CN112342383B - Separation and recovery method of nickel, cobalt, manganese and lithium in ternary waste - Google Patents
Separation and recovery method of nickel, cobalt, manganese and lithium in ternary waste Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 75
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 67
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000002699 waste material Substances 0.000 title claims abstract description 64
- 239000011572 manganese Substances 0.000 title claims abstract description 59
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 43
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000000926 separation method Methods 0.000 title claims abstract description 30
- 239000010941 cobalt Substances 0.000 title claims abstract description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000011084 recovery Methods 0.000 title claims description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 98
- 239000000243 solution Substances 0.000 claims abstract description 82
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 74
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000002002 slurry Substances 0.000 claims abstract description 59
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000001556 precipitation Methods 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 26
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 24
- 238000005649 metathesis reaction Methods 0.000 claims abstract description 22
- 239000012045 crude solution Substances 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 238000004537 pulping Methods 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 14
- 239000012445 acidic reagent Substances 0.000 claims abstract description 7
- 230000032683 aging Effects 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 69
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 37
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 28
- -1 hydrogen ions Chemical class 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910001437 manganese ion Inorganic materials 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 239000002893 slag Substances 0.000 claims description 5
- 229910018661 Ni(OH) Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 5
- 239000003513 alkali Substances 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 description 24
- 238000002386 leaching Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- 238000001914 filtration Methods 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- 229940085991 phosphate ion Drugs 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 6
- YUCQNFPMKWVCCP-UHFFFAOYSA-H cobalt(2+) manganese(2+) nickel(2+) diphosphate Chemical compound P(=O)([O-])([O-])[O-].[Ni+2].[Co+2].[Mn+2].P(=O)([O-])([O-])[O-] YUCQNFPMKWVCCP-UHFFFAOYSA-H 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 3
- 229910013716 LiNi Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 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 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000159 nickel phosphate Inorganic materials 0.000 description 1
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- 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
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- 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
-
- 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
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- 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
- C22B47/00—Obtaining manganese
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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Abstract
本发明属于锂电池回收技术领域，公开了一种三元废料中镍钴锰与锂的分离回收方法，具体包括以下步骤：(1)含锂溶液的制取：将三元废料加水制浆，制浆后加入磷酸混合溶液调节浆液pH<4，然后加入还原剂进行反应，反应完全后加入碱试剂A调节pH至7.0～11.0，然后分离得到含锂溶液和滤渣A；(2)镍钴锰精制溶液的制取：将步骤(1)得到的滤渣A加水进行制浆，制浆后加入三价铁盐进行复分解反应，反应完成后加酸试剂调节体系pH至1.9～2.0，进行陈化、分离得到镍钴锰粗溶液和滤渣B，继续往镍钴锰粗溶液加入碱试剂B调节pH至4.0～5.0进行沉淀，分离得到镍钴锰精制溶液和滤渣C。
The invention belongs to the technical field of lithium battery recycling, and discloses a method for separating and recycling nickel, cobalt, manganese and lithium in ternary waste, which specifically includes the following steps: (1) preparation of a lithium-containing solution: adding water to the ternary waste to make pulp, After pulping, phosphoric acid mixed solution is added to adjust the pH of the slurry to <4, and then a reducing agent is added for the reaction. After the reaction is complete, an alkali reagent A is added to adjust the pH to 7.0-11.0, and then the lithium-containing solution and filter residue A are obtained by separation; (2) Nickel-Cobalt-Manganese Preparation of the refined solution: adding water to the filter residue A obtained in step (1) for pulping, adding ferric salt to carry out metathesis reaction after pulping, adding an acid reagent to adjust the pH of the system to 1.9-2.0 after the reaction is completed, and performing aging, The nickel-cobalt-manganese crude solution and the filter residue B are obtained by separation, and the alkaline reagent B is added to the nickel-cobalt-manganese crude solution to adjust the pH to 4.0-5.0 for precipitation, and the nickel-cobalt-manganese refined solution and the filter residue C are obtained by separation.
Description
技术领域technical field
本发明涉及锂电池回收技术领域，特别是涉及一种三元废料中镍钴锰与锂的分离回收方法。The invention relates to the technical field of lithium battery recycling, in particular to a method for separating and recycling nickel, cobalt, manganese and lithium in ternary waste.
背景技术Background technique
随着电动汽车和大规模储能市场的快速发展，锂离子电池的销量快速增长，随之产生的废旧锂离子电池数量也日益增长。其中，三元正极锂离子电池含有镍、钴、锰、锂等有价金属，具有较高的回收价值。在湿法冶金技术中，废旧锂离子电池正极材料浸出后，有价金属元素均以离子态存在于浸出液中，如进一步资源化，需选择性地将不同的有价金属镍、钴、锰、锂等进行分离。With the rapid development of the electric vehicle and large-scale energy storage market, the sales of lithium-ion batteries are increasing rapidly, and the amount of waste lithium-ion batteries is also increasing. Among them, the ternary cathode lithium-ion battery contains valuable metals such as nickel, cobalt, manganese, and lithium, and has high recycling value. In the hydrometallurgical technology, after leaching the cathode material of waste lithium-ion batteries, the valuable metal elements exist in the leaching solution in the ionic state. Lithium, etc. are separated.
现有的三元废料中镍钴锰与锂分离技术是：将三元废料进行还原浸出，得到镍、钴、锰、锂四种金属元素的硫酸盐溶液，然后采用P204或P507作为萃取剂、260#溶剂油作为稀释剂，将镍、钴、锰三种元素一次性萃取走，然后再采用硫酸溶液反萃，得到含镍、钴、锰三种元素的硫酸盐溶液，从而实现镍钴锰与锂元素的分离。但是萃取过程繁琐、效率低下，且需要使用大量的萃取试剂，其价格高、废盐量大易污染环境、有机溶剂易挥发导致操作条件较差，同时该分离技术得到的含锂溶液中钠含量较高，难以直接用于制备高纯锂盐产品。The separation technology of nickel, cobalt, manganese and lithium in the existing ternary waste is as follows: reducing and leaching the ternary waste to obtain a sulfate solution of four kinds of metal elements of nickel, cobalt, manganese and lithium, and then using P204 or P507 as extractant, 260# solvent oil is used as a diluent to extract the three elements of nickel, cobalt and manganese at one time, and then back-extract with sulfuric acid solution to obtain a sulfate solution containing three elements of nickel, cobalt and manganese, so as to realize nickel, cobalt and manganese. Separation from Lithium. However, the extraction process is cumbersome, low in efficiency, and requires a large amount of extraction reagents. The high price, the large amount of waste salt, and the easy pollution of the environment, and the volatile organic solvents lead to poor operating conditions. At the same time, the sodium content in the lithium-containing solution obtained by this separation technology It is difficult to directly use it to prepare high-purity lithium salt products.
因此，进一步开发低成本、绿色化、高效率、可工业化的镍钴锰与锂分离技术是当前三元废料中有价金属回收领域需要解决的问题。Therefore, the further development of low-cost, green, high-efficiency, and industrializable nickel-cobalt-manganese and lithium separation technology is a problem that needs to be solved in the field of valuable metal recovery from ternary waste.
发明内容SUMMARY OF THE INVENTION
为了克服上述现有技术的缺点与不足，本发明目的是提供一种工艺简单、绿色环保、高效率的三元废料中镍钴锰与锂的分离回收方法。In order to overcome the shortcomings and deficiencies of the above-mentioned prior art, the purpose of the present invention is to provide a method for separating and recovering nickel, cobalt, manganese and lithium in ternary wastes with simple process, green environmental protection and high efficiency.
为实现上述发明目的，本发明采用如下技术方案：For realizing the above-mentioned purpose of the invention, the present invention adopts following technical scheme:
一种三元废料中镍钴锰与锂的分离回收方法，包括以下步骤：A method for separating and recovering nickel, cobalt, manganese and lithium in a ternary waste material, comprising the following steps:
(1)含锂溶液的制取：将三元废料加水制浆，制浆后加入磷酸混合溶液调节浆液pH<4，然后加入还原剂进行反应，反应完全后加入碱试剂A调节pH至7.0～11.0，然后分离得到含锂溶液和滤渣A；(1) Preparation of lithium-containing solution: add water to the ternary waste to make pulp, add phosphoric acid mixed solution after pulping to adjust the pH of the slurry to <4, then add a reducing agent to react, and after the reaction is complete, add alkaline reagent A to adjust the pH to 7.0～ 11.0, then separate to obtain lithium-containing solution and filter residue A;
(2)镍钴锰精制溶液的制取：将步骤(1)得到的滤渣A加水进行制浆，制浆后加入三价铁盐进行复分解反应，反应完成后加酸试剂调节体系pH至1.9～2.0，进行陈化、分离得到镍钴锰粗溶液和滤渣B，继续往镍钴锰粗溶液加入碱试剂B调节pH至4.0～5.0进行沉淀，分离得到镍钴锰精制溶液和滤渣C。(2) Preparation of nickel-cobalt-manganese refined solution: adding water to the filter residue A obtained in step (1) for pulping, adding ferric salt to carry out metathesis reaction after pulping, and adding acid reagent after the reaction is completed to adjust the pH of the system to 1.9～ 2.0, carry out aging and separation to obtain nickel-cobalt-manganese crude solution and filter residue B, continue to add alkali reagent B to the nickel-cobalt-manganese crude solution to adjust pH to 4.0-5.0 for precipitation, and separate to obtain nickel-cobalt-manganese refined solution and filter residue C.
优选的，步骤(1)中所述的三元废料与水的液固比为1.5:1～10:1。Preferably, the liquid-solid ratio of the ternary waste material and water described in step (1) is 1.5:1 to 10:1.
优选的，步骤(1)中所述的制浆可采用搅拌方式进行，所述的搅拌以120～900r/min的搅拌速度，搅拌0.5～2h。Preferably, the slurry preparation in step (1) can be carried out by stirring, and the stirring is carried out at a stirring speed of 120-900 r/min for 0.5-2 h.
优选的，步骤(1)中所述的磷酸混合溶液可由包括磷酸加上硫酸、盐酸、硝酸等中的至少一种混合得到。Preferably, the phosphoric acid mixed solution described in step (1) can be obtained by mixing phosphoric acid with at least one of sulfuric acid, hydrochloric acid, nitric acid and the like.
优选的，所述的磷酸混合溶液中PO4 3-离子的摩尔浓度为1～4mol/L；所述的磷酸混合溶液中H+离子的总摩尔浓度为2～6mol/L。Preferably, the molar concentration of PO 4 3- ions in the phosphoric acid mixed solution is 1-4 mol/L; the total molar concentration of H + ions in the phosphoric acid mixed solution is 2-6 mol/L.
优选的，步骤(1)中所述的还原剂可包括Na2S、Na2SO3、Na2S2O3、H2O2等中的至少一种。Preferably, the reducing agent in step (1) may include at least one of Na 2 S, Na 2 SO 3 , Na 2 S 2 O 3 , H 2 O 2 and the like.
优选的，步骤(1)中所述的磷酸混合溶液的加入量以磷酸根离子与镍钴锰离子总反应当量的1.0～1.05倍，以氢离子为反应当量的1.0～1.1倍计算加入；所述的还原剂的加入量为反应当量的1.0～2.0倍。Preferably, the amount of phosphoric acid mixed solution added in step (1) is calculated as 1.0 to 1.05 times the total reaction equivalent of phosphate ions and nickel, cobalt and manganese ions, and 1.0 to 1.1 times the reaction equivalent of hydrogen ions; The added amount of the reducing agent is 1.0 to 2.0 times the reaction equivalent.
优选的，步骤(1)中所述的反应在反应温度50～80℃，搅拌速度120～900r/min的条件下反应1～5h。Preferably, the reaction described in step (1) is carried out under the conditions of a reaction temperature of 50 to 80° C. and a stirring speed of 120 to 900 r/min for 1 to 5 hours.
优选的，步骤(1)中所述的碱试剂A可包括NaOH、KOH、NH4OH、LiOH等中的至少一种。Preferably, the alkaline reagent A described in step (1) may include at least one of NaOH, KOH, NH 4 OH, LiOH and the like.
优选的，步骤(1)中所述的分离可采用过滤、离心等常规操作进行。Preferably, the separation described in step (1) can be performed by conventional operations such as filtration and centrifugation.
进一步的，步骤(1)中得到的含锂溶液可用于生产锂盐，得到的滤渣A为镍钴锰磷酸盐、碳粉、粘结剂等的混合固体。Further, the lithium-containing solution obtained in step (1) can be used to produce lithium salt, and the obtained filter residue A is a mixed solid of nickel-cobalt-manganese phosphate, carbon powder, binder and the like.
优选的，步骤(2)中所述的制浆过程中滤渣A与水的液固比为1.5:1～10:1。Preferably, the liquid-solid ratio of filter residue A to water in the pulping process described in step (2) is 1.5:1 to 10:1.
优选的，步骤(2)中所述的制浆通过搅拌进行，所述的搅拌速度为120～900r/min，搅拌时间为0.5～2h。Preferably, the slurry preparation in step (2) is performed by stirring, the stirring speed is 120-900 r/min, and the stirring time is 0.5-2 h.
优选的，步骤(2)中所述的三价铁盐可包括FeCl3、Fe2(SO4)3、Fe(NO3)3等中的至少一种。Preferably, the ferric salt described in step (2) may include at least one of FeCl 3 , Fe 2 (SO 4 ) 3 , Fe(NO 3 ) 3 and the like.
优选的，步骤(2)中所述的复分解反应中三价铁盐的加入量以铁离子与磷酸根离子反应当量的1.0～1.2倍计算加入。Preferably, the amount of ferric salt added in the metathesis reaction described in step (2) is calculated and added at 1.0 to 1.2 times the reaction equivalent of iron ions and phosphate ions.
优选的，步骤(2)中所述的复分解反应的反应温度为50～80℃，反应时间为1～5h。Preferably, the reaction temperature of the metathesis reaction described in step (2) is 50-80° C., and the reaction time is 1-5 h.
优选的，步骤(2)中所述的复分解反应过程中可进行搅拌，搅拌速度为120～900r/min。Preferably, stirring can be performed during the metathesis reaction process described in step (2), and the stirring speed is 120-900 r/min.
优选的，步骤(2)中所述的酸试剂可包括HCl、H2SO4、HNO3等中的至少一种。Preferably, the acid reagent described in step (2) may include at least one of HCl, H 2 SO 4 , HNO 3 and the like.
优选的，步骤(2)中所述的陈化时间为0.5～2.0h。Preferably, the aging time described in step (2) is 0.5-2.0h.
优选的，步骤(2)中所述的滤渣B可采用稀酸进行洗渣，洗渣后得到的洗水可用于下次制浆。Preferably, the filter residue B described in step (2) can be washed with dilute acid, and the washing water obtained after washing the residue can be used for the next pulping.
优选的，所述的稀酸可包括稀盐酸、稀硫酸、稀硝酸等中的至少一种。Preferably, the dilute acid may include at least one of dilute hydrochloric acid, dilute sulfuric acid, and dilute nitric acid.
优选的，所述的洗渣过程中，控制体系的pH值为2.0～4.0。Preferably, in the slag washing process, the pH value of the control system is 2.0-4.0.
优选的，步骤(2)中所述的碱试剂B可包括NaOH、NH4OH、Ni(OH)2、Mn(OH)2、Co(OH)2等中的至少一种。Preferably, the alkaline reagent B described in step (2) may include at least one of NaOH, NH 4 OH, Ni(OH) 2 , Mn(OH) 2 , Co(OH) 2 and the like.
优选的，步骤(2)中所述的分离可采用过滤、离心等常规操作进行。Preferably, the separation described in step (2) can be performed by conventional operations such as filtration and centrifugation.
相比于现有技术，本发明具有如下优点和技术效果：Compared with the prior art, the present invention has the following advantages and technical effects:
(1)本发明技术方案中采用了混合磷酸溶液对三元废料中的锂元素进行选择性浸取，同时利用磷酸铁的沉淀趋势远强于磷酸镍、磷酸钴、磷酸锰的特点，一步法完成从滤渣分离镍钴锰元素和镍钴锰磷酸盐转换成镍钴锰溶液实现高值化的操作。本发明提供的镍钴锰和锂的分离回收方法具有工艺简单、成本低、镍钴锰锂回收率高、设备要求低，且控制精度要求低，废盐量少且为固体状态，无需蒸发干燥处理等优点。(1) in the technical scheme of the present invention, a mixed phosphoric acid solution is used to selectively leaching the lithium element in the ternary waste, and the precipitation trend of utilizing iron phosphate is far stronger than the characteristics of nickel phosphate, cobalt phosphate and manganese phosphate, and the one-step method Completed the operation of separating nickel-cobalt-manganese elements and nickel-cobalt-manganese phosphates from filter residues and converting them into nickel-cobalt-manganese solutions to achieve high value. The method for separating and recovering nickel, cobalt, manganese and lithium provided by the invention has the advantages of simple process, low cost, high recovery rate of nickel, cobalt, manganese and lithium, low equipment requirements, low control precision requirements, less waste salt and solid state, and no need for evaporation and drying. processing advantages.
(2)本发明技术方案无需使用萃取试剂，避免引入有机相造成回收的含锂溶液和镍钴锰溶液的不纯，避免因使用大量萃取试剂而产生的COD废水和硫酸钠废盐，减少了环境污染。(2) The technical scheme of the present invention does not need to use extraction reagents, avoids the impurity of the lithium-containing solution and nickel-cobalt-manganese solution that is recovered due to the introduction of an organic phase, avoids COD waste water and sodium sulfate waste salt generated due to the use of a large amount of extraction reagents, reduces the Environmental pollution.
附图说明Description of drawings
图1为本发明实施例1三元废料中镍钴锰与锂分离回收的工艺流程图。Fig. 1 is the process flow diagram of the separation and recovery of nickel, cobalt, manganese and lithium in the ternary waste material in Example 1 of the present invention.
具体实施方式Detailed ways
下面结合附图用具体实施方式和实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。如无特别说明，本发明中所有原料和试剂均为市购常规的原料、试剂。实施例中各组分的用量以质量体积份计，g、mL。The present invention will be described in further detail below with specific embodiments and examples in conjunction with the accompanying drawings, but the embodiments of the present invention are not limited thereto. Unless otherwise specified, all raw materials and reagents in the present invention are commercially available conventional raw materials and reagents. The consumption of each component in the examples is in terms of parts by mass and volume, g, mL.
含锂溶液的制取：Preparation of lithium-containing solution:
根据本发明的一实施例，将三元废料与水进行制浆，三元废料中的各元素浸出率随着液固比的增大而增大，但是当液固比达到一定比例后继续增加，浸出率变化不大，因此为了保持较高浸出率和节省试剂的使用，本发明的三元废料与水的液固比为1.5:1～10:1，优选为4:1～6:1。According to an embodiment of the present invention, the ternary waste is pulped with water, and the leaching rate of each element in the ternary waste increases with the increase of the liquid-solid ratio, but continues to increase when the liquid-solid ratio reaches a certain ratio , the leaching rate does not change much, so in order to maintain a high leaching rate and save the use of reagents, the liquid-solid ratio of the ternary waste and water of the present invention is 1.5:1-10:1, preferably 4:1-6:1 .
根据本发明的一实施例，三元废料与水制浆过程中采用搅拌的方式使三元废料与水混合均匀，所述的搅拌速度为120～900r/min，搅拌时间为0.5～2h。为了更好的将三元废料分散于水中，还可对浆液进行超声处理和加热处理，比如在50～60℃，超声功率500～1000W条件下处理30min～120min。According to an embodiment of the present invention, the ternary waste is mixed with water evenly by stirring during the pulping process of the ternary waste and water. The stirring speed is 120-900r/min, and the stirring time is 0.5-2h. In order to better disperse the ternary waste in water, ultrasonic treatment and heat treatment can also be carried out on the slurry, for example, treatment at 50-60°C and ultrasonic power of 500-1000W for 30min-120min.
进一步的，在制浆前可对三元废料进行预处理。所述的预处理可包括以下步骤：将三元废料在380～500℃下加热处理30～120min。粘结剂一般为有机高分子化合物，如PDVF，其结构和化学性质稳定，不溶于强酸强碱，因此在三元废料进行酸浸反应过程中容易形成灰层，不利于有价金属的浸出。采用高温处理的方式可将粘结剂分解，使镍钴锰锂活性材料充分暴露，分散性提高，从而提高浸出率。Further, the ternary waste can be pretreated before pulping. The pretreatment may include the following steps: heating the ternary waste at 380-500° C. for 30-120 min. The binder is generally an organic polymer compound, such as PDVF, which has stable structure and chemical properties, and is insoluble in strong acid and alkali, so it is easy to form a gray layer during the acid leaching reaction of ternary waste, which is not conducive to the leaching of valuable metals. The binder can be decomposed by high-temperature treatment, so that the nickel-cobalt-manganese-lithium active material is fully exposed, and the dispersibility is improved, thereby increasing the leaching rate.
根据本发明的一实施例，采用磷酸混合溶液联合还原剂对三元废料进行选择性浸取反应。所述的还原剂可包括Na2S、Na2SO3、Na2S2O3、H2O2等中的至少一种。三元废料中的主要活性材料为LiNi1-x-yCoxMnyO2(x+y<1)，其中过渡金属元素Ni、Co和Mn化学价为+2、+3和+4价，需要将Co3+、Mn4+还原成低价才能被酸完全溶解。所述的磷酸混合溶液由磷酸加上硫酸、盐酸、硝酸等中的至少一种制备得到。其中，硫酸、盐酸、硝酸等为强酸，容易将LiNi1-x- yCoxMnyO2中的Li、Ni、Co、Mn元素以金属离子形式浸出到溶液中，同时为反应体系提供H+，并调节反应体系的pH<4；磷酸主要为反应体系提供PO4 3+，与Ni2+、Co2+、Mn2+生成磷酸盐沉淀，而Li+与PO4 3+在pH<4的条件下不能沉淀，以离子形式存在于溶液中，从而实现了三元废料的选择性浸取，将Ni、Co、Mn元素与Li元素进行分离。According to an embodiment of the present invention, the ternary waste is selectively leached by using a phosphoric acid mixed solution combined with a reducing agent. The reducing agent may include at least one of Na 2 S, Na 2 SO 3 , Na 2 S 2 O 3 , H 2 O 2 and the like. The main active material in the ternary waste is LiNi 1-xy Co x Mn y O 2 (x+y<1), in which the chemical valences of transition metal elements Ni, Co and Mn are +2, +3 and +4, which require Only by reducing Co 3+ and Mn 4+ to low price can they be completely dissolved by acid. The phosphoric acid mixed solution is prepared from phosphoric acid plus at least one of sulfuric acid, hydrochloric acid, nitric acid and the like. Among them, sulfuric acid, hydrochloric acid, nitric acid, etc. are strong acids, which are easy to leach Li, Ni, Co, and Mn elements in LiNi 1-x- y Co x Mn y O 2 into the solution in the form of metal ions, and at the same time provide H for the reaction system. + , and adjust the pH of the reaction system <4; phosphoric acid mainly provides PO 4 3+ for the reaction system, and forms phosphate precipitation with Ni 2+ , Co 2+ , Mn 2+ , while Li + and PO 4 3+ are at pH< Under the conditions of 4, it cannot be precipitated and exists in the solution in the form of ions, thereby realizing the selective leaching of ternary wastes and separating Ni, Co, Mn elements from Li elements.
以H2O2作为还原剂为例，反应方程式如下：Taking H 2 O 2 as the reducing agent as an example, the reaction equation is as follows:
6LiMeO2+18H++4PO4 3-+3H2O2→6Li++2(Me)3(PO4)2↓+12H2O+3O2↑6LiMeO 2 +18H + +4PO 4 3- +3H 2 O 2 →6Li + +2(Me) 3 (PO 4 ) 2 ↓+12H 2 O+3O 2 ↑
其中Me为Ni、Co、Mn。Wherein Me is Ni, Co, Mn.
根据本发明的一实施例，还原剂的加入量为反应当量的1.0～2.0倍，充足的还原剂加入量，目的在于使高价Co、Mn彻底被还原成低价，提高Co、Mn溶出率；磷酸混合溶液的加入量以磷酸根离子为反应当量的1.0～1.05倍，氢离子的总加入量为反应当量的1.0～1.1倍计算加入，充足的酸加入量主要目的在于使Ni、Co、Mn完全沉淀，提高分离效率。According to an embodiment of the present invention, the added amount of the reducing agent is 1.0 to 2.0 times the reaction equivalent, and the sufficient amount of the reducing agent added is for the purpose of making high-priced Co and Mn completely reduced to low-priced and improving the dissolution rate of Co and Mn; The addition amount of the phosphoric acid mixed solution is 1.0 to 1.05 times the reaction equivalent of phosphate ions, and the total addition amount of hydrogen ions is calculated to be 1.0 to 1.1 times the reaction equivalent. The main purpose of sufficient acid addition is to make Ni, Co, Mn Complete precipitation to improve separation efficiency.
根据本发明的一实施例，在反应完全后加入碱试剂A调节pH至7.0～11.0，所述的碱试剂B包括NaOH、KOH、NH4OH、LiOH等中的至少一种，主要目的在于进一步将磷酸镍钴锰沉淀完全和体系除杂，减少含锂溶液的杂质。According to an embodiment of the present invention, after the reaction is completed, an alkaline reagent A is added to adjust the pH to 7.0-11.0, and the alkaline reagent B includes at least one of NaOH, KOH, NH 4 OH, LiOH, etc. The main purpose is to further The nickel-cobalt-manganese phosphate is completely precipitated and impurities are removed from the system to reduce impurities in the lithium-containing solution.
根据本发明的一实施例，在碱试剂A调节pH至7.0～11.0后，进行过滤操作得到含锂溶液和滤渣A。According to an embodiment of the present invention, after the pH of the alkaline reagent A is adjusted to 7.0-11.0, a filtration operation is performed to obtain a lithium-containing solution and a filter residue A.
镍钴锰精制溶液的制取：Preparation of nickel-cobalt-manganese refined solution:
根据本发明的一实施例，将滤渣A与水进行制浆，制浆过程中滤渣A与水的质量比为1.5:1～10:1，制浆通过搅拌进行，所述的搅拌速度为120～900r/min，搅拌时间为0.5～2h。滤渣A为磷酸镍钴锰盐沉淀、碳粉、粘结剂等的混合固体，制浆目的在于使磷酸镍钴锰沉淀充分分散于溶液中，提高反应效率。According to an embodiment of the present invention, filter residue A and water are pulped, and the mass ratio of filter residue A to water in the pulping process is 1.5:1 to 10:1, and the pulping is performed by stirring, and the stirring speed is 120 ～900r/min, stirring time is 0.5～2h. The filter residue A is a mixed solid of nickel-cobalt-manganese phosphate precipitate, carbon powder, binder, etc. The purpose of pulping is to fully disperse the nickel-cobalt-manganese phosphate precipitate in the solution and improve the reaction efficiency.
根据本发明的一实施例，制浆后加入三价铁盐进行复分解反应，所述的三价铁盐可包括FeCl3、Fe2(SO4)3、Fe(NO3)3等中的至少一种。利用FePO4的沉淀趋势远强于Ni3(PO4)2、Co3(PO4)2、Mn3(PO4)2的特点，通过复分解反应，将Li、Ni、Co元素从固体沉淀中置换成离子形式溶于溶液中，从而使Li、Ni、Co元素与碳粉、粘结剂等杂质进行分离，得到镍钴锰粗溶液和滤渣B。According to an embodiment of the present invention, after pulping, a ferric salt is added to perform a metathesis reaction, and the ferric salt may include at least one of FeCl 3 , Fe 2 (SO 4 ) 3 , Fe(NO 3 ) 3 and the like A sort of. Taking advantage of the precipitation tendency of FePO 4 is much stronger than that of Ni 3 (PO 4 ) 2 , Co 3 (PO 4 ) 2 , Mn 3 (PO 4 ) 2 , Li, Ni and Co elements are removed from the solid precipitation through metathesis reaction. It is replaced by ionic form and dissolved in the solution, so that Li, Ni, Co elements are separated from impurities such as carbon powder and binder, and a coarse nickel-cobalt-manganese solution and filter residue B are obtained.
复分解反应的反应方程式如下：The reaction equation for the metathesis reaction is as follows:
Me3(PO4)2+2Fe3++2H2O→FePO4·2H2O↓+3Me2+ Me 3 (PO 4 ) 2 +2Fe 3+ +2H 2 O→FePO 4 ·2H 2 O↓+3Me 2+
其中Me为Ni、Co、Mn。Wherein Me is Ni, Co, Mn.
根据本发明的一实施例，复分解反应中三价铁盐的加入量为反应当量的1.0～1.2倍。加入足量的三价铁盐目的在于将Ni3(PO4)2、Co3(PO4)2、Mn3(PO4)2中的Ni、Co、Mn元素完全置换出来，提高浸出效率。According to an embodiment of the present invention, the amount of ferric salt added in the metathesis reaction is 1.0-1.2 times the reaction equivalent. The purpose of adding a sufficient amount of ferric salt is to completely replace the elements Ni, Co and Mn in Ni 3 (PO 4 ) 2 , Co 3 (PO 4 ) 2 and Mn 3 (PO 4 ) 2 to improve the leaching efficiency.
根据本发明的一实施例，复分解反应完全后，加入酸试剂调节体系pH至1.9～2.0，陈化0.5～2.0h。所述的酸试剂可包括可包括盐酸、硫酸、硝酸等中的至少一种。陈化过程中，使FePO4·2H2O沉淀小晶粒逐渐溶解，大晶粒逐渐长大，随着小晶粒的溶解，被吸附、吸留和包藏在FePO4·2H2O沉淀沉淀内部中的Ni、Co、Mn离子可重新溶入体系中，从而提高了Ni、Co、Mn的回收率和FePO4·2H2O沉淀晶体的纯度。According to an embodiment of the present invention, after the metathesis reaction is completed, an acid reagent is added to adjust the pH of the system to 1.9-2.0, and the system is aged for 0.5-2.0 h. The acid reagent may include at least one of hydrochloric acid, sulfuric acid, nitric acid, and the like. During the aging process, the small crystal grains of FePO 4 · 2H 2 O precipitates are gradually dissolved, and the large grains gradually grow up . Ni, Co and Mn ions in the interior can be redissolved into the system, thereby improving the recovery rate of Ni, Co and Mn and the purity of FePO 4 ·2H 2 O precipitated crystals.
根据本发明的一实施例，采用稀酸对所述的滤渣B进行洗渣，洗渣后得到的洗水可用于下次滤渣A制浆。所述的稀酸可为稀硫酸、稀盐酸、稀硝酸等中的至少一种。所述的洗渣过程中，控制体系的pH值为2.0～4.0。其中滤渣B为FePO4·2H2O沉淀和碳粉、粘结剂等杂质的混合固体，采用稀强酸对滤渣B进行洗涤，可将滤渣B中的FePO4·2H2O沉淀溶解在洗水中，重新用于滤渣A与水的制浆，为复分解反应提供Fe3+进行反应，使试剂得到充分利用，减少试剂浪费，节约成本。According to an embodiment of the present invention, the filter residue B is washed with dilute acid, and the washing water obtained after washing the residue can be used for the next time the filter residue A is pulped. The dilute acid can be at least one of dilute sulfuric acid, dilute hydrochloric acid, and dilute nitric acid. In the slag washing process, the pH value of the control system is 2.0-4.0. The filter residue B is a mixed solid of FePO 4 ·2H 2 O precipitation and impurities such as carbon powder and binder. Dilute strong acid is used to wash the filter residue B, and the FePO 4 ·2H 2 O precipitate in the filter residue B can be dissolved in the washing water. , reused for pulping filter residue A and water, providing Fe 3+ for the metathesis reaction to react, making full use of reagents, reducing waste of reagents and saving costs.
根据本发明的一实施例，镍钴锰粗溶液加入碱试剂调节pH至4.0～5.0进行沉淀。由于在复分解反应过程中，为了将Ni、Co、Mn浸出完全，加入了过量的三价铁盐，因此在镍钴锰粗溶液中还存在Fe3+，因此加入碱试剂使Fe3+生成Fe(OH)3(滤渣C)沉淀除杂，由于Fe(OH)3的沉淀趋势远远强于Ni(OH)2、Co(OH)2、Mn(OH)2，因此在反应体系pH为4.0～5.0的条件下，加入的碱试剂优先与Fe3+生成Fe(OH)3沉淀，从而可以过滤得到镍钴锰精制溶液。According to an embodiment of the present invention, an alkaline reagent is added to the nickel-cobalt-manganese crude solution to adjust the pH to 4.0-5.0 for precipitation. In the process of metathesis reaction, in order to completely leaching Ni, Co and Mn, excess ferric salt was added, so Fe 3+ still existed in the crude nickel-cobalt-manganese solution, so an alkaline reagent was added to make Fe 3+ generate Fe (OH) 3 (filter residue C) was precipitated to remove impurities. Since the precipitation trend of Fe(OH) 3 was much stronger than that of Ni(OH) 2 , Co(OH) 2 and Mn(OH) 2 , the pH of the reaction system was 4.0 Under the condition of ~5.0, the added alkali reagent preferentially reacts with Fe 3+ to form Fe(OH) 3 precipitation, so that the nickel-cobalt-manganese refined solution can be obtained by filtration.
以下是具体实施例，对本发明三元废料中镍钴锰与锂的分离回收方法进一步说明，其中实施例所采用的三元废料为中Li的含量为7.2％，Ni的含量为20.3％，Co的含量为20.5％，Mn的含量为19.0％。The following is a specific example, the separation and recovery method of nickel, cobalt, manganese and lithium in the ternary waste of the present invention is further described, wherein the ternary waste used in the embodiment is that the content of Li is 7.2%, the content of Ni is 20.3%, and the content of Co is 20.3%. The content of Mn is 20.5%, and the content of Mn is 19.0%.
实施例1：三元废料中镍钴锰与锂的分离回收方法Embodiment 1: the separation and recovery method of nickel cobalt manganese and lithium in ternary waste material
(1)含锂溶液的制取：将三元废料与水进行搅拌制浆，液固比为6:1，在600r/min的搅拌速度下搅拌1h得到浆液，然后往浆液中加入磷酸混合溶液(磷酸与硫酸混合，控制磷酸根离子的加入量为磷酸根离子与镍钴锰离子总反应当量的1.05倍，氢离子的总加入量为反应当量的1.1倍)调节体系pH<4，继续加入H2O2(H2O2加入量为反应当量的1.5倍)，在反应温度为65℃，搅拌速度为600r/min的条件下反应3h，反应完成后加入LiOH调节体系pH为9.0进一步沉淀除杂，过滤得到含锂溶液和滤渣A。(1) Preparation of lithium-containing solution: stirring the ternary waste material and water to make a slurry with a liquid-solid ratio of 6:1, stirring for 1 h at a stirring speed of 600 r/min to obtain a slurry, and then adding a phosphoric acid mixed solution to the slurry (mix phosphoric acid and sulfuric acid, control the addition amount of phosphate ions to be 1.05 times the total reaction equivalent of phosphate ions and nickel cobalt manganese ions, and the total addition amount of hydrogen ions to be 1.1 times the reaction equivalent) Adjust pH of the system <4, continue to add H 2 O 2 (the amount of H 2 O 2 added is 1.5 times the reaction equivalent), react for 3 hours at a reaction temperature of 65° C. and a stirring speed of 600 r/min. After the reaction is completed, add LiOH to adjust the pH of the system to 9.0 for further precipitation Remove impurities and filter to obtain lithium-containing solution and filter residue A.
(2)镍钴锰精制溶液的制取：将步骤(1)得到的滤渣A加水进行制浆，液固比为6:1，在600r/min的搅拌速度下搅拌1h得到浆液，然后往浆液中加入Fe2(SO4)3(Fe2(SO4)3加入量为铁离子与磷酸根离子反应当量的1.1倍)进行复分解反应，在反应温度为65℃，搅拌速度为600r/min的条件下反应3h，然后加入H2SO4调节体系pH值为1.9，陈化1h，过滤得到镍钴锰粗溶液和滤渣B，然后往镍钴锰粗溶液中加入Mn(OH)2调节体系pH值为4.5进行沉淀除杂，过滤得到镍钴锰精制溶液和滤渣C；(2) Preparation of the nickel-cobalt-manganese refined solution: add water to the filter residue A obtained in step (1) to make a slurry with a liquid-solid ratio of 6:1, stir for 1 hour at a stirring speed of 600 r/min to obtain a slurry, and then put the slurry into the slurry. Add Fe 2 (SO 4 ) 3 (the amount of Fe 2 (SO 4 ) 3 is 1.1 times the reaction equivalent of iron ion and phosphate ion) to carry out metathesis reaction, and the reaction temperature is 65 ℃, and the stirring speed is 600r/min. The reaction was carried out under the conditions for 3h, then H 2 SO 4 was added to adjust the pH value of the system to 1.9, aged for 1 h, and filtered to obtain a nickel-cobalt-manganese crude solution and filter residue B, and then Mn(OH) 2 was added to the nickel-cobalt-manganese crude solution to adjust the pH of the system The value is 4.5 to carry out precipitation and impurity removal, and filter to obtain nickel-cobalt-manganese refined solution and filter residue C;
(3)洗渣：将步骤(2)得到的滤渣B用pH值为3.0的稀硫酸进行洗渣，洗渣后得到的洗水用于下一次滤渣A与水的制浆。(3) washing residue: the filter residue B obtained in step (2) is washed with dilute sulfuric acid with a pH value of 3.0, and the washing water obtained after washing the residue is used for the next pulping of filter residue A and water.
图1为实施例1三元废料镍钴锰与锂分离回收的工艺流程图。Fig. 1 is the process flow diagram of the separation and recovery of ternary waste nickel-cobalt-manganese and lithium in Example 1.
实施例2：三元废料中镍钴锰与锂的分离回收方法Embodiment 2: the separation and recovery method of nickel cobalt manganese and lithium in ternary waste material
(1)含锂溶液的制取：将三元废料与水进行搅拌制浆，液固比为1.5:1，在900r/min的搅拌速度下搅拌0.5h得到浆液，然后往浆液中加入磷酸混合溶液(磷酸与盐酸混合，控制磷酸根离子的加入量为磷酸根离子与镍钴锰离子总反应当量的1.0倍，氢离子的总加入量为反应当量的1.0倍)调节体系pH<4，继续加入Na2S(Na2S加入量为反应当量的1.0倍)，在反应温度为80℃，搅拌速度为900r/min的条件下反应5h，反应完成后加入NaOH调节体系pH值为11.0进一步沉淀除杂，过滤得到含锂溶液和滤渣A。(1) Preparation of lithium-containing solution: stir the ternary waste material and water to make slurry, the liquid-solid ratio is 1.5:1, stir for 0.5h at a stirring speed of 900r/min to obtain a slurry, and then add phosphoric acid to the slurry to mix Solution (mix phosphoric acid and hydrochloric acid, control the addition amount of phosphate ions to be 1.0 times the total reaction equivalent of phosphate ions and nickel cobalt manganese ions, and the total addition amount of hydrogen ions to 1.0 times the reaction equivalent) to adjust the pH of the system <4, continue Add Na 2 S (the amount of Na 2 S added is 1.0 times the reaction equivalent), and react for 5 hours at a reaction temperature of 80 ° C and a stirring speed of 900 r/min. After the reaction is completed, add NaOH to adjust the pH of the system to 11.0 for further precipitation Remove impurities and filter to obtain lithium-containing solution and filter residue A.
(2)镍钴锰精制溶液的制取：将步骤(1)得到的滤渣A加水进行制浆，液固比为1.5:1，在900r/min的搅拌速度下搅拌0.5h得到浆液，然后往浆液中加入FeCl3(FeCl3加入量为铁离子与磷酸根离子反应当量的1.0倍)进行复分解反应，在反应温度为80℃，搅拌速度为900r/min的条件下反应5h，然后加入HCl调节体系pH值为2.0，陈化2h，过滤得到镍钴锰粗溶液和滤渣B，然后往镍钴锰粗溶液中加入Co(OH)2调节体系pH值为4.0进行沉淀除杂，过滤得到镍钴锰精制溶液和滤渣C。(2) Preparation of nickel-cobalt-manganese refined solution: add water to the filter residue A obtained in step (1) for slurrying, the liquid-solid ratio is 1.5:1, and stir for 0.5h at a stirring speed of 900r/min to obtain a slurry, and then to FeCl 3 (the amount of FeCl 3 added is 1.0 times the reaction equivalent of iron ions and phosphate ions) is added to the slurry to carry out metathesis reaction, and the reaction is carried out for 5 hours at a reaction temperature of 80 ° C and a stirring speed of 900 r/min, and then HCl is added to adjust The pH value of the system is 2.0, aged for 2 hours, and filtered to obtain a coarse nickel-cobalt-manganese solution and filter residue B. Then, Co(OH) 2 is added to the coarse nickel-cobalt-manganese solution to adjust the pH value of the system to 4.0 to carry out precipitation and impurity removal, and filter to obtain nickel-cobalt manganese. Manganese Refined Solution and Filter Residue C.
实施例3：三元废料中镍钴锰与锂的分离回收方法Embodiment 3: the separation and recovery method of nickel cobalt manganese and lithium in ternary waste material
(1)含锂溶液的制取：将三元废料与水进行搅拌制浆，液固比为10:1，在120r/min的搅拌速度下搅拌2h得到浆液，然后往浆液中加入磷酸混合溶液(磷酸与硝酸混合，控制磷酸根离子的加入量为磷酸根离子与镍钴锰离子总反应当量的1.03倍，氢离子的总加入量为反应当量的1.05倍)调节体系pH<4，继续加入Na2SO3(Na2SO3加入量为反应当量的2.0倍)，在反应温度为50℃，搅拌速度为120r/min的条件下反应1h，反应完成后加入NH4OH调节体系pH值为7.0进一步沉淀除杂，过滤得到含锂溶液和滤渣A。(1) Preparation of lithium-containing solution: The ternary waste and water are stirred to make a slurry, the liquid-solid ratio is 10:1, and the slurry is obtained by stirring for 2 hours at a stirring speed of 120 r/min, and then phosphoric acid mixed solution is added to the slurry. (mix phosphoric acid and nitric acid, control the addition amount of phosphate ions to be 1.03 times the total reaction equivalent of phosphate ions and nickel cobalt manganese ions, and the total addition amount of hydrogen ions is 1.05 times the reaction equivalent) Adjust pH of the system <4, continue to add Na 2 SO 3 (the amount of Na 2 SO 3 added is 2.0 times the reaction equivalent), react for 1 hour at a reaction temperature of 50° C. and a stirring speed of 120 r/min. After the reaction is completed, add NH 4 OH to adjust the pH of the system. 7.0 Further precipitation and impurity removal, and filtration to obtain a lithium-containing solution and filter residue A.
(2)镍钴锰精制溶液的制取：将步骤(1)得到的滤渣A加水进行制浆，液固比为10:1，在120r/min的搅拌速度下搅拌2h得到浆液，然后往浆液中加入Fe(NO3)3(Fe(NO3)3加入量为铁离子与磷酸根离子反应当量的1.05倍)进行复分解反应，在反应温度为50℃，搅拌速度为900r/min的条件下反应1h，然后加入HNO3调节体系pH值为1.9，陈化0.5h，过滤得到镍钴锰粗溶液和滤渣B，然后往镍钴锰粗溶液中加入Ni(OH)2调节体系pH值为5.0进行沉淀除杂，过滤得到镍钴锰精制溶液和滤渣C。(2) Preparation of nickel-cobalt-manganese refined solution: add water to the filter residue A obtained in step (1) to make a slurry with a liquid-solid ratio of 10:1, stir for 2h at a stirring speed of 120r/min to obtain a slurry, and then put the slurry into the slurry. Fe(NO 3 ) 3 (the amount of Fe(NO 3 ) 3 added is 1.05 times the reaction equivalent of iron ions and phosphate ions) to carry out metathesis reaction, under the conditions of reaction temperature of 50 ° C and stirring speed of 900 r/min React for 1h, then add HNO 3 to adjust the pH of the system to 1.9, age for 0.5h, filter to obtain a nickel-cobalt-manganese crude solution and filter residue B, and then add Ni(OH) 2 to the nickel-cobalt-manganese crude solution to adjust the pH of the system to 5.0 Carry out precipitation and impurity removal, and filter to obtain nickel-cobalt-manganese refined solution and filter residue C.
实施例4：三元废料中镍钴锰与锂的分离回收方法Embodiment 4: the separation and recovery method of nickel cobalt manganese and lithium in ternary waste material
(1)含锂溶液的制取：将三元废料在500℃条件下预处理80min，然后与水进行搅拌制浆，液固比为4:1，在600r/min的搅拌速度下搅拌1h得到浆液，然后往浆液中加入磷酸混合溶液(磷酸与硫酸混合，控制磷酸根离子的加入量为磷酸根离子与镍钴锰离子总反应当量的1.05倍，氢离子的总加入量为反应当量的1.1倍)调节体系pH<4，继续加入H2O2(H2O2加入量为反应当量的1.5倍)，在反应温度为65℃，搅拌速度为600r/min的条件下反应3h，反应完成后加入KOH调节体系pH为9.0进一步沉淀除杂，过滤得到含锂溶液和滤渣A。(1) Preparation of lithium-containing solution: The ternary waste was pretreated at 500 ° C for 80 minutes, and then stirred with water to make a slurry. The liquid-solid ratio was 4:1, and stirred at a stirring speed of 600r/min for 1 hour slurry, then add phosphoric acid mixed solution (phosphoric acid is mixed with sulfuric acid, control the addition of phosphate ion to be 1.05 times of the total reaction equivalent of phosphate ion and nickel-cobalt-manganese ion, and the total addition of hydrogen ion is 1.1 of the reaction equivalent. times) adjust the pH of the system to <4, continue to add H 2 O 2 (the amount of H 2 O 2 added is 1.5 times the reaction equivalent), react for 3 hours at a reaction temperature of 65°C and a stirring speed of 600 r/min, the reaction is completed KOH was then added to adjust the pH of the system to 9.0 for further precipitation and impurity removal, and a lithium-containing solution and filter residue A were obtained by filtration.
(2)镍钴锰精制溶液的制取：将步骤(1)得到的滤渣A加水进行制浆，液固比为6:1，在600r/min的搅拌速度下搅拌1h得到浆液，然后往浆液中加入Fe2(SO4)3(Fe2(SO4)3加入量为铁离子与磷酸根离子反应当量的1.1倍)进行复分解反应，在反应温度为65℃，搅拌速度为600r/min的条件下反应3h，然后加入H2SO4调节体系pH值为1.9，陈化1h，过滤得到镍钴锰粗溶液和滤渣B，然后往镍钴锰粗溶液中加入NH4OH调节体系pH值为4.5进行沉淀除杂，过滤得到镍钴锰精制溶液和滤渣C。(2) Preparation of the nickel-cobalt-manganese refined solution: add water to the filter residue A obtained in step (1) to make a slurry with a liquid-solid ratio of 6:1, stir for 1 hour at a stirring speed of 600 r/min to obtain a slurry, and then put the slurry into the slurry. Add Fe 2 (SO 4 ) 3 (the amount of Fe 2 (SO 4 ) 3 is 1.1 times the reaction equivalent of iron ion and phosphate ion) to carry out metathesis reaction, and the reaction temperature is 65 ℃, and the stirring speed is 600r/min. The reaction was carried out for 3 hours under the conditions, and then H 2 SO 4 was added to adjust the pH of the system to 1.9, aged for 1 hour, and filtered to obtain a nickel-cobalt-manganese crude solution and filter residue B, and then NH 4 OH was added to the nickel-cobalt-manganese crude solution to adjust the pH of the system. 4.5 carry out precipitation and impurity removal, and filter to obtain nickel-cobalt-manganese refined solution and filter residue C.
对比例1：Comparative Example 1:
(1)含锂溶液的制取：将三元废料与水进行搅拌制浆，液固比为6:1，在600r/min的搅拌速度下搅拌1h得到浆液，然后往浆液中加入磷酸混合溶液(磷酸与硫酸混合，控制磷酸根离子的加入量为磷酸根离子与镍钴锰离子总反应当量的1.2倍，氢离子的总加入量为反应当量的1.5倍)调节体系pH<4，继续加入H2O2(H2O2加入量为反应当量的1.5倍)，在反应温度为65℃，搅拌速度为600r/min的条件下反应3h，反应完成后加入LiOH调节体系pH为9.0进一步沉淀除杂，过滤得到含锂溶液和滤渣A。(1) Preparation of lithium-containing solution: stirring the ternary waste material and water to make a slurry with a liquid-solid ratio of 6:1, stirring for 1 h at a stirring speed of 600 r/min to obtain a slurry, and then adding a phosphoric acid mixed solution to the slurry (The phosphoric acid and sulfuric acid are mixed, and the added amount of phosphate ions is controlled to be 1.2 times the total reaction equivalent of phosphate ions and nickel, cobalt and manganese ions, and the total added amount of hydrogen ions is 1.5 times the reaction equivalent) Adjust the pH of the system <4, continue to add H 2 O 2 (the amount of H 2 O 2 added is 1.5 times the reaction equivalent), react for 3 hours at a reaction temperature of 65° C. and a stirring speed of 600 r/min. After the reaction is completed, add LiOH to adjust the pH of the system to 9.0 for further precipitation Remove impurities and filter to obtain lithium-containing solution and filter residue A.
(2)镍钴锰精制溶液的制取：将步骤(1)得到的滤渣A加水进行制浆，液固比为6:1，在600r/min的搅拌速度下搅拌1h得到浆液，然后往浆液中加入Fe2(SO4)3(Fe2(SO4)3加入量为铁离子与磷酸根离子反应当量的1.1倍)进行复分解反应，在反应温度为65℃，搅拌速度为600r/min的条件下反应3h，然后加入H2SO4调节体系pH值为1.9，陈化1h，过滤得到镍钴锰粗溶液和滤渣B，然后往镍钴锰粗溶液中加入Mn(OH)2调节体系pH值为4.5进行沉淀除杂，过滤得到镍钴锰精制溶液和滤渣C。(2) Preparation of the nickel-cobalt-manganese refined solution: add water to the filter residue A obtained in step (1) to make a slurry with a liquid-solid ratio of 6:1, stir for 1 hour at a stirring speed of 600 r/min to obtain a slurry, and then put the slurry into the slurry. Add Fe 2 (SO 4 ) 3 (the amount of Fe 2 (SO 4 ) 3 is 1.1 times the reaction equivalent of iron ion and phosphate ion) to carry out metathesis reaction, and the reaction temperature is 65 ℃, and the stirring speed is 600r/min. The reaction was carried out under the conditions for 3h, then H 2 SO 4 was added to adjust the pH value of the system to 1.9, aged for 1 h, and filtered to obtain a nickel-cobalt-manganese crude solution and filter residue B, and then Mn(OH) 2 was added to the nickel-cobalt-manganese crude solution to adjust the pH of the system When the value is 4.5, precipitation and impurity removal are carried out, and the nickel-cobalt-manganese refined solution and filter residue C are obtained by filtration.
对比例2：Comparative Example 2:
(1)含锂溶液的制取：将三元废料与水进行搅拌制浆，液固比为6:1，在600r/min的搅拌速度下搅拌1h得到浆液，然后往浆液中加入磷酸混合溶液(磷酸与硫酸混合，控制磷酸根离子的加入量为磷酸根离子与镍钴锰离子总反应当量的0.9倍，氢离子的总加入量为反应当量的0.9倍)调节体系pH<4，继续加入H2O2(H2O2加入量为反应当量的1.5倍)，在反应温度为65℃，搅拌速度为600r/min的条件下反应3h，反应完成后加入LiOH调节体系pH为9.0进一步沉淀除杂，过滤得到含锂溶液和滤渣A。(1) Preparation of lithium-containing solution: stirring the ternary waste material and water to make a slurry with a liquid-solid ratio of 6:1, stirring for 1 h at a stirring speed of 600 r/min to obtain a slurry, and then adding a phosphoric acid mixed solution to the slurry (mix phosphoric acid and sulfuric acid, control the addition of phosphate ions to be 0.9 times the total reaction equivalent of phosphate ions and nickel cobalt manganese ions, and the total addition of hydrogen ions to 0.9 times the reaction equivalent) Adjust pH of the system <4, continue to add H 2 O 2 (the amount of H 2 O 2 added is 1.5 times the reaction equivalent), react for 3 hours at a reaction temperature of 65° C. and a stirring speed of 600 r/min. After the reaction is completed, add LiOH to adjust the pH of the system to 9.0 for further precipitation Remove impurities and filter to obtain lithium-containing solution and filter residue A.
(2)镍钴锰精制溶液的制取：将步骤(1)得到的滤渣A加水进行制浆，液固比为6:1，在600r/min的搅拌速度下搅拌1h得到浆液，然后往浆液中加入Fe2(SO4)3(Fe2(SO4)3加入量为铁离子与磷酸根离子反应当量的1.1倍)进行复分解反应，在反应温度为65℃，搅拌速度为600r/min的条件下反应3h，然后加入H2SO4调节体系pH值为1.9，陈化1h，过滤得到镍钴锰粗溶液和滤渣B，然后往镍钴锰粗溶液中加入Mn(OH)2调节体系pH值为4.5进行沉淀除杂，过滤得到镍钴锰精制溶液和滤渣C。(2) Preparation of the nickel-cobalt-manganese refined solution: add water to the filter residue A obtained in step (1) to make a slurry with a liquid-solid ratio of 6:1, stir for 1 hour at a stirring speed of 600 r/min to obtain a slurry, and then put the slurry into the slurry. Add Fe 2 (SO 4 ) 3 (the amount of Fe 2 (SO 4 ) 3 is 1.1 times the reaction equivalent of iron ion and phosphate ion) to carry out metathesis reaction, and the reaction temperature is 65 ℃, and the stirring speed is 600r/min. The reaction was carried out under the conditions for 3h, then H 2 SO 4 was added to adjust the pH value of the system to 1.9, aged for 1 h, and filtered to obtain a nickel-cobalt-manganese crude solution and filter residue B, and then Mn(OH) 2 was added to the nickel-cobalt-manganese crude solution to adjust the pH of the system When the value is 4.5, precipitation and impurity removal are carried out, and the nickel-cobalt-manganese refined solution and filter residue C are obtained by filtration.
对比例3：Comparative Example 3:
(1)含锂溶液的制取：将三元废料与水进行搅拌制浆，液固比为6:1，在600r/min的搅拌速度下搅拌1h得到浆液，然后往浆液中加入磷酸混合溶液(磷酸与硫酸混合，控制磷酸根离子的加入量为磷酸根离子与镍钴锰离子总反应当量的1.05倍，氢离子的总加入量为反应当量的1.1倍)调节体系pH<4，继续加入H2O2(H2O2加入量为反应当量的3.0倍)，在反应温度为65℃，搅拌速度为600r/min的条件下反应3h，反应完成后加入LiOH调节体系pH为9.0进一步沉淀除杂，过滤得到含锂溶液和滤渣A。(1) Preparation of lithium-containing solution: stirring the ternary waste material and water to make a slurry with a liquid-solid ratio of 6:1, stirring for 1 h at a stirring speed of 600 r/min to obtain a slurry, and then adding a phosphoric acid mixed solution to the slurry (mix phosphoric acid and sulfuric acid, control the addition amount of phosphate ions to be 1.05 times the total reaction equivalent of phosphate ions and nickel cobalt manganese ions, and the total addition amount of hydrogen ions to be 1.1 times the reaction equivalent) Adjust pH of the system <4, continue to add H 2 O 2 (the amount of H 2 O 2 added is 3.0 times the reaction equivalent), react for 3 hours at a reaction temperature of 65° C. and a stirring speed of 600 r/min. After the reaction is completed, add LiOH to adjust the pH of the system to 9.0 for further precipitation Remove impurities and filter to obtain lithium-containing solution and filter residue A.
(2)镍钴锰精制溶液的制取：将步骤(1)得到的滤渣A加水进行制浆，液固比为6:1，在600r/min的搅拌速度下搅拌1h得到浆液，然后往浆液中加入Fe2(SO4)3(Fe2(SO4)3加入量为铁离子与磷酸根离子反应当量的1.1倍)进行复分解反应，在反应温度为65℃，搅拌速度为600r/min的条件下反应3h，然后加入H2SO4调节体系pH值为1.9，陈化1h，过滤得到镍钴锰粗溶液和滤渣B，然后往镍钴锰粗溶液中加入Mn(OH)2调节体系pH值为4.5进行沉淀除杂，过滤得到镍钴锰精制溶液和滤渣C。(2) Preparation of the nickel-cobalt-manganese refined solution: add water to the filter residue A obtained in step (1) to make a slurry with a liquid-solid ratio of 6:1, stir for 1 hour at a stirring speed of 600 r/min to obtain a slurry, and then put the slurry into the slurry. Add Fe 2 (SO 4 ) 3 (the amount of Fe 2 (SO 4 ) 3 is 1.1 times the reaction equivalent of iron ion and phosphate ion) to carry out metathesis reaction, and the reaction temperature is 65 ℃, and the stirring speed is 600r/min. The reaction was carried out under the conditions for 3h, then H 2 SO 4 was added to adjust the pH value of the system to 1.9, aged for 1 h, and filtered to obtain a nickel-cobalt-manganese crude solution and filter residue B, and then Mn(OH) 2 was added to the nickel-cobalt-manganese crude solution to adjust the pH of the system When the value is 4.5, precipitation and impurity removal are carried out, and the nickel-cobalt-manganese refined solution and filter residue C are obtained by filtration.
对比例4：Comparative Example 4:
(1)含锂溶液的制取：将三元废料与水进行搅拌制浆，液固比为6:1，在600r/min的搅拌速度下搅拌1h得到浆液，然后往浆液中加入磷酸溶液调节体系pH<4，继续加入H2O2(H2O2加入量为反应当量的1.5倍)，在反应温度为65℃，搅拌速度为600r/min的条件下反应3h，反应完成后加入LiOH调节体系pH为9.0进一步沉淀除杂，过滤得到含锂溶液和滤渣A。(1) Preparation of lithium-containing solution: stirring the ternary waste material and water to make a slurry with a liquid-solid ratio of 6:1, stirring for 1 hour at a stirring speed of 600 r/min to obtain a slurry, and then adding phosphoric acid solution to the slurry to adjust The pH of the system is less than 4, continue to add H 2 O 2 (the amount of H 2 O 2 is 1.5 times the reaction equivalent), react for 3 hours at a reaction temperature of 65 ° C and a stirring speed of 600 r/min, and add LiOH after the reaction is completed. The pH of the system was adjusted to 9.0 for further precipitation and impurity removal, and the lithium-containing solution and filter residue A were obtained by filtration.
(2)镍钴锰精制溶液的制取：将步骤(1)得到的滤渣A加水进行制浆，液固比为6:1，在600r/min的搅拌速度下搅拌1h得到浆液，然后往浆液中加入Fe2(SO4)3(Fe2(SO4)3加入量为铁离子与磷酸根离子反应当量的1.1倍)进行复分解反应，在反应温度为65℃，搅拌速度为600r/min的条件下反应3h，然后加入H2SO4调节体系pH值为1.9，陈化1h，过滤得到镍钴锰粗溶液和滤渣B，然后往镍钴锰粗溶液中加入Mn(OH)2调节体系pH值为4.5进行沉淀除杂，过滤得到镍钴锰精制溶液和滤渣C。(2) Preparation of the nickel-cobalt-manganese refined solution: add water to the filter residue A obtained in step (1) to make a slurry with a liquid-solid ratio of 6:1, stir for 1 hour at a stirring speed of 600 r/min to obtain a slurry, and then put the slurry into the slurry. Add Fe 2 (SO 4 ) 3 (the amount of Fe 2 (SO 4 ) 3 is 1.1 times the reaction equivalent of iron ion and phosphate ion) to carry out metathesis reaction, and the reaction temperature is 65 ℃, and the stirring speed is 600r/min. The reaction was carried out under the conditions for 3h, then H 2 SO 4 was added to adjust the pH value of the system to 1.9, aged for 1 h, and filtered to obtain a nickel-cobalt-manganese crude solution and filter residue B, and then Mn(OH) 2 was added to the nickel-cobalt-manganese crude solution to adjust the pH of the system When the value is 4.5, precipitation and impurity removal are carried out, and the nickel-cobalt-manganese refined solution and filter residue C are obtained by filtration.
将实施例1、对比例1、对比例2、对比例3中得到的含锂溶液和滤渣A进行Li元素进行含量分析，结果如表1。The lithium-containing solution and filter residue A obtained in Example 1, Comparative Example 1, Comparative Example 2, and Comparative Example 3 were subjected to Li element content analysis, and the results are shown in Table 1.
表1含锂溶液和滤渣A中的Li元素含量Table 1 Li element content in lithium-containing solution and filter residue A
由表1数据可看出，①与实施例1相比，对比例1的磷酸混合溶液的加入量过多，多余的PO4 3+与Li+在后续调节pH至7.0～11.0除杂的过程中，由于从酸性条件转为碱性条件，PO4 3+与Li+生成Li3PO4沉淀析出，导致含锂溶液中的Li含量降低，滤渣A中的Li含量升高；②与实施例1相比，对比例2的磷酸混合溶液的加入量不足，三元废料中的Li元素浸出量降低，从而导致含锂溶液中的Li含量降低，滤渣A中的Li含量升高，进一步的，由于PO4 3+不足，会使酸浸出的Ni、Co、Mn离子没有被完全沉淀，导致含锂溶液中的Ni、Co、Mn杂质含量升高；③与实施例1相比，对比例3加入反应当量3.0倍的还原剂，但是含锂溶液中的Li含量并没有显著性的增加，进一步的，如果还原剂的加入量不足，三元废料中的高价Co、Mn不能彻底被还原成低价，由于高价Co、Mn不能被酸浸出，会导致Co、Mn回收率下降，因此为了节约资源，同时保证Co、Mn回收率，在本发明的技术方案中控制还原剂的加入量为反应当量的1.0～2.0倍。From the data in Table 1, it can be seen that (1) compared with Example 1, the amount of phosphoric acid mixed solution added in Comparative Example 1 was too much, and the excess PO 4 3+ and Li + were subsequently adjusted to pH 7.0-11.0 The process of removing impurities , due to the change from acidic conditions to alkaline conditions, PO 4 3+ and Li + generate Li 3 PO 4 to precipitate out, resulting in a decrease in the Li content in the lithium-containing solution, and an increase in the Li content in the filter residue A; ② and Example Compared with 1, the addition amount of the phosphoric acid mixed solution of Comparative Example 2 is insufficient, and the leaching amount of Li element in the ternary waste is reduced, thereby causing the Li content in the lithium-containing solution to decrease, and the Li content in the filter residue A to increase. Further, Due to insufficient PO 4 3+ , the Ni, Co, and Mn ions leached by acid will not be completely precipitated, resulting in an increase in the content of Ni, Co, and Mn impurities in the lithium-containing solution; ③Compared with Example 1, Comparative Example 3 Adding a reducing agent with a reaction equivalent of 3.0 times, but the Li content in the lithium-containing solution does not increase significantly. Further, if the amount of reducing agent added is insufficient, the high-valent Co and Mn in the ternary waste cannot be completely reduced to low levels. Since high-priced Co and Mn cannot be leached by acid, the recovery rate of Co and Mn will decrease. Therefore, in order to save resources and ensure the recovery rate of Co and Mn at the same time, in the technical scheme of the present invention, the added amount of the control reducing agent is the reaction equivalent 1.0 to 2.0 times.
将实施例1-4制备得到的含锂溶液和镍钴锰精制溶液进行Ni、Co、Mn、Li含量测定，计算三元废料中Ni、Co、Mn、Li的回收率，结果如表2。The lithium-containing solution and nickel-cobalt-manganese refined solution prepared in Examples 1-4 were subjected to Ni, Co, Mn, and Li content determination, and the recovery rate of Ni, Co, Mn, and Li in the ternary waste was calculated. The results are shown in Table 2.
表2三元废料中Ni、Co、Mn、Li的回收率The recovery rate of Ni, Co, Mn, Li in table 2 ternary waste
由表2数据可以看出，对比例4中采用单独的磷酸对三元废料进行浸出，由于磷酸为无机弱酸，对Ni、Co、Mn等过渡金属的浸出效果不佳，因此本发明采用磷酸混合强酸作为浸出液提高三元废料中Ni、Co、Mn、Li的浸出率，浸出的Ni、Co、Mn离子才能与PO4 3-形成磷酸镍钴锰沉淀，是本技术方案一步法分离回收镍钴锰溶液的前提，从而提高Ni、Co、Mn的回收率。As can be seen from the data in Table 2, in Comparative Example 4, separate phosphoric acid is used to leach the ternary waste, because phosphoric acid is an inorganic weak acid, and the leaching effect of transition metals such as Ni, Co, Mn is not good, so the present invention adopts phosphoric acid to mix. Strong acid is used as leaching solution to improve the leaching rate of Ni, Co, Mn and Li in the ternary waste, and the leached Ni, Co and Mn ions can form nickel-cobalt-manganese phosphate precipitation with PO 4 3- , which is the one-step separation and recovery of nickel and cobalt in this technical scheme The premise of manganese solution, thereby improving the recovery rate of Ni, Co, Mn.
由表2实施例1-4的数据可看出，本技术方案的的Ni、Co、Mn、Li回收率较高，能够很好的完成三元废料中镍钴锰与锂的分离回收，解决了现有技术中采用萃取剂进行分离回收导致的成本高，环境污染大的技术问题，本发明技术方案具有工艺简单、成本低、镍钴锰锂回收率高、设备要求低，且控制精度要求低，废盐量少且为固体状态，无需蒸发干燥处理等优点。As can be seen from the data of Examples 1-4 in Table 2, the Ni, Co, Mn, Li recovery rates of this technical solution are relatively high, and the separation and recovery of nickel, cobalt, manganese and lithium in the ternary waste can be well completed, and the solution is to solve the problem. The technical problems of high cost and large environmental pollution caused by the use of extractant for separation and recovery in the prior art are solved. Low salt, less waste salt and solid state, no need for evaporative drying and other advantages.
上述实施例为本发明探索的最优实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above-mentioned embodiments are the best embodiments of the present invention, but the embodiments of the present invention are not limited by the above-mentioned embodiments, and any other changes, modifications, substitutions, and combinations made without departing from the spirit and principle of the present invention , simplification, all should be equivalent replacement modes, and are all included in the protection scope of the present invention.
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Denomination of invention: Separation and Recovery Method of Nickel, Cobalt, Manganese and Lithium in Ternary Waste Effective date of registration: 20230424 Granted publication date: 20220812 Pledgee: Huaxia Bank Co.,Ltd. Jingmen Branch Pledgor: Hubei Jinquan New Material Co.,Ltd. Registration number: Y2023980039070 |
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Granted publication date: 20220812 Pledgee: Huaxia Bank Co.,Ltd. Jingmen Branch Pledgor: Hubei Jinquan New Material Co.,Ltd. Registration number: Y2023980039070 |
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Denomination of invention: Separation and recovery methods of nickel, cobalt, manganese, and lithium from ternary waste materials Granted publication date: 20220812 Pledgee: CITIC Bank Limited by Share Ltd. Wuhan branch Pledgor: Hubei Jinquan New Material Co.,Ltd. Registration number: Y2024980060245 |
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