CN118006900A - Method for removing impurities from acid leaching solution of waste ternary lithium battery - Google Patents
Method for removing impurities from acid leaching solution of waste ternary lithium battery Download PDFInfo
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- CN118006900A CN118006900A CN202410024275.2A CN202410024275A CN118006900A CN 118006900 A CN118006900 A CN 118006900A CN 202410024275 A CN202410024275 A CN 202410024275A CN 118006900 A CN118006900 A CN 118006900A
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- 238000002386 leaching Methods 0.000 title claims abstract description 111
- 239000012535 impurity Substances 0.000 title claims abstract description 107
- 239000002253 acid Substances 0.000 title claims abstract description 83
- 238000000034 method Methods 0.000 title claims abstract description 70
- 239000002699 waste material Substances 0.000 title claims abstract description 40
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 32
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 63
- -1 fluorine ions Chemical class 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 238000002156 mixing Methods 0.000 claims abstract description 36
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 30
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 239000011737 fluorine Substances 0.000 claims abstract description 29
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 29
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 17
- 238000000926 separation method Methods 0.000 claims abstract description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 257
- 239000011656 manganese carbonate Substances 0.000 claims description 34
- 229940093474 manganese carbonate Drugs 0.000 claims description 34
- 235000006748 manganese carbonate Nutrition 0.000 claims description 34
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 34
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- 238000005245 sintering Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 9
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 9
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 9
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 8
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 6
- FDFPDGIMPRFRJP-UHFFFAOYSA-K trichlorolanthanum;heptahydrate Chemical compound O.O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[La+3] FDFPDGIMPRFRJP-UHFFFAOYSA-K 0.000 claims description 6
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 4
- 244000105624 Arachis hypogaea Species 0.000 claims description 4
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 4
- 235000018262 Arachis monticola Nutrition 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 4
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 4
- 235000011613 Pinus brutia Nutrition 0.000 claims description 4
- 241000018646 Pinus brutia Species 0.000 claims description 4
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910001437 manganese ion Inorganic materials 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims description 4
- 235000020232 peanut Nutrition 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 3
- 241000609240 Ambelania acida Species 0.000 claims description 2
- 244000068988 Glycine max Species 0.000 claims description 2
- 235000010469 Glycine max Nutrition 0.000 claims description 2
- 240000007049 Juglans regia Species 0.000 claims description 2
- 235000009496 Juglans regia Nutrition 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 239000003929 acidic solution Substances 0.000 claims description 2
- 239000010905 bagasse Substances 0.000 claims description 2
- 235000013399 edible fruits Nutrition 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- 235000020234 walnut Nutrition 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 16
- 229910052751 metal Inorganic materials 0.000 abstract description 13
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 127
- 239000011572 manganese Substances 0.000 description 69
- 229910052748 manganese Inorganic materials 0.000 description 69
- 239000010941 cobalt Substances 0.000 description 68
- 229910017052 cobalt Inorganic materials 0.000 description 68
- 229910052759 nickel Inorganic materials 0.000 description 68
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 60
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 59
- 238000001914 filtration Methods 0.000 description 33
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 18
- 239000000084 colloidal system Substances 0.000 description 18
- 229910001416 lithium ion Inorganic materials 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 235000021110 pickles Nutrition 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229960004887 ferric hydroxide Drugs 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The application particularly discloses a method for removing impurities from an acid leaching solution of a waste ternary lithium battery. The method comprises the following steps: step one: mixing the ternary acid leaching solution with hydrazine hydrate, wherein the stoichiometric ratio of the hydrazine hydrate to impurity copper ions in the ternary acid leaching solution is 2.4-2.6:1, carrying out solid-liquid separation after reaction to obtain a first solution; step two: the first solution and the first carbonate are mixed according to the weight ratio of 1: mixing 0.1-0.15, controlling the pH of the reaction system to be more than or equal to 5.0, and carrying out solid-liquid separation after the reaction to obtain a second solution; step three: mixing the second solution with a fluorine removing agent, wherein the weight ratio of the fluorine removing agent to impurity fluorine ions in the second solution is 3-10:1, carrying out solid-liquid separation after the reaction to obtain a third solution; wherein the defluorinating agent comprises any one of poly N, N (trihydroxy silicon ureidopropyl) urea and lanthanum-carrying biochar. The application has the advantages of improving the recovery rate of valuable metal elements nickel cobalt manganese, reducing recovery procedures and saving recovery cost.
Description
Technical Field
The invention relates to the technical field of lithium ion battery recovery and regeneration, in particular to a method for removing impurities from an acid leaching solution of a waste ternary lithium battery.
Background
The lithium ion battery is widely applied to the fields of 3C and new energy automobiles, and plays a vital role in realizing sustainable development of environmental day marks, reducing air pollution problems and coping with gradual climate deterioration. However, the service life of the lithium ion battery is generally 5-8 years, and as the service life of the lithium ion battery is terminated, the number of obsolete lithium ion batteries is gradually increased, and if the obsolete lithium ion batteries cannot be properly treated, the obsolete lithium ion batteries not only cause waste of valuable metal resources such as manganese, cobalt, nickel, lithium and the like, which is not beneficial to benign development of the lithium ion battery industry, but also cause serious pollution to the environment. Therefore, the research of the resource recovery technology of the waste lithium ion battery is very important and practical.
In the recovery of the ternary lithium battery, the ternary lithium battery is subjected to disassembly, crushing, high-temperature calcination, reduction and acid leaching to obtain ternary acid leaching liquid, and the ternary acid leaching liquid contains a large amount of copper ion impurities, aluminum ion impurities (metal on a battery pole piece) and impurity fluoride ions. At present, most existing methods use iron powder to replace impurity copper ions in ternary pickling liquid, then hydrogen peroxide is added, pH is adjusted to remove impurity iron ions and impurity aluminum ions, and finally an aluminum series fluorine removing agent is added to remove impurity fluorine ions; the impurity removing process is long in operation time, a large amount of colloid can be produced in the impurity removing stage, the filtering cost is increased, the generated colloid can take away a large amount of valuable metal elements of nickel, cobalt and manganese in the filtering operation, the recovery procedure and the recovery cost are increased, and the recovery rate of the valuable metal elements of nickel, cobalt and manganese is also reduced.
Disclosure of Invention
In order to reduce the generation of colloid ions in the process of removing impurities from ternary pickling liquid, improve the recovery rate of valuable metal elements nickel cobalt manganese, reduce recovery procedures and save recovery cost, the application provides a method for removing impurities from the acid leaching liquid of a waste ternary lithium battery.
The application provides a method for removing impurities from acid leaching liquid of waste ternary lithium batteries, which adopts the following technical scheme:
a method for removing impurities from acid leaching liquid of waste ternary lithium batteries comprises the following steps:
step one: mixing the ternary acid leaching solution with hydrazine hydrate, wherein the stoichiometric ratio of the hydrazine hydrate to impurity copper ions in the ternary acid leaching solution is 2.4-2.6:1, for example, may be 2.4: 1. 2.5: 1. 2.6:1, but not limited to the listed values, other non-listed values within the range of values are equally applicable, and solid-liquid separation after reaction to obtain a first solution;
Step two: the first solution and the first carbonate are mixed according to the weight ratio of 1:0.1-0.15, for example, can be 1:0.1, 1:0.11, 1:0.13, 1:0.15, but not limited to the recited values, other non-recited values within the range of values are equally applicable, the pH of the reaction system is controlled to be equal to or more than 5.0, for example, 5.0, 5.2, 5.5, 6.2 and 6.5, but not limited to the recited values, other non-recited values within the range of values are equally applicable, and solid-liquid separation is carried out after the reaction to obtain a second solution;
Step three: mixing the second solution with a fluorine removing agent, wherein the weight ratio of the fluorine removing agent to impurity fluorine ions in the second solution is 3-10:1, for example, may be 3: 1.5:1. 8: 1. 10:1, but not limited to the recited values, other non-recited values within the range of values are equally applicable, and solid-liquid separation after reaction to obtain a third solution;
Wherein the defluorinating agent comprises any one of poly N, N (trihydroxy silicon ureidopropyl) urea and lanthanum-carrying biochar. The ternary acid leaching solution refers to the acid leaching solution of the waste ternary lithium battery.
According to the application, the hydrazine hydrate is used for reacting the impurity copper ions in the ternary pickling liquid to generate elemental copper, and excessive hydrazine hydrate can also react with oxygen to decompose, so that water and nitrogen are produced, new impurities are not introduced, the elemental copper can be filtered along with the filtering operation, and meanwhile, the hydrazine hydrate can also play a role in increasing the pH value of a reaction system, thereby being beneficial to pH value adjustment in the second step. And secondly, after the fluorine removing agent is added, new impurities are not introduced while fluorine ions are adsorbed, the fluorine removing agent is not dissolved in the pickle liquor, and the fluorine removing agent can be directly removed from the mixed solution as filter residues after filtration. Compared with the impurity removing method in the prior art, the impurity removing method has the advantages that only aluminum hydroxide colloid is generated in the reaction process of the second step, the quantity of the colloid is small, the filtering cost can be reduced, the filtering time can be shortened, and the quantity of nickel, cobalt and manganese taken away in the process of filtering aluminum hydroxide is small due to the fact that the quantity of the aluminum hydroxide colloid is small, so that the purity of the third solution is improved, and the recovery rate of nickel, cobalt and manganese is improved.
Preferably, the poly-N, N (trihydroxy silicon ureidopropyl) urea is prepared by a method comprising the steps of: mixing gamma-ureidopropyl triethoxysilane, hydrazine hydrate and a catalyst, and heating to obtain the poly-N, N (trihydroxy silicon ureidopropyl) urea.
Preferably, the stoichiometric ratio of gamma-ureidopropyltriethoxysilane, hydrazine hydrate and catalyst is 2-3:1-2:1, for example, may be 2:1: 1. 3:2: 1. 2:2: 1. 3:1:1, but is not limited to, the recited values, other non-recited values within the range of values are equally applicable; the heating temperature is 30-35 ℃, the heating time is 65-72h, for example, the heating temperature can be 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃, 35 ℃, and the heating time can be 65h, 66h, 68h, 70h and 72h, but the heating temperature is not limited to the listed values, and other values not listed in the numerical range are applicable. The catalyst is ammonia water, the concentration of the ammonia water is 25wt% to 28wt%, for example, 25wt%, 25.8wt%, 26.5wt%, 27wt%, 28wt%, but the catalyst is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the lanthanum-loaded biochar is prepared by a method comprising the following steps: cleaning, drying and crushing the biological matrix to obtain pretreated powder; screening treatment is also carried out after the crushing treatment. The pretreated powder is mixed with lanthanum chloride heptahydrate according to the stoichiometric ratio of 5-8:2-2.5, for example, can be 5: 2.5: 2.8, 8:2. 8:2.5, 7: 2. 7.5:2.2, but not limited to the values listed, other values not listed in the numerical range are equally applicable, and the impregnated sample is obtained by impregnating after adding water, wherein the mass ratio of the solid powder to the water in the impregnated sample is 10-15:1, for example, may be 10: 1. 11: 1. 13: 1. 15:1, but not limited to the values recited, other values not recited in the range of values are equally applicable, with a dipping time of 10-20 minutes; and drying, sintering and cooling the immersed sample to obtain the lanthanum-carrying biochar.
Preferably, the biological matrix comprises at least one of peanut shell, hull, rice hull, walnut shell, oak shell, bagasse, red residue, soybean residue, straw pine needle, pine cone, and fruit tree branch; the stoichiometric ratio of the pretreatment powder to the lanthanum chloride heptahydrate is 5-10:2-3; for example, it may be 5: 2. 5: 3. 10: 2. 10: 3. 7:2.5, 8:2.8, but not limited to the values recited, other non-recited values within the range of values are equally applicable, the temperature during sintering is 450-550 ℃, the sintering time is 1-1.5 hours, for example, the sintering temperature may be 450 ℃, 480 ℃, 500 ℃, 510 ℃, 530 ℃, 550 ℃, the sintering time may be 1 hour, 1.1 hour, 1.2 hours, 1.3 hours, 1.5 hours, but not limited to the values recited, and other non-recited values within the range of values are equally applicable. The impregnated sample is dried at 100-110 ℃ for 2-3 hours, for example, the drying temperature can be 100 ℃, 102 ℃, 106 ℃, 108 ℃, 109 ℃, 110 ℃, and the drying time can be 2 hours, 2.2 hours, 2.5 hours, 2.8 hours and 3 hours, but the method is not limited to the listed values, and other non-listed values in the numerical range are applicable; after the sintering is cooled, the sintered product is washed 2 to 3 times by deionized water and then dried at 100 to 110 ℃, for example, the drying temperature can be 100 ℃, 102 ℃, 106 ℃, 108 ℃, 109 ℃ and 110 ℃, but the sintered product is not limited to the listed values, and other non-listed values in the numerical range are applicable to obtain the lanthanum-carrying biochar.
Preferably, the reaction temperature in the first step is 24-26 ℃ and the reaction time is 0.5-1h; the reaction temperature in the second step is 80-90 ℃ and the reaction time is 2-3h; the reaction temperature in the third step is 64-66 ℃, and the reaction time is 1-1.5h. For example, the reaction temperature in the first step may be 24 ℃,25 ℃,26 ℃, the reaction time may be 0.5h, 0.6h, 0.7h, 0.8h, 1h, the reaction temperature in the second step may be 80 ℃, 85 ℃, 90 ℃, the reaction time may be 2h, 2.3h, 2.5h, 2.8h, 3h, the reaction temperature in the third step may be 64 ℃, 65 ℃, 66 ℃, and the reaction time may be 1h, 1.2h, 1.3h, 1.5h, but not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
Preferably, the first carbonate used in the second step includes at least one of manganese carbonate, nickel carbonate, and cobalt carbonate.
By using the carbonate, manganese ions, nickel ions and cobalt ions are introduced into the reaction system while generating aluminum hydroxide colloid, so that the aluminum hydroxide colloid can be recycled and utilized in accordance with valuable metal elements to be recycled in the ternary pickle liquor, and new impurity ions are not introduced.
Preferably, in the second step, the pH of the reaction system is controlled by adding a second carbonate to the reaction system; the second carbonate comprises at least one of manganese carbonate, nickel carbonate and cobalt carbonate.
The addition of the second carbonate enables the pH value of the reaction system to be more than or equal to 5.0, impurity ions in the pickle liquor can be completely removed, and the generated aluminum hydroxide colloid can be stably present and not dissolved, so that the impurity aluminum ions are completely removed, no new impurity is introduced in the impurity removal process, and the impurity removal process is easier to filter than other methods.
Preferably, the acidic solution used for preparing the ternary acidic leaching solution comprises any one of sulfuric acid, hydrochloric acid and nitric acid, and the initial concentration of the hydrogen ions in the acidic leaching solution is more than 0.1mol/L, for example, 0.1mol/L, 0.12mol/L, 0.14mol/L, 0.16mol/L and 0.2mol/L, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, in the third solution, the loss rate of nickel ions in the third solution is equal to or less than 0.17wt%, for example, 0.17wt%, 0.15wt%, 0.13wt%, 0.11wt%, 0.09wt%, 0.05wt%, 0.01wt%, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable, the loss rate of cobalt ions is equal to or less than 0.39wt%, for example, 0.39wt%, 0.33wt%, 0.25wt%, 0.18wt%, 0.09wt%, 0.05wt%, 0.01wt%, but not limited to the recited values, and the loss rate of manganese ions is equal to or less than 0.45wt%, for example, 0.45wt%, 0.35wt%, 0.25wt%, 0.15wt%, 0.09wt%, 0.05wt%, and 0.01wt%, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
The method has the advantages that the quantity of the generated colloid is small, the quantity of valuable metal elements carried away by the colloid during filtering is reduced, the raw materials input during the impurity removing process contain the metal elements of ternary materials, the loss of the valuable metal caused by the filtering colloid can be compensated to a certain extent, and the loss rate of nickel ions, cobalt ions and manganese ions is reduced to an extremely low level.
Preferably, the content of the impurity copper ion in the third solution is 10ppm or less, for example, 10ppm, 8ppm, 6ppm, 5ppm, 4ppm, 3ppm, 1ppm, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable, and the content of the impurity aluminum ion is 30ppm or less, for example, 30ppm, 25ppm, 18ppm, 12ppm, 9ppm, 3ppm, 1ppm, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable, and the content of the impurity fluoride ion is 30ppm or less, for example, 30ppm, 25ppm, 18ppm, 12ppm, 9ppm, 3ppm, 1ppm, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
The third solution obtained by the method has high purity of the leaching solution, and the formed mother solution of nickel, cobalt and manganese can be used for preparing three materials again.
Preferably, the third solution can be used to recover mother liquor of nickel, cobalt and manganese to prepare ternary regenerated material again.
Drawings
Fig. 1 is a process flow diagram of an implementation of the method for removing impurities from an acid leaching solution of a waste ternary lithium battery.
Detailed Description
For a better understanding and implementation, the technical solutions of the present invention will be clearly and completely described below in connection with examples, it being obvious that the described examples are only some, but not all, examples of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximations that may vary depending upon the desired properties to be obtained.
As used herein, "and/or" means one or all of the elements mentioned.
The use of "including" and "comprising" herein encompasses both the situation in which only the elements are mentioned and the situation in which other elements not mentioned are present in addition to the elements mentioned.
All percentages in the present invention are by weight unless otherwise indicated.
As used in this specification, the terms "a," "an," "the," and "the" are intended to include "at least one" or "one or more," unless otherwise specified. For example, "a component" refers to one or more components, and thus more than one component may be considered and possibly employed or used in the practice of the embodiments.
Examples
Example 1
The defluorinating agent used in the embodiment is poly-N, N (trihydroxy silicon ureidopropyl) urea, and is prepared by the following steps:
Gamma-ureidopropyltriethoxysilane, hydrazine hydrate and 25wt% ammonia water are mixed according to the stoichiometric ratio of 2:1:1, heating at 30 ℃ for 72 hours to obtain poly N, N (trihydroxy silicon ureidopropyl) urea.
A method for removing impurities from acid leaching liquid of waste ternary lithium batteries comprises the following steps:
Step one: 1000mL of sulfuric acid leaching solution of the waste ternary lithium ion battery (namely ternary acid leaching solution) is taken, the initial pH value of the ternary acid leaching solution is 1, and the element content is shown in table 1; mixing the ternary acid leaching solution with hydrazine hydrate, wherein the stoichiometric ratio of the hydrazine hydrate to impurity copper ions in the ternary acid leaching solution is 2.5:1, reacting for 1h at 25 ℃ and filtering to obtain a first solution;
Step two: the first solution and manganese carbonate are mixed according to the weight ratio of 1:0.1, controlling the pH of the reaction system to be 6, reacting for 2 hours at 85 ℃, and filtering to obtain a second solution;
Step three: mixing the second solution with poly (N, N (trihydroxy silicon ureidopropyl) urea, wherein the weight ratio of poly (N, N (trihydroxy silicon ureidopropyl) urea to impurity fluoride ions in the second solution is 10:1, reacting at 65 ℃ for 1.2 hours, and filtering to obtain a third solution.
The loss rate of nickel, cobalt and manganese in the above-mentioned impurity removal process was 0.17wt%, 0.36wt% and 0.44wt%, respectively, and the contents of the respective elements in the first, second and third solutions were shown in table 1.
TABLE 1 solution composition Table of example 1 (mg/L)
Nickel loss ratio wt% = (nickel content in leachate-nickel content in third solution)/nickel content in leachate×100% = (79253.33 ×1000×10 -6-79277.15×998×10-6)/(79253.33×1000×10-6) ×100% = 0.17%;
Cobalt loss ratio wt% = (cobalt content in leachate-cobalt content in third solution)/cobalt content in leachate×100% = (20617.03 ×1000×10 -6-20583.98×998×10-6)/(20617.03×1000×10-6) ×100% = 0.36%;
Manganese loss ratio wt% = (manganese content in leachate+manganese carbonate content added in first solution-manganese content in third solution)/(manganese content in leachate+manganese carbonate content added in first solution) )×100％＝(10520.98×1000×10-6+1000×1.1×0.1/114.95×54.94-62943.41×998×10-6)/(10520.98×1000×10-6+1000×1.1×0.1/114.95×54.94)×100％＝0.44％;
Wherein the content of manganese carbonate added in the first solution = the volume of leachate x the density of the solution x 0.1 x the relative atomic mass of manganese/the relative molecular mass of manganese carbonate; the density of the solution refers to the density of the leaching solution, and the value is 1.1g/cm 3.
From the above table, the ternary acid leaching solution is subjected to step-by-step selective impurity removal in the embodiment, and then the molar ratio of nickel, cobalt and manganese in the system is adjusted to be reused for preparing the ternary material precursor.
Example 2
The fluorine removing agent used in the embodiment is lanthanum-loaded biochar, and is prepared by the following steps:
cleaning peanut shells, drying, crushing and screening to obtain pretreated powder with uniform particle size; the pretreated powder and lanthanum chloride heptahydrate are mixed according to the stoichiometric ratio of 5:2, mixing and placing the mixture in a beaker, adding water, stirring and mixing, and soaking for 15 minutes to obtain a soaked sample (the mass ratio of solid powder to water in the soaked sample is 15:1); and (3) placing the immersed sample in a 105 ℃ oven for drying for 3 hours, placing in a 500 ℃ muffle furnace for sintering for 1 hour, cooling after sintering, cleaning for 3 times by deionized water, and placing in the 105 ℃ oven for drying for 2 hours to obtain the lanthanum-loaded biochar.
A method for removing impurities from acid leaching liquid of waste ternary lithium batteries comprises the following steps:
Step one: 1000mL of sulfuric acid leaching solution of the waste ternary lithium ion battery (namely ternary acid leaching solution) is taken, the initial pH value of the ternary acid leaching solution is 1.2, and the element content is shown in table 2; mixing the ternary acid leaching solution with hydrazine hydrate, wherein the stoichiometric ratio of the hydrazine hydrate to impurity copper ions in the ternary acid leaching solution is 2.4:1, reacting at 26 ℃ for 0.5h, and filtering to obtain a first solution;
step two: the first solution and nickel carbonate are mixed according to the weight ratio of 1:0.15, controlling the pH of the reaction system to be 5.6, reacting for 3 hours at 80 ℃, and filtering to obtain a second solution;
Step three: mixing the second solution with the lanthanum-carrying biochar, wherein the weight ratio of the lanthanum-carrying biochar to impurity fluoride ions in the second solution is 3:1, reacting at 64 ℃ for 1.5 hours, and filtering to obtain a third solution.
The loss rate of nickel, cobalt and manganese in the above-mentioned impurity removal process was 0.17wt%, 0.36wt% and 0.42wt%, respectively, and the contents of the respective elements in the first, second and third solutions were shown in table 2.
TABLE 2 solution composition Table of example 2 (mg/L)
Nickel loss ratio wt% = (nickel content in leachate+nickel carbonate content added in first solution-nickel content in third solution)/(nickel content in leachate+nickel carbonate content added in first solution) )×100％＝(79194.25×1000×10-6+1000×1.1×0.15/118.7×58.69-163779.1×980×10-6)/(79194.25×1000×10-6+1000×1.1×0.15/118.7×58.69)×100％＝0.17％;
Cobalt loss ratio wt% = (cobalt content in leachate-cobalt content in third solution)/cobalt content in leachate×100% = (20526.7 ×1000×10 -6-20870.21×980×10-6)/(20526.7×1000×10-6) ×100% = 0.36%;
Manganese loss ratio wt% = (manganese content in leachate-manganese content in third solution)/manganese content in leachate×100% = (10441.76 ×1000×10 -6-10610.11×980×10-6)/(10441.76×1000×10-6) ×100% = 0.42%;
Wherein the content of nickel carbonate added in the first solution = volume of leachate x density of solution x 0.15 x relative atomic mass of nickel/relative molecular mass of nickel carbonate; the density of the solution refers to the density of the leaching solution, and the value is 1.1g/cm 3.
From the above table, the ternary acid leaching solution is subjected to step-by-step selective impurity removal in the embodiment, and then the molar ratio of nickel, cobalt and manganese in the system is adjusted to be reused for preparing the ternary material precursor.
Example 3
The defluorinating agent used in the embodiment is poly-N, N (trihydroxy silicon ureidopropyl) urea, and is prepared by the following steps:
Gamma-ureidopropyltriethoxysilane, hydrazine hydrate and 28wt% ammonia water are mixed according to the stoichiometric ratio of 3:2:1, heating at 35 ℃ for 65 hours to obtain poly N, N (trihydroxy silicon ureidopropyl) urea.
A method for removing impurities from acid leaching liquid of waste ternary lithium batteries comprises the following steps:
Step one: 1000mL of sulfuric acid leaching solution of the waste ternary lithium ion battery (namely ternary acid leaching solution) is taken, the initial pH value of the ternary acid leaching solution is 1.3, and the element content is shown in table 3; mixing the ternary acid leaching solution with hydrazine hydrate, wherein the stoichiometric ratio of the hydrazine hydrate to impurity copper ions in the ternary acid leaching solution is 2.6:1, reacting for 1h at 24 ℃ and filtering to obtain a first solution;
step two: the first solution and cobalt carbonate are mixed according to the weight ratio of 1:0.12, controlling the pH of the reaction system to be 5.2, reacting for 2 hours at 90 ℃, and filtering to obtain a second solution;
Step three: mixing the second solution with poly (N, N (trihydroxy silicon ureidopropyl) urea, wherein the weight ratio of poly (N, N (trihydroxy silicon ureidopropyl) urea to impurity fluoride ions in the second solution is 8:1, after reaction at 66 ℃ for 1h, filtering to obtain a third solution.
The loss rate of nickel, cobalt and manganese in the above-mentioned impurity removal process was 0.16wt%, 0.38wt% and 0.43wt%, respectively, and the contents of the respective elements in the first, second and third solutions were shown in table 3.
TABLE 3 solution composition Table of example 3 (mg/L)
Nickel loss ratio wt% = (nickel content in leachate-nickel content in third solution)/nickel content in leachate×100% = (79174.32 ×1000×10 -6-80660.86×980×10-6)/(79174.32×1000×10-6) ×100% = 0.16%;
Cobalt loss ratio wt% = (cobalt content in leachate+cobalt carbonate content added in first solution-cobalt content in third solution)/(cobalt content in leachate+cobalt carbonate content added in first solution) )×100％＝(20476.2×1000×10-6+1000×1.1×0.12/118.94×58.93-87296.5×980×10-6)/(20476.2×1000×10-6+1000×1.1×0.12/118.94×58.93)×100％＝0.38％;
Manganese loss ratio wt% = (manganese content in leachate-manganese content in third solution)/manganese content in leachate×100% = (10433.52 ×1000×10 -6-10600.67×980×10-6)/(10433.52×1000×10-6) ×100% = 0.43%;
Wherein the content of cobalt carbonate added in the first solution = volume of leach solution x density of solution x 0.12 x relative atomic mass of cobalt/relative molecular mass of cobalt carbonate; the density of the solution refers to the density of the leaching solution, and the value is 1.1g/cm 3.
From the above table, the ternary acid leaching solution is subjected to step-by-step selective impurity removal in the embodiment, and then the molar ratio of nickel, cobalt and manganese in the system is adjusted to be reused for preparing the ternary material precursor.
Example 4
The defluorinating agent used in the embodiment is poly-N, N (trihydroxy silicon ureidopropyl) urea, and is prepared by the following steps:
Gamma-ureidopropyltriethoxysilane, hydrazine hydrate and 25wt% ammonia water are mixed according to the stoichiometric ratio of 2:1:1, heating at 30 ℃ for 72 hours to obtain poly N, N (trihydroxy silicon ureidopropyl) urea.
The fluorine removing agent used in the embodiment is lanthanum-loaded biochar, and is prepared by the following steps:
Cleaning peanut shells, drying, crushing and screening to obtain pretreated powder with uniform particle size; the pretreated powder and lanthanum chloride heptahydrate are mixed according to the stoichiometric ratio of 10:3, mixing and placing the mixture in a beaker, adding water, stirring and mixing, and soaking for 10 minutes to obtain a soaked sample (the mass ratio of solid powder to water in the soaked sample is 10:1); and (3) placing the immersed sample in a 110 ℃ oven for drying for 2 hours, placing in a 550 ℃ muffle furnace for sintering for 1 hour, cooling after sintering, cleaning for 3 times by deionized water, and placing in a 100 ℃ oven for drying for 3 hours to obtain the lanthanum-loaded biochar.
A method for removing impurities from acid leaching liquid of waste ternary lithium batteries comprises the following steps:
Step one: 1000mL of sulfuric acid leaching solution of the waste ternary lithium ion battery (namely ternary acid leaching solution) is taken, the initial pH value of the ternary acid leaching solution is 1, and the element content is shown in table 4; mixing the ternary acid leaching solution with hydrazine hydrate, wherein the stoichiometric ratio of the hydrazine hydrate to impurity copper ions in the ternary acid leaching solution is 2.5:1, reacting at 25 ℃ for 0.8h, and filtering to obtain a first solution;
step two: the first solution and manganese carbonate are mixed according to the weight ratio of 1:0.14, controlling the pH of the reaction system to be 5.5, reacting for 2.5 hours at 85 ℃, and filtering to obtain a second solution;
Step three: mixing the second solution with a fluorine removing agent (the mass ratio of poly-N, N (trihydroxy-silicon ureidopropyl) urea to lanthanum-carrying biochar in the fluorine removing agent is 1:1), wherein the weight ratio of poly-N, N (trihydroxy-silicon ureidopropyl) urea to lanthanum-carrying biochar to impurity fluoride ions in the second solution is 6:1, reacting at 65 ℃ for 1.2 hours, and filtering to obtain a third solution.
The loss rate of nickel, cobalt and manganese in the above-mentioned impurity removal process was 0.17wt%, 0.39wt% and 0.45wt%, respectively, and the contents of the respective elements in the first, second and third solutions were shown in table 4.
TABLE 4 Table 4 solution composition of example 4 (mg/L)
Nickel loss ratio wt% = (nickel content in leachate-nickel content in third solution)/nickel content in leachate×100% = (79253.33 ×1000×10 -6-79676.33×993×10-6)/(79253.33×1000×10-6) ×100% = 0.17%;
Cobalt loss ratio wt% = (cobalt content in leachate-cobalt content in third solution)/cobalt content in leachate×100% = (20617.03 ×1000×10 -6-20681.39×993×10-6)/(20617.03×1000×10-6) ×100% = 0.39%;
Manganese loss ratio wt% = (manganese content in leachate+manganese carbonate content added in first solution-manganese content in third solution)/(manganese content in leachate+manganese carbonate content added in first solution) )×100％＝(10520.98×1000×10-6+1000×1.1×0.14/114.95×54.94-84336.6×993×10-6)/(10520.98×1000×10-6+1000×1.1×0.14/114.95×54.94)×100％＝0.45％;
Wherein the content of manganese carbonate added in the first solution = volume of leachate x density of solution x 0.14 x relative atomic mass of manganese/relative molecular mass of manganese carbonate; the density of the solution refers to the density of the leaching solution, and the value is 1.1g/cm 3.
From the above table, the ternary acid leaching solution is subjected to step-by-step selective impurity removal in the embodiment, and then the molar ratio of nickel, cobalt and manganese in the system is adjusted to be reused for preparing the ternary material precursor.
Example 5
The fluorine scavenger used in this example was poly N, N (trishydroxy silylurypropyl) urea and was identical to the procedure for the preparation of poly N, N (trishydroxy silylurypropyl) urea in example 1.
A method for removing impurities from acid leaching liquid of waste ternary lithium batteries comprises the following steps:
step one: 1000mL of sulfuric acid leaching solution of the waste ternary lithium ion battery (namely ternary acid leaching solution) is taken, the initial pH value of the ternary acid leaching solution is 1, and the element content is shown in table 5; mixing the ternary acid leaching solution with hydrazine hydrate, wherein the stoichiometric ratio of the hydrazine hydrate to impurity copper ions in the ternary acid leaching solution is 2.5:1, reacting at 25 ℃ for 1h, and then carrying out solid-liquid separation to obtain a first solution;
Step two: the first solution and the ferric carbonate are mixed according to the weight ratio of 1:0.1, controlling the pH of the reaction system to be 5.5, reacting at 85 ℃ for 2 hours, and then carrying out solid-liquid separation to obtain a second solution;
Step three: mixing the second solution with poly (N, N (trihydroxy silicon ureidopropyl) urea and lanthanum-carrying biochar, wherein the weight ratio of the poly (N, N (trihydroxy silicon ureidopropyl) urea to lanthanum-carrying biochar to impurity fluoride ions in the second solution is 10:1, reacting at 65 ℃ for 1.2 hours, and then carrying out solid-liquid separation to obtain a third solution.
The loss rate of nickel, cobalt and manganese in the above-mentioned impurity removal process was 1.14wt%, 1.35wt% and 2.41wt%, respectively, and the contents of the respective elements in the first, second and third solutions were shown in table 5.
TABLE 5 solution composition Table of example 5 (mg/L)
Nickel loss wt% = (nickel content in leachate-nickel content in third solution)/nickel content in leachate x 100% = (79253.33 x 1000 x 10 -6-77574.1×1010×10-6)/(79253.33×1000×10-6) x100% = 1.14%;
cobalt loss wt% = (cobalt content in leachate-cobalt content in third solution)/cobalt content in leachate x 100% = (20617.03 x 1000 x 10 -6-20137.33×1010×10-6)/(20617.03×1000×10-6) x100% = 1.35%;
manganese loss ratio wt% = (manganese content in leachate-manganese content in third solution)/manganese content in leachate×100% = (10520.98 ×1000×10× 10 -6-10165.77×1010×10-6)/(10520.98×1000×10-6) ×100% = 2 41%;
From the table, after the ternary acid leaching solution is subjected to step-by-step selective impurity removal in the embodiment, the iron carbonate introduced in the second step introduces impurity iron into the reaction system while controlling the pH value of the reaction system, so that the weight of the colloid generated in the second step can be increased to a certain extent, the amount of nickel, cobalt and manganese adsorbed by the colloid is increased, and the loss of nickel, cobalt and manganese in the impurity removal process is increased.
Comparative example 1
A method for removing impurities from acid leaching liquid of waste ternary lithium batteries comprises the following steps:
Step one: 1000mL of sulfuric acid leaching solution of the waste ternary lithium ion battery (namely ternary acid leaching solution) is taken, the initial pH value of the ternary acid leaching solution is 1, and the element content is shown in Table 6; mixing the ternary acid leaching solution with iron powder, wherein the stoichiometric ratio of the iron powder to impurity copper ions in the ternary acid leaching solution is 1.2:1, reacting for 1h at 25 ℃ and filtering to obtain a first solution;
Step two: mixing the first solution with hydrogen peroxide (the hydrogen peroxide dosage is 1.2 times of the theoretical dosage of ferrous oxide ions), and then mixing the first solution with manganese carbonate according to the weight ratio of 1:0.14, controlling the pH of the reaction system to be 5.5, reacting for 2.5 hours at 85 ℃, and filtering to obtain a second solution;
Step three: mixing the second solution with aluminum sulfate, wherein the weight ratio of aluminum sulfate to impurity fluoride ions in the second solution is 30:1, reacting at 65 ℃ for 1.2 hours, and filtering to obtain a third solution.
The loss rate of nickel, cobalt and manganese in the above-mentioned impurity removal process was 1.25wt%, 1.39wt% and 2.45wt%, respectively, and the contents of the respective elements in the first, second and third solutions were shown in table 6.
TABLE 6 solution composition Table (mg/L) of comparative example 1
Nickel loss wt% = (nickel content in leachate-nickel content in third solution)/nickel content in leachate x 100% = (79253.33 x 1000 x 10 -6-78262.66×1000×10-6)/(79253.33×1000×10-6) x100% = 1 25%;
cobalt loss wt% = (cobalt content in leachate-cobalt content in third solution)/cobalt content in leachate x 100% = (20617.03 x 1000 x 10 x -6-20330.45×1000×10-6)/(20617.03×1000×10-6) x100% = 1 39%;
Manganese loss ratio wt% = (manganese content in leachate+manganese carbonate content added in first solution-manganese content in third solution)/(manganese content in leachate+manganese carbonate content added in first solution) )×100％＝(10520.98×1000×10-6+1000×1.1×0.14/114.95×54.94-82063.75×1000×10-6)/(10520.98×1000×10-6+1000×1.1×0.14/114.95×54.94)×100％＝2.45％;
Wherein the content of manganese carbonate added in the first solution = volume of leachate x density of solution x 0.14 x relative atomic mass of manganese/relative molecular mass of manganese carbonate; the density of the solution refers to the density of the leaching solution, and the value is 1.1g/cm 3.
From the above table, after the ternary acid leaching solution is subjected to step-by-step selective impurity removal in the comparative example, iron ions and aluminum ions introduced in the impurity removal process can generate ferric hydroxide colloid and aluminum hydroxide colloid, and a large amount of nickel, cobalt and manganese can be adsorbed in the impurity removal process, so that serious loss of nickel, cobalt and manganese is generated.
Comparative example 2
The fluorine scavenger used in this comparative example was poly N, N (trishydroxy silylurypropyl) urea, and was identical to the procedure for the preparation of poly N, N (trishydroxy silylurypropyl) urea in example 1.
A method for removing impurities from acid leaching liquid of waste ternary lithium batteries comprises the following steps:
Step one: 1000mL of sulfuric acid leaching solution of the waste ternary lithium ion battery (namely ternary acid leaching solution) is taken, the initial pH value of the ternary acid leaching solution is 1, and the element content is shown in Table 7; mixing the ternary acid leaching solution with iron powder, wherein the stoichiometric ratio of the iron powder to impurity copper ions in the ternary acid leaching solution is 1.2:1, reacting for 1h at 25 ℃ and filtering to obtain a first solution;
Step two: mixing the first solution with hydrogen peroxide (the hydrogen peroxide dosage is 1.2 times of the theoretical dosage of ferrous oxide ions), and then mixing the first solution with manganese carbonate according to the weight ratio of 1:0.1, controlling the pH of the reaction system to be 5.5, reacting for 2 hours at 85 ℃, and filtering to obtain a second solution;
step three: mixing the second solution with poly (N, N (trihydroxy silicon ureidopropyl) urea, wherein the weight ratio of poly (N, N (trihydroxy silicon ureidopropyl) urea to impurity fluoride ions in the second solution is 10:1, reacting at 65 ℃ for 1h, and filtering to obtain a third solution.
The loss rate of nickel, cobalt and manganese in the above-mentioned impurity removal process was 0.96wt%, 1.03wt% and 1.31wt%, respectively, and the contents of the respective elements in the first, second and third solutions were shown in table 7.
TABLE 7 solution composition Table (mg/L) of comparative example 2
Nickel loss ratio wt% = (nickel content in leachate-nickel content in third solution)/nickel content in leachate×100% = (79253.33 ×1000×10 -6-77715.34×1010×10-6)/(79253.33×1000×10-6) ×100% = 0.96%;
Cobalt loss ratio wt% = (cobalt content in leachate-cobalt content in third solution)/cobalt content in leachate×100% = (20617.03 ×1000×10 -6-20202.65×1010×10-6)/(20617.03×1000×10-6) ×100% = 1.03%;
manganese loss ratio wt% = (manganese content in leachate+manganese carbonate content added in first solution-manganese content in third solution)/(manganese content in leachate+manganese carbonate content added in first solution) )×100％＝(10520.98×1000×10-6+1000×1.1×0.1/114.95×54.94-61652.08×1010×10-6)/(10520.98×1000×10-6+1000×1.1×0.1/114.95×54.94)×100％＝1.31％;
Wherein the content of manganese carbonate added in the first solution = the volume of leachate x the density of the solution x 0.1 x the relative atomic mass of manganese/the relative molecular mass of manganese carbonate; the density of the solution refers to the density of the leaching solution, and the value is 1.1g/cm 3.
As can be seen from the above table, after the step-by-step selective impurity removal of the ternary acidic leaching solution in the comparative example, although the impurity content in the finally obtained third solution can meet the recovery requirement, iron ions are introduced into the system in the first step, and the iron ions can generate ferric hydroxide colloid to adsorb nickel, cobalt and manganese in the ternary acidic leaching solution in the second step, so that the loss of nickel, cobalt and manganese in the impurity removal process is excessive.
Comparative example 3
A method for removing impurities from acid leaching liquid of waste ternary lithium batteries comprises the following steps:
Step one: 1000mL of sulfuric acid leaching solution of the waste ternary lithium ion battery (namely ternary acid leaching solution) is taken, the initial pH value of the ternary acid leaching solution is 1, and the element content is shown in Table 8; mixing the ternary acid leaching solution with hydrazine hydrate, wherein the stoichiometric ratio of the hydrazine hydrate to impurity copper ions in the ternary acid leaching solution is 2.5:1, reacting for 1h at 25 ℃ and filtering to obtain a first solution;
Step two: the first solution and manganese carbonate are mixed according to the weight ratio of 1:0.1, controlling the pH of the reaction system to be 5.5, reacting for 2 hours at 85 ℃, and filtering to obtain a second solution;
step three: mixing the second solution with aluminum sulfate, wherein the weight ratio of aluminum sulfate to impurity fluoride ions in the second solution is 30:1, reacting at 65 ℃ for 1h, and filtering to obtain a third solution.
The loss rate of nickel, cobalt and manganese in the above-mentioned impurity removal process was 0.66wt%, 0.71wt% and 0.80wt%, respectively, and the contents of the respective elements in the first, second and third solutions were shown in table 8.
TABLE 8 solution composition Table of comparative example 3 (mg/L)
Nickel loss ratio wt% = (nickel content in leachate-nickel content in third solution)/nickel content in leachate×100% = (79253.33 ×1000×10 -6-77566.76×1015×10-6)/(79253.33×1000×10-6) ×100% = 0.66%;
cobalt loss ratio wt% = (cobalt content in leachate-cobalt content in third solution)/cobalt content in leachate×100% = (20617.03 ×1000×10 -6-20168.13×1015×10-6)/(20617.03×1000×10-6) ×100% = 0.71%;
manganese loss ratio wt% = (manganese content in leachate+manganese carbonate content added in first solution-manganese content in third solution)/(manganese content in leachate+manganese carbonate content added in first solution) )×100％＝(10520.98×1000×10-6+1000×1.1×0.1/114.95×54.94-61665.4×1015×10-6)/(10520.98×1000×10-6+1000×1.1×0.1/114.95×54.94)×100％＝0.80％;
Wherein the content of manganese carbonate added in the first solution = the volume of leachate x the density of the solution x 0.1 x the relative atomic mass of manganese/the relative molecular mass of manganese carbonate; the density of the solution refers to the density of the leaching solution, and the value is 1.1g/cm 3.
From the above table, after the ternary acid leaching solution is subjected to step-by-step selective impurity removal in the comparative example, although the impurity content in the finally obtained third solution can meet the recovery requirement, aluminum sulfate can generate aluminum hydroxide colloid in a reaction system when being used as a fluorine removing agent, and nickel, cobalt and manganese in the acid leaching solution can be adsorbed while fluorine ions are adsorbed, so that the loss of nickel, cobalt and manganese in the impurity removal process is excessive.
Comparative example 4
The fluorine scavenger used in this comparative example was poly N, N (trishydroxy silylurypropyl) urea, and was identical to the procedure for the preparation of poly N, N (trishydroxy silylurypropyl) urea in example 1.
A method for removing impurities from acid leaching liquid of waste ternary lithium batteries comprises the following steps:
Step one: 1000mL of sulfuric acid leaching solution of the waste ternary lithium ion battery (namely ternary acid leaching solution) is taken, the initial pH value of the ternary acid leaching solution is 1, and the element content is shown in Table 9; mixing the ternary acid leaching solution with hydrazine hydrate, wherein the stoichiometric ratio of the hydrazine hydrate to impurity copper ions in the ternary acid leaching solution is 2.5:1, reacting for 1h at 25 ℃ and filtering to obtain a first solution;
Step two: the first solution and manganese carbonate are mixed according to the weight ratio of 1:0.1, adding a proper amount of dilute sulfuric acid to control the pH of the reaction system to 3.5, reacting at 85 ℃ for 2 hours, and filtering to obtain a second solution;
step three: mixing the second solution with poly (N, N (trihydroxy silicon ureidopropyl) urea, wherein the weight ratio of poly (N, N (trihydroxy silicon ureidopropyl) urea to impurity fluoride ions in the second solution is 10:1, reacting at 65 ℃ for 1h, and filtering to obtain a third solution.
The loss rate of nickel, cobalt and manganese in the above-mentioned impurity removal process was 0.11wt%, 0.11wt% and 0.37wt%, respectively, and the contents of the respective elements in the first, second and third solutions were shown in table 9.
TABLE 9 solution composition Table (mg/L) of comparative example 4
Nickel loss ratio wt% = (nickel content in leachate-nickel content in third solution)/nickel content in leachate×100% = (79253.33 ×1000×10 -6-79965.81×990×10-6)/(79253.33×1000×10-6) ×100% = 0.11%;
Cobalt loss ratio wt% = (cobalt content in leachate-cobalt content in third solution)/cobalt content in leachate×100% = (20617.03 ×1000×10 -6-20802.38×990×10-6)/(20617.03×1000×10-6) ×100% = 0.11%;
Manganese loss ratio wt% = (manganese content in leachate+manganese carbonate content added in first solution-manganese content in third solution)/(manganese content in leachate+manganese carbonate content added in first solution) )×100％＝(10520.98×1000×10-6+1000×1.1×0.1/114.95×54.94-63496.66×990×10-6)/(10520.98×1000×10-6+1000×1.1×0.1/114.95×54.94)×100％＝0.37％;
Wherein the content of manganese carbonate added in the first solution = the volume of leachate x the density of the solution x 0.1 x the relative atomic mass of manganese/the relative molecular mass of manganese carbonate; the density of the solution refers to the density of the leaching solution, and the value is 1.1g/cm 3.
From the above table, the pH value of the reaction system in the second step of the step-by-step selective impurity removal of the ternary acidic leaching solution in this embodiment is too low, so that the aluminum and fluorine impurities in the acidic leaching solution cannot be effectively removed, and the aluminum and fluorine contents in the third solution exceed the recovery standard.
Test method
1. Testing of the content of elemental aluminum in solution
Analyzing the content of aluminum element in the solution by using inductively coupled plasma spectrometry (ICP-OES); the ICP-OES instrument used in the application is OPTIMA 8000 (Perkinelmer Co., U.S.A.), which is mainly used for measuring the concentration of metallic element aluminum in the leaching solution.
2. Fluorine content test in solution
IC is a liquid chromatography method for separating and detecting by utilizing the ionic nature of a substance to be detected, and is mainly used for analyzing the mass concentration of anions and cations in a solution. The IC instrument used in this experiment was ICS-5000 (American thermoelectric instruments Co.) and was used to measure the mass concentration of nonmetallic fluorine in the leachate.
3. Testing the content of nickel, cobalt, manganese, copper and iron elements in the solution
Analyzing the content of nickel, cobalt, manganese, copper and iron elements in the solution by using Atomic Absorption Spectrophotometry (AAS); AAS is a metal elemental analysis that quantifies the effect of atomic vapors in the ground state of matter on the absorption of characteristic radiation. The AAS instrument used in the experiment is 4510F (Shanghai electric instruments Co., ltd.) and is mainly used for measuring the mass concentration of metallic elements of nickel, cobalt, manganese, copper and iron in the leaching solution.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention, but these modifications or substitutions are all within the scope of the present invention.
Claims (11)
1. A method for removing impurities from acid leaching liquid of waste ternary lithium batteries is characterized by comprising the following steps: the method comprises the following steps:
step one: mixing the ternary acid leaching solution with hydrazine hydrate, wherein the stoichiometric ratio of the hydrazine hydrate to impurity copper ions in the ternary acid leaching solution is 2.4-2.6:1, carrying out solid-liquid separation after reaction to obtain a first solution;
step two: the first solution and the first carbonate are mixed according to the weight ratio of 1: mixing 0.1-0.15, controlling the pH of the reaction system to be more than or equal to 5.0, and carrying out solid-liquid separation after the reaction to obtain a second solution;
Step three: mixing the second solution with a fluorine removing agent, wherein the weight ratio of the fluorine removing agent to impurity fluorine ions in the second solution is 3-10:1, carrying out solid-liquid separation after the reaction to obtain a third solution;
wherein the defluorinating agent comprises any one of poly N, N (trihydroxy silicon ureidopropyl) urea and lanthanum-carrying biochar.
2. The method for removing impurities from the acid leaching solution of the waste ternary lithium battery according to claim 1, which is characterized by comprising the following steps: the poly-N, N (trihydroxy silicon ureidopropyl) urea is prepared by adopting a method comprising the following steps: mixing gamma-ureidopropyl triethoxysilane, hydrazine hydrate and a catalyst, and heating to obtain the poly-N, N (trihydroxy silicon ureidopropyl) urea.
3. The method for removing impurities from the acid leaching solution of the waste ternary lithium battery according to claim 2, which is characterized by comprising the following steps: the stoichiometric ratio of the gamma-ureidopropyltriethoxysilane, the hydrazine hydrate and the catalyst is 2-3:1-2:1, a step of; the heating temperature is 30-35 ℃, and the heating time is 65-72h.
4. The method for removing impurities from the acid leaching solution of the waste ternary lithium battery according to claim 1, which is characterized by comprising the following steps: the lanthanum-loaded biochar is prepared by a method comprising the following steps: cleaning, drying and crushing the biological matrix to obtain pretreated powder; the pretreated powder is mixed with lanthanum chloride heptahydrate according to the stoichiometric ratio of 5-8:2-2.5, adding water, and soaking to obtain a soaked sample; and drying, sintering and cooling the immersed sample to obtain the lanthanum-carrying biochar.
5. The method for removing impurities from the acid leaching solution of the waste ternary lithium battery according to claim 4, which is characterized in that: the biological matrix comprises at least one of peanut shell, rice shell, walnut shell, oak shell, bagasse, red residue, soybean residue, straw pine needle, pine cone and fruit branch; the stoichiometric ratio of the pretreatment powder to the lanthanum chloride heptahydrate is 5-10:2-3; the temperature in the sintering process is 450-550 ℃, and the sintering time is 1-1.5h.
6. The method for removing impurities from the acid leaching solution of the waste ternary lithium battery according to claim 1, which is characterized by comprising the following steps: the reaction temperature in the first step is 24-26 ℃ and the reaction time is 0.5-1h; the reaction temperature in the second step is 80-90 ℃ and the reaction time is 2-3h; the reaction temperature in the third step is 64-66 ℃, and the reaction time is 1-1.5h.
7. The method for removing impurities from the acid leaching solution of the waste ternary lithium battery according to claim 1, which is characterized by comprising the following steps: the first carbonate used in the second step comprises at least one of manganese carbonate, nickel carbonate and cobalt carbonate.
8. The method for removing impurities from the acid leaching solution of the waste ternary lithium battery according to claim 1, which is characterized by comprising the following steps: in the second step, the pH of the reaction system is controlled by adding a second carbonate into the reaction system; the second carbonate comprises at least one of manganese carbonate, nickel carbonate and cobalt carbonate.
9. The method for removing impurities from the acid leaching solution of the waste ternary lithium battery according to claim 1, which is characterized by comprising the following steps: the acidic solution used for preparing the ternary acidic leaching solution comprises any one of sulfuric acid, hydrochloric acid and nitric acid, and the initial concentration of the hydrogen ions in the acidic leaching solution is more than 0.1mol/L.
10. The method for removing impurities from the acid leaching solution of the waste ternary lithium battery according to any one of claims 1 to 9, which is characterized by comprising the following steps: in the third solution, the loss rate of nickel ions is less than or equal to 0.17wt%, the loss rate of cobalt ions is less than or equal to 0.39wt%, and the loss rate of manganese ions is less than or equal to 0.45wt%.
11. The method for removing impurities from the acid leaching solution of the waste ternary lithium battery according to any one of claims 1 to 9, which is characterized by comprising the following steps: in the third solution, the content of the impurity copper ions is less than or equal to 10ppm, the content of the impurity aluminum ions is less than or equal to 30ppm, and the content of the impurity fluorine ions is less than or equal to 30ppm.
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