL/h. And stopping dynamic adsorption when the outflow of lithium ions is detected.
And then pumping deionized water at a flow rate of 2mL/min until no lithium ions flow out, and completing the desorption of the lithium ions.
In this example, the adsorption capacity of the lithium adsorbent was 10.53mg/g.
Example 3
Synthesis and lithium adsorption application of porous hydroxy carbonate lithium adsorbent
Adding 0.1mol/L dispersant (PEO, PEG, surfactant) to 1.2mol/L AlCl 3 ·6H 2 O solution (1000 m 1) is fully mixed and the temperature is controlled to be 50-Between 60 ℃, then 2mol/L NH 4 HCO 3 The solution (1000 mL) was added to the above solution at a rate of 2mL/min, the stirring rate was controlled, and the pH of the mixed solution was measured at about 9 with a pH acidometer, aged for 12 hours, cooled to room temperature after the reaction was completed, filtered, washed with deionized water continuously, and the wet powder was dried in an oven at 60 ℃. Finally obtain the powder product of NH 4 AlCO 3 (OH) 2 The scanning electron microscope SEM is shown in figure 2, and the elemental analysis is shown in figure 3.
The product is further ground and then sealed and stored for standby. And then granulating by using a polyacrylonitrile method, loading the granulated adsorbent into a custom-made adsorption column with the inner diameter of 2.5cm and the height of 85cm, and pumping 1000mg/L lithium chloride solution from the lower end of the adsorption column by using a peristaltic pump with the pumping speed of 60mL/h. And stopping dynamic adsorption when the outflow of lithium ions is detected.
And then pumping deionized water at a flow rate of 2mL/min until no lithium ions flow out, and completing the desorption of the lithium ions.
In this example, the adsorption capacity of the lithium adsorbent was 9.56mg/g.
Example 4
Synthesis of hydroxycarbonate lithium adsorbent and lithium adsorption application
0.5mol of aluminum ammonium sulfate, 0.3mol of potassium bicarbonate, 0.8mol of urea and 0.1mol of sodium dodecyl sulfate surfactant are weighed and dissolved in 2000mL of water, the pH value is regulated to 9-9.5, and the mixture is stirred uniformly and then placed in a hydrothermal reaction kettle for reaction for 12 hours at 95 ℃.
After the reaction was completed, cooled to room temperature, filtered, and washed with deionized water continuously until the pH of the supernatant water was near 7. After washing, the wet powder was dried in an oven at 60 ℃. The powder product KAlCO is finally obtained 3 (OH) 2 The product is further ground and then sealed and stored for standby.
Then granulating by utilizing a calcium alginate method, loading the granulated adsorbent into a custom-made adsorption column with the inner diameter of 2cm and the height of 75cm, and pumping 1000mg/L lithium chloride solution from the lower end of the adsorption column by a peristaltic pump with the pumping speed of 60mL/h. And stopping dynamic adsorption when the outflow of lithium ions is detected.
Deionized water was then pumped in at a flow rate of 2.5mL/min until no lithium ions were eluted, completing desorption.
The lithium adsorption capacity of the lithium adsorbent in this example was 7.79mg/g.
In addition, the lithium adsorbent provided in this example was applied to the eastern Ji Naier salt lake brine for adsorption, and the ion concentration changes before and after adsorption are shown in table 1, as is clear from the results, the lithium adsorbent provided in this example has high selectivity for lithium ions.
Meanwhile, the inventors all carried out the same salt lake brine adsorption on the lithium adsorbents prepared in the previous examples, and all showed the same remarkable lithium selectivity.
TABLE 1 ion concentration variation before and after adsorption in Dongtai Ji Naier salt lake brine
Example 5
Synthesis of hydroxycarbonate lithium adsorbent and lithium adsorption application
Taking 0.0104 mol.L -1 1000ml of sodium carbonate and 1000ml of 0.017mol/L aluminum sulfate solution are mixed and stirred continuously, the temperature of the mixed solution is controlled at 95 ℃, the pH value is about 10, and the mixed solution is carried out for 6 hours.
After the reaction was completed, cooled to room temperature, aged for 8 hours, filtered, and continuously washed with deionized water until the pH of the supernatant water was approximately 7. After washing, the wet powder was dried in an oven at 60 ℃. Finally obtain the powder product NaAlCO 3 (OH) 2 The product is further ground and then sealed and stored for standby.
Then granulating by calcium alginate method, loading the granulated adsorbent into an adsorption column with an inner diameter of 3cm and a height of 85cm, pumping 500mg/L lithium chloride solution from the lower end of the adsorption column by peristaltic pump, and pumping at a speed of 60mL/h. And stopping dynamic adsorption when the outflow of lithium ions is detected.
And then pumping deionized water at a flow rate of 5mL/min until no lithium ions flow out, and completing the desorption of the lithium ions.
In this example, the adsorption capacity of the lithium adsorbent was 7.83mg/g.
Example 6
Synthesis of hydroxycarbonate lithium adsorbent and lithium adsorption application
Taking 0.3 mol.L -1 The potassium bicarbonate and the 0.1mol/L aluminum hydroxide solution were mixed in 1000ml portions, and the mixture was stirred continuously, the temperature of the mixed solution was controlled at 180℃and the pH was controlled at about 10, and the mixture was allowed to proceed for 6 hours.
After the reaction was completed, cooled to room temperature, aged for 10 hours, filtered, and continuously washed with deionized water until the pH of the supernatant water was approximately 7. After washing, the wet powder was dried in an oven at 60 ℃. The powder product KAlCO is finally obtained 3 (OH) 2 The product is further ground and then sealed and stored for standby.
Then granulating by calcium alginate method, loading the granulated adsorbent into an adsorption column with an inner diameter of 3cm and a height of 75cm, pumping 1000mg/L lithium chloride solution from the lower end of the adsorption column by peristaltic pump, and pumping at a speed of 70mL/h. And stopping dynamic adsorption when the outflow of lithium ions is detected.
And then pumping deionized water at a flow rate of 4mL/min until no lithium ions flow out, and completing the desorption of the lithium ions.
In this example, the adsorption capacity of the lithium adsorbent was 10.16mg/g.
Example 7
Synthesis of hydroxycarbonate lithium adsorbent and lithium adsorption application
Taking 0.3 mol.L -1 Potassium carbonate, 0.1 mol.L -1 Ammonium bicarbonate and 0.1mol/L ferric sulfate solution (1000 ml) are mixed, and the mixed solution is continuously stirred, the temperature of the mixed solution is controlled at 90 ℃, the pH value is controlled at about 10, and the mixed solution is carried out for 9 hours.
Cooling to room temperature after the reaction is finished, aging for 11 hours, filtering, continuously using deionized waterWashing until the pH of the supernatant water approaches 7. After washing, the wet powder was dried in an oven at 60 ℃. Finally obtain the powder product KFECO 3 (OH) 2 The product is further ground and then sealed and stored for standby.
Then granulating by calcium alginate method, loading the granulated adsorbent into an adsorption column with an inner diameter of 2cm and a height of 75cm, pumping 500mg/L lithium chloride solution from the lower end of the adsorption column by peristaltic pump, and pumping at a speed of 70mL/h. And stopping dynamic adsorption when the outflow of lithium ions is detected.
And then pumping deionized water at a flow rate of 6mL/min until no lithium ions flow out, and completing the desorption of the lithium ions.
In this example, the adsorption capacity of the lithium adsorbent was 8.76mg/g.
Example 8
Synthesis of hydroxycarbonate lithium adsorbents and lithium adsorption applications.
2000ml of ammonium bicarbonate solution with the concentration of 1.5mol/L is prepared by deionized water at 35 ℃, the pH value of the solution is regulated to be about 9.5 by ammonia water, 2000ml of aluminum nitrate solution with the concentration of 0.3mol/L is dropwise added into the ammonium bicarbonate solution by a peristaltic pump, and the reaction is carried out for 10 hours at 55 ℃.
Finally, white sediment is obtained, the prepared white sediment is kept stand for aging, washed by deionized water and dried to obtain a sample. Finally obtain white powder product of NH 4 Al(OH) 2 CO 3 。
Then granulating by using the calcium alginate method in example 1. The granulated adsorbent is filled into an adsorption column with the inner diameter of 2.5cm and the height of 75cm, and 300mg/L of lithium chloride solution is pumped into the adsorption column from the lower end by a peristaltic pump to be dynamically adsorbed, wherein the pumping speed is 45mL/h. And stopping dynamic adsorption when the outflow of lithium ions is detected.
And then pumping deionized water at a flow rate of 4mL/min until no lithium ions flow out, and completing the desorption of the lithium ions.
In this example, the adsorption capacity of the above-mentioned lithium adsorbent was 8.23mg/g.
Based on the above examples, it is clear that the present invention finds for the first time the use of hydroxycarbonates as lithium adsorbents. The preparation method of the lithium adsorbent provided by the embodiment of the invention does not need a lithium source for preparation, and the required raw materials are easy to obtain and low in cost; the prepared lithium adsorbent has high structural strength, low solution loss, long cycle life, strong ion interference resistance and higher adsorption capacity; meanwhile, when the lithium adsorbent provided by the invention is used for extracting lithium ions, the process flow is simple and easy to implement, the equipment cost requirement is low, water can be used for desorption, and the lithium adsorbent is environment-friendly and has good economic benefit.
Particularly, the hydroxycarbonate lithium ion used in the embodiment of the invention has high adsorption quantity, good selectivity, strong anti-interference ion performance (especially boron anion interference), long cycle life, low solution loss and good regeneration performance, and is especially suitable for extracting lithium ions from salt lake brine or seawater. The hydroxy carbonate lithium adsorbent is synthesized without a lithium source, has low cost and shows excellent selective adsorption performance in practical salt lake brine. The process has simple whole flow, high efficiency and low cost.
Furthermore, the above examples illustrate that different hydroxycarbonates obtained based on various steps and/or parameters may have significant lithium adsorptivity, and thus, the hydroxycarbonates provided by the present invention have wide applicability as lithium adsorbents and should not be limited to specific sources or preparation methods.
It should be understood that the above embodiments are merely for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and implement the same according to the present invention without limiting the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (13)
1. Use of a hydroxycarbonate as a lithium sorbent, comprising:
providing a lithium adsorbent;
contacting a solution to be extracted containing lithium ions with the lithium adsorbent so that the lithium ions in the solution to be extracted are adsorbed by the lithium adsorbent;
wherein the lithium adsorbent comprises hydroxycarbonate, and the chemical formula of the hydroxycarbonate is MXCO 3 (OH) 2 Wherein M is selected from NH 4 + 、Na + And K + X is selected from Al 3+ 、Fe 3+ 、Cr 3+ 、Ga 3+ Any one of the following.
2. The use according to claim 1, wherein the hydroxycarbonate comprises NH 4 AlCO 3 (OH) 2 、NaAlCO 3 (OH) 2 、KAlCO 3 (OH) 2 、NH 4 CrCO 3 (OH) 2 、NaCrCO 3 (OH) 2 、KCrCO 3 (OH) 2 、NH 4 FeCO 3 (OH) 2 、NaFeCO 3 (OH) 2 、KFeCO 3 (OH) 2 、NH 4 GaCO 3 (OH) 2 、NaGaCO 3 (OH) 2 KGaCO 3 (OH) 2 Any one or a combination of two or more of them.
3. The use according to claim 1, wherein the lithium adsorbent further comprises a carrier, and the hydroxycarbonate is dispersed on the carrier and shaped by granulation.
4. The use according to claim 1, wherein the amount of adsorption of lithium ions by the lithium adsorbent is 7-15mg/g.
5. The use according to claim 1, wherein the preparation method of the lithium adsorbent comprises:
constructing a reaction system comprising M ions, X ions and carbonate ions and/or bicarbonate ions, wherein the M ions comprise NH 4 + 、Na + And K + Any one or more than two of the above, X ions comprise Al 3+ 、Fe 3+ 、Cr 3+ And Ga 3+ Any one or a combination of two or more of them;
and (3) carrying out precipitation reaction on the reaction system to obtain the lithium adsorbent.
6. The use according to claim 5, wherein the precipitation reaction is carried out at a temperature of 25-180 ℃ for a time of 2-24 hours and at a ph of 9-10.5.
7. The use according to claim 5, further comprising: and drying and grinding the lithium adsorbent obtained by the precipitation reaction, and granulating.
8. The use according to claim 7, wherein the lithium adsorbent is formed by granulating by dispersing it in a carrier solution and crosslinking it with calcium ions.
9. The use according to claim 5, characterized in that the reaction system further comprises a surfactant and/or ammonia and/or urea.
10. The use according to claim 9, wherein the concentration of surfactant in the reaction system is 0.01-4mol/L.
11. The use according to claim 9, characterized in that the total concentration of ammonia and urea in the reaction system is 0.1-10mol/L.
12. The use according to claim 9, further comprising:
and enabling desorption liquid to be in contact with the lithium adsorbent so as to enable lithium ions adsorbed in the lithium adsorbent to be desorbed into the desorption liquid.
13. The use of claim 12, wherein the desorption liquid comprises water.
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