CN117431402A - Method for efficiently separating and recycling valuable metals in waste ternary anode material - Google Patents
Method for efficiently separating and recycling valuable metals in waste ternary anode material Download PDFInfo
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- CN117431402A CN117431402A CN202311396362.2A CN202311396362A CN117431402A CN 117431402 A CN117431402 A CN 117431402A CN 202311396362 A CN202311396362 A CN 202311396362A CN 117431402 A CN117431402 A CN 117431402A
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- valuable metals
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- cobalt
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- manganese
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 71
- 239000002184 metal Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 65
- 150000002739 metals Chemical class 0.000 title claims abstract description 57
- 239000002699 waste material Substances 0.000 title claims abstract description 57
- 238000004064 recycling Methods 0.000 title claims abstract description 15
- 239000010405 anode material Substances 0.000 title claims description 15
- 238000002386 leaching Methods 0.000 claims abstract description 69
- 239000000243 solution Substances 0.000 claims abstract description 51
- 238000001556 precipitation Methods 0.000 claims abstract description 46
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 31
- 239000012535 impurity Substances 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 29
- 238000001179 sorption measurement Methods 0.000 claims abstract description 29
- 239000010406 cathode material Substances 0.000 claims abstract description 22
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 19
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 19
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 18
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 17
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 15
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 15
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002893 slag Substances 0.000 claims abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 20
- 230000009467 reduction Effects 0.000 claims description 9
- 238000003795 desorption Methods 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 150000002772 monosaccharides Chemical class 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 150000002016 disaccharides Chemical class 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000010979 pH adjustment Methods 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 28
- 238000000926 separation method Methods 0.000 abstract description 23
- 238000011084 recovery Methods 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 27
- 229910021645 metal ion Inorganic materials 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000706 filtrate Substances 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 229920005989 resin Polymers 0.000 description 17
- 229910052759 nickel Inorganic materials 0.000 description 16
- 230000000694 effects Effects 0.000 description 15
- 229910001416 lithium ion Inorganic materials 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 14
- 239000011572 manganese Substances 0.000 description 14
- -1 aluminum ions Chemical class 0.000 description 13
- 229910052748 manganese Inorganic materials 0.000 description 12
- 239000010949 copper Substances 0.000 description 8
- 238000000605 extraction Methods 0.000 description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 6
- 229910001431 copper ion Inorganic materials 0.000 description 6
- 239000008103 glucose Substances 0.000 description 6
- 150000007524 organic acids Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 4
- 229930006000 Sucrose Natural products 0.000 description 4
- 239000005720 sucrose Substances 0.000 description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910001428 transition metal ion Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IJRKANNOPXMZSG-SSPAHAAFSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O.OC(=O)CC(O)(C(O)=O)CC(O)=O IJRKANNOPXMZSG-SSPAHAAFSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- NXPZICSHDHGMGT-UHFFFAOYSA-N [Co].[Mn].[Li] Chemical compound [Co].[Mn].[Li] NXPZICSHDHGMGT-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- QUXFOKCUIZCKGS-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphinic acid Chemical compound CC(C)(C)CC(C)CP(O)(=O)CC(C)CC(C)(C)C QUXFOKCUIZCKGS-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 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 1
- 238000013507 mapping Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Classifications
-
- 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
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0423—Halogenated acids or salts thereof
-
- 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
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- 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
-
- 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
- C22B47/00—Obtaining manganese
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for efficiently separating and recycling valuable metals in waste ternary cathode materials, which comprises the steps of reducing and leaching the waste ternary cathode materials by adopting inorganic dilute acid and an organic reducing agent to obtain a metal mixed solution; strictly controlling the pH value and the temperature of the metal mixed solution to carry out selective precipitation and impurity removal to obtain iron-rich aluminum slag and nickel-cobalt-manganese-lithium enrichment solution; and (3) adsorbing nickel ions, cobalt ions and manganese ions in the nickel-cobalt-manganese-lithium enriched liquid by adopting cation exchange resin, and then analyzing to obtain the nickel-cobalt-manganese enriched liquid, wherein the adsorption residual liquid is the lithium enriched liquid. The method can realize the efficient separation and recovery of valuable metals in the waste ternary waste, reduces the use cost of the reducing agent, and has simple process flow and obvious economic and environmental benefits.
Description
Technical Field
The invention relates to a method for recycling waste ternary cathode materials, in particular to a method for comprehensively recycling valuable metals in waste ternary cathode materials, and belongs to the technical field of waste battery resource recycling.
Background
The ternary lithium ion battery is widely applied to the fields of portable electronic products, new energy automobiles and the like because of the advantages of high energy density, low self-discharge rate, high working voltage and the like. However, lithium ion batteries are used as a consumable product, and the annual consumption increases year by year, and the scrapping amount increases year by year. The waste ternary lithium ion battery mainly comprises an anode, a cathode, an organic electrolyte and a diaphragm. The positive electrode of the battery contains a large amount of valuable metals such as nickel, cobalt, manganese and lithium, so that the recycling of the valuable metals in the waste ternary lithium ion battery becomes a hot spot of current research.
Currently, hydrometallurgy is the most commonly used method for recycling waste ternary cathode materials, and valuable metals in a solid phase are dissolved mainly by using acid liquor, so that the valuable metals are transferred into a liquid phase. Since nickel, cobalt and manganese in the waste ternary anode material exist in the form of high-valence metal oxide, a reducing agent is needed to be added in the acid leaching process to improve the leaching efficiency. In the prior art, a leaching system consisting of hydrogen peroxide and sulfuric acid has been industrially used, but hydrogen peroxide as a reducing agent can reduce the carry-over of impurity ions, but has the disadvantages of unstable storage, relatively high price, easy tank overflow in the leaching process, and the like. Therefore, the organic acid leaching system with mild leaching conditions, low price and higher leaching efficiency becomes a research hot spot, and mainly comprises organic acid, inorganic reducing agent, organic acid, organic reducing agent, inorganic acid, organic reducing agent and the like, and no matter which leaching system is selected, the ternary acid leaching solution obtained after the leaching process contains a large amount of organic matters. However, the existing high-efficiency separation and recovery of nickel, cobalt and manganese basically adopts a solvent extraction method, and the extraction and separation effects of the Cyanex272 extractant on nickel and cobalt are remarkable, so that the method is widely applied to enterprises. However, the residue of organic matters in the pickle liquor tends to cause a series of problems such as low extraction efficiency, emulsification of the extractant and the like. Therefore, the separation and recovery of valuable metals such as nickel, cobalt, manganese, lithium and the like in an acidic organic solution becomes a difficult problem puzzling the industry.
Chinese patent (CN 108913873A) discloses a method for recovering high added value metal from waste nickel-cobalt-manganese lithium ion batteries, which comprises the steps of thoroughly placing waste ternary lithium ion batteries, disassembling to obtain positive electrode powder, and performing heat treatment on the positive electrode powder to remove impurities such as conductive agents, binders and the like. And then carrying out mechanical-chemical synergistic activation on the positive electrode powder after heat treatment and the active additive, and carrying out reduction acid leaching on the activated positive electrode powder and citric acid-glucose, wherein valuable metals nickel cobalt manganese lithium in the acid leaching solution are sequentially precipitated step by step. The method adopts an acid leaching system consisting of organic acid and organic reducing agent to realize efficient leaching of valuable metals, but the subsequent separation and recovery of valuable metals adopts a chemical precipitation method, the process flow is long and complex, the loss of valuable metals is larger, and especially the ionic radius of Li is smaller, and the valuable metals are easy to adsorb and coprecipitate to cause loss.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide the method for efficiently separating and recycling the valuable metals in the waste ternary anode material, which adopts a process combining organic matter reduction acid leaching, high-temperature precipitation impurity removal and ion exchange separation, can realize the efficient separation and recycling of the valuable metals in the waste ternary waste, reduces the use cost of the reducing agent, has simple process flow and obvious economic benefit and environmental protection benefit.
In order to achieve the technical aim, the invention provides a method for efficiently separating and recycling valuable metals in waste ternary anode materials, which comprises the following steps:
1) Reducing and leaching the waste ternary anode material by adopting inorganic dilute acid and an organic reducing agent to obtain a metal mixed solution;
2) The pH value of the metal mixed solution is adjusted to 3-5, precipitation and impurity removal are carried out for 30-150 min at the temperature of 30-95 ℃ to obtain iron-rich aluminum slag and nickel-cobalt-manganese-lithium enrichment solution;
3) And (3) adsorbing nickel ions, cobalt ions and manganese ions in the nickel-cobalt-manganese-lithium enriched liquid by adopting cation exchange resin, and then analyzing to obtain the nickel-cobalt-manganese enriched liquid, wherein the adsorption residual liquid is the lithium enriched liquid.
The method for efficiently separating and recycling the valuable metals in the waste ternary anode material provided by the invention comprises three main steps of reduction acid leaching, high-temperature impurity removal and resin separation, so that the efficient separation and recycling of the valuable metals can be realized, the cost can be reduced, and the process flow is simplified. More specifically, the method comprises the steps of carrying out reduction acid leaching by using inorganic dilute acid and organic reducing agent, so that efficient leaching of valuable metals in waste ternary waste can be realized, the leaching efficiency of metals is obviously improved by adding the organic reducing agent, the leaching rates of lithium ions, nickel ions, cobalt ions and manganese ions with higher values can reach more than 98%, but the leaching rates of impurity metal ions such as aluminum ions, iron ions and copper ions are also very high, and the method adopts a high-temperature precipitation method for separating the impurity metal ions. A large amount of organic matters are remained in the solution system for removing the impurity metal ions, and the organic matters contain oxygen-containing groups and have certain complexation effect on the transition metal ions, so that the transition metal ions cannot be separated from the lithium ions by adopting a conventional extraction method. In order to avoid the influence of residual organic matters on metal ion extraction and separation in the leaching process, the method adopts cation exchange resin adsorption to realize the separation of lithium ions from nickel ions, cobalt ions and manganese ions, the lithium ions can be independently recovered for preparing lithium carbonate, and the nickel ions, the cobalt ions and the manganese ions can be directly used for preparing ternary cathode materials, so that the efficient separation and recovery of valuable metals in the waste ternary cathode materials are truly realized.
As a preferable embodiment, the concentration of the inorganic dilute acid is 1.0 to 4.0mol/L. If the concentration of the inorganic dilute acid is too low, more volume of the inorganic dilute acid is required to complete the leaching process, and if the concentration of the inorganic dilute acid is too high, more lye is required to neutralize the acidity to complete the neutralization precipitation process, which increases the acid-base consumption cost.
As a preferred embodiment, the inorganic dilute acid includes at least one of dilute phosphoric acid, dilute sulfuric acid, and dilute nitric acid.
As a preferred embodiment, the organic reducing agent is a saccharide compound, and the saccharide compound specifically includes at least one of monosaccharide, disaccharide, and polysaccharide. Such as at least one of glucose, sucrose, cellulose. As a more preferable scheme, the consumption of the organic reducing agent is 4-24% of the mass of the waste ternary cathode material. More specifically, the organic reducing agent may be a waste material rich in glucose, sucrose, cellulose, or other biological organic substances, or may be a commercial reagent such as analytical grade glucose, sucrose, cellulose, or the like, and most preferably the organic reducing agent is a monosaccharide. The advantages of using organic reducing agents over conventional reducing agents such as hydrogen peroxide are: the leaching process has milder conditions (hydrogen peroxide is used as a reducing agent to react vigorously and is easy to overflow), lower price, more stable storage and the like.
As a preferred embodiment, the conditions for the reduction leaching are: the liquid-solid ratio is 6-14 mL/g, the leaching temperature is 333K-363K, and the leaching time is 30-240 min. The feasibility of the reduction acid leaching section is analyzed through thermodynamics, the influence of different factors on leaching is explored through a large number of experiments, and the efficient leaching of valuable metals in the waste ternary anode material can be realized under the optimized reduction leaching condition.
As a preferred embodiment, the cation exchange resin comprises a strong acid cation resin and/or a weak acid cation resin. The cation exchange resins are specifically selected from D001, D732, and D113. The weak acid cation resin D113 has larger adsorption capacity and selectivity for adsorbing nickel ions, cobalt ions and manganese ions, is not influenced by organic matters and lithium ions in the adsorption process, and is more beneficial to selectively adsorbing the nickel ions, the cobalt ions and the manganese ions from complex mixed metal ion solution containing organic matters.
As a preferred embodiment, the conditions of the adsorption are: the pH value is 3-5, the temperature is room temperature, and the time is 30-180 min. Further preferably, the pH is 4.75 to 5. The influence of pH on the adsorption effect is relatively large, and if the pH is too high, the hydrolysis and precipitation of nickel ions, cobalt ions and manganese ions are easy to cause, and if the pH is too low, the adsorption capacity and adsorption selectivity to nickel ions, cobalt ions and manganese ions are reduced based on the influence of acid protons, so that the selective and efficient adsorption of the cation exchange resin to nickel ions, cobalt ions and manganese ions is more facilitated in a preferable pH range.
The invention adopts cation exchange resin to adsorb, which can realize the high-efficiency separation of lithium ion, nickel ion, cobalt ion and manganese ion, and the residual organic matters in the solution system do not influence the exchange process of the cation exchange resin on metal ion, thereby overcoming the technical defect that the traditional organic acid leaching system is difficult to efficiently separate transition metal ion by adopting an extraction method.
As a preferable scheme, the desorption adopts dilute sulfuric acid or dilute hydrochloric acid as a desorption solution, and the concentration of the desorption solution is 1-3 mol/L.
As a preferred embodiment, the pH adjustment is performed using sodium hydroxide solution.
As a preferable scheme, the conditions for precipitation and impurity removal are as follows: the pH value of the metal mixed solution is adjusted to 4.75-5, the temperature is 75-90 ℃ and the time is 120-150 min. A large number of experiments show that the precipitation efficiency of almost all metal ions increases to different degrees with increasing pH, but the precipitation efficiency of copper ions, aluminum ions and iron ions is greatly influenced by pH, particularly aluminum ions and copper ions, and when the pH reaches 4.75-5, the precipitation efficiency is obviously increased and greatly differs from the precipitation efficiency of nickel ions, cobalt ions and manganese ions, so that the optimal pH range is controlled within the range of 4.75-5. In the process of precipitation impurity removal, under a certain pH condition, the higher the temperature and the longer the time are, the lower the precipitation efficiency of nickel ions, cobalt ions and manganese ions is, and the precipitation efficiency of impurity metal ions such as copper ions, aluminum ions and iron ions is basically unchanged, so that the precipitation of the impurity metal ions such as copper ions, aluminum ions and iron ions is realized on the basis of the minimum precipitation efficiency of nickel ions, cobalt ions and manganese ions, and the loss of useful metal ions is reduced.
The invention provides a method for efficiently separating and recycling valuable metals in waste ternary anode materials, which comprises the following steps:
organic matter reduction acid leaching process (S1): adding a certain amount of waste ternary anode powder into a dilute sulfuric acid solution with a certain concentration, adding a certain amount of organic reducing agent into the solution, placing the solution in a constant-temperature water bath for reaction for a period of time, and performing solid-liquid separation after the acid leaching reaction reaches equilibrium to obtain metal mixed solution and carbon slag.
High temperature precipitation impurity removal process (S2): and (3) slowly adjusting the pH value of the metal mixed solution obtained in the step (S1) by adopting a dilute sodium hydroxide solution or dilute ammonia water, placing the adjusted mixed solution in a constant-temperature water bath, raising the temperature to a set temperature, reacting for a certain time under a constant-temperature condition, and carrying out solid-liquid separation after the precipitation reaction reaches equilibrium to obtain nickel-rich cobalt-manganese-lithium filtrate and iron-rich aluminum slag.
Ion exchange process (S3): adding a certain amount of dry resin into the nickel-cobalt-manganese-lithium-rich mixed solution, placing the mixed solution into a constant-temperature oscillating box for reacting for a period of time, analyzing the adsorbed resin by adopting a dilute sulfuric acid solution, and precipitating the obtained nickel-cobalt-manganese-rich solution to synthesize a ternary precursor, and concentrating the adsorbed solution to precipitate and synthesize lithium carbonate.
Compared with the prior art, the invention has the beneficial technical effects that:
(1) The invention provides a novel method for realizing efficient separation and recovery of valuable metals in waste ternary cathode materials, which adopts organic reducing agent and inorganic dilute acid to realize efficient leaching of valuable metals in waste ternary cathode materials, on the basis, selective precipitation of aluminum ions, iron ions, copper ions and other impurity metal ions is realized through a high-temperature precipitation method, and then efficient separation of lithium ions, nickel ions, cobalt ions, manganese ions and the like in an organic solution system is realized through adsorption of cation exchange resin, so that high-purity nickel-cobalt-manganese enrichment liquid and lithium enrichment liquid are finally obtained, and the method can be directly used for preparing ternary cathode materials and lithium carbonate.
(2) The traditional waste ternary anode material adopts a leaching system consisting of sulfuric acid and hydrogen peroxide, although hydrogen peroxide is taken as a reducing agent, the efficient leaching of valuable metals in the waste ternary anode material can be realized, impurity ions are not introduced, the hydrogen peroxide is high in price, the problems of groove overflow and the like are easily caused in a severe reaction process, the leaching system consisting of an organic reducing agent and an organic acid can realize the efficient leaching of the valuable metals, but the organic leaching liquid enters a traditional extraction separation system, the extraction effect is influenced, and the impurity metal ions in the leaching system are difficult to precipitate. On the one hand, the invention realizes the selective precipitation of impurity metal ions by adopting a high-temperature precipitation method, reduces the loss of valuable metal ions such as nickel ions, cobalt ions, manganese ions, lithium ions and the like while removing the impurity metal ions efficiently, and on the other hand, adopts cation exchange resin adsorption to realize the separation of lithium ions from nickel ions, cobalt ions and manganese ions, thereby avoiding the influence of residual organic matters on the extraction and separation of metal ions in the leaching process.
(3) The method for efficiently separating and recovering the valuable metals in the waste ternary anode material reduces the use cost of the reducing agent, has simple process flow, and has high recovery rate of the valuable metals, obvious economic benefit and environmental protection benefit.
Drawings
For a clearer description of embodiments of the invention or of the solutions of the prior art, reference will be made to the accompanying drawings which are used in the description of embodiments or of the prior art, it being obvious to a person skilled in the art that other drawings can be obtained from these without inventive effort.
FIG. 1 is an XRD pattern of the waste ternary cathode material of example 1.
FIG. 2 shows the effect of different initial pH, reaction time, reaction temperature on the precipitation impurity removal process; the optimal precipitation conditions can be obtained from the results in fig. 2 as follows: the initial pH value is 5, the reaction time is 120min, the reaction temperature is 75 ℃, under the condition, the precipitation rate of valuable metal nickel cobalt manganese lithium is below 3%, and the precipitation rate of impurity metal is higher than 90%.
FIG. 3 is an SEM of the waste ternary cathode material before and after leaching (a: waste ternary cathode material, b: leached residue); by comparing the waste before leaching and after leaching, the waste ternary material is a regular round particle before leaching, and after reducing acid leaching, the spherical particle is destroyed, and the structure is porous and irregular.
FIG. 4 is an SEM image of the cation exchange resin of example 1 before and after adsorption; before adsorption, the surface structure of the cation exchange resin is loose and porous, after valuable metals are adsorbed, a plurality of fine particles are distributed in gaps of the surface porous structure, and the fine particles are determined to be valuable metals nickel cobalt manganese through a further Mapping graph.
FIG. 5 is a graph showing the effect of different initial pH values in the solution after removal of impurities on the adsorption effect of the resin; adsorption capacity Q of resin to valuable metals by raising pH of nickel-cobalt-manganese-lithium-rich filtrate e The separation coefficient beta (Me/Li) of the valuable metals Me (Ni, co and Mn) and Li is gradually increased, which shows that the valuable metals Me (Ni, co and Mn) and Li have a better separation effect when the pH value is close to 5.
FIG. 6 is an XRD pattern of the lithium carbonate product of example 1; by comparing with XRD card of standard lithium carbonate, it can be seen that the prepared lithium carbonate product has high crystallinity and low impurity content.
Detailed Description
To describe the technical contents, the achieved objects and effects of the present invention in detail, the following embodiments are described in conjunction with the accompanying drawings.
Example 1
Step 1: the waste ternary battery is pretreated to obtain waste ternary powder, and the content of each component in the obtained powder is as follows: 2.73% Al,1.31% Fe,0.22% Cu,24.9% Ni,9.1% Co,14.3% Mn,5.86% Li. 5g of waste ternary powder is taken, 3mol/L sulfuric acid solution is added according to a liquid-solid ratio of 12mL/g, 1g of organic reducer glucose is added into the waste ternary powder, the powder is leached at room temperature for 3 hours, and the leaching rate of metal ions in the obtained filtrate is 87.35% of Al, 99.8% of Fe, 99.2% of Cu, 99.6% of Li, 98.5% of Ni, 99.4% of Co and 98.9% of Mn.
Step 2: the pH value in the organic leaching solution is regulated to be 5 by a 1mol/L dilute sodium hydroxide solution, the reaction is carried out for 30min at 30 ℃, the precipitation rate of metal ions in the filtrate after the reaction is Al 95%, fe 89.5%, cu 88.9%, and the concentration of other valuable metals (Ni, co, mn, li) is basically unchanged.
Step 3: adding 20g of dry D113 resin into 100mL of nickel-cobalt-manganese-lithium-enriched filtrate, placing the filtrate in a constant-temperature oscillating box indoors for reaction for 6 hours, after adsorption reaches equilibrium, resolving the adsorption resin by using 1mol/L of dilute sulfuric acid solution to obtain a nickel-cobalt-manganese-enriched solution, precipitating the nickel-cobalt-manganese-enriched solution by ammonia water to synthesize a nickel-cobalt-manganese precursor, returning the lithium-enriched solution (4088 mg/L Li) to the step 1 for Li enrichment, and precipitating to synthesize a lithium carbonate product. The recovery rate of nickel, cobalt and manganese is 97%, 98% and 97%, respectively, and the recovery rate of lithium can reach 99% after cyclic enrichment.
Example 2
Step 1: the waste ternary battery is pretreated to obtain waste ternary powder, and the content of each component in the obtained powder is as follows: 2.73% Al,1.31% Fe,0.22% Cu,24.9% Ni,9.1% Co,14.3% Mn,5.86% Li. 5g of waste ternary powder is taken, 2mol/L sulfuric acid solution is added according to a liquid-solid ratio of 10mL/g, 3g of organic reducer glucose is added into the waste ternary powder, the powder is leached at room temperature for 3 hours, and the leaching rate of metal ions in the obtained filtrate is 86.65% of Al, 98.2% of Fe, 98.5% of Cu, 98.9% of Li, 99.1% of Ni, 99.1% of Co and 99.2% of Mn.
Step 2: the pH value in the organic leaching solution is regulated to be 5 by a 1mol/L dilute sodium hydroxide solution, the reaction is carried out for 30min at 30 ℃, and the concentration of 94.6% of Al, 86.1% of Fe, 87.3% of Cu and other valuable metals (Ni, co, mn and Li) in the filtrate is basically unchanged after the reaction.
Step 3: and adding 20g of dry D113 resin into 100mL of nickel-cobalt-manganese-lithium-enriched filtrate, placing the filtrate in a constant-temperature oscillating box indoors for reaction for 6 hours, after adsorption reaches equilibrium, resolving the adsorption resin by using 1mol/L of dilute sulfuric acid solution to obtain a nickel-cobalt-manganese-enriched solution, precipitating the nickel-cobalt-manganese-enriched solution, synthesizing a nickel-cobalt-manganese precursor by ammonia water, returning the lithium-enriched solution (3879 mg/L Li) to the step 1 for Li enrichment, and then precipitating to synthesize a lithium carbonate product.
Example 3
Step 1 is the same as in example 1:
in the step 2, the pH values of the organic leaching solution are respectively 3.75, 4, 4.5, 4.75 and 5, the reaction is carried out for 30min at 30 ℃, and the precipitation rate of metal ions in the filtrate after the reaction is shown as a in figure 2. As the pH value increases, the precipitation rate of impurity metal ions Al, fe and Cu increases, a better removal effect is achieved, but the precipitation rate of valuable metals is higher, and the precipitation conditions need to be further optimized.
Example 4
Step 1 is the same as in example 1:
in the step 2, the pH value of the organic leaching solution is regulated to be 5, and the organic leaching solution is respectively reacted for 30, 60, 90, 120 and 150 minutes at room temperature, and the precipitation rate of metal ions in the filtrate after the reaction is shown as b in figure 2. With the increase of the reaction time, the precipitation rate of impurity metal ions Al, fe and Cu is not greatly changed, but the precipitation rate of valuable metals is gradually reduced, mainly the concentration of the valuable metals in the organic leaching solution is too high, and the precipitation loss is easily caused by local overbasing in the process of regulating the pH. Thus, extending the reaction time is advantageous for redissolving the hydroxide precipitate of the metal of value with reduced losses.
Example 5
Step 1 is the same as in example 1:
in the step 2, the pH value of the organic leaching solution is regulated to be 5, and the organic leaching solution is respectively reacted for 120min at 30, 45, 60, 75 and 90 ℃, and the precipitation rate of metal ions in the filtrate after the reaction is shown as c in figure 2. As the reaction temperature increases, the precipitation of the impurity metals Al, fe and Cu is not changed much, while the precipitation rate of the valuable metals is slightly reduced, which shows that the increase of the temperature is favorable for redissolving the hydroxide precipitation of the valuable metals, and the result is similar to the result under different reaction time.
Example 6
Step 1 is the same as in example 1;
step 2 is the same as in example 1;
in the step 3, the pH value of the nickel-cobalt-manganese-lithium-enriched filtrate is adjusted to 3.25, 3.5, 3.75, 4.25, 4.75 and 5.2, and an equal amount of 20g of dry D113 resin is added to 100mL of the adjusted filtrate at room temperature to perform adsorption reaction, wherein the adsorption performance of the resin on valuable metals is shown in the following figure 5. As the pH increases, the adsorption capacity of the resin for the valuable metals Me (Ni, co, mn) gradually increases. The separation coefficient beta (Me/Li) of valuable metals Me (Ni, co and Mn) and Li is gradually increased, and the pH value of the adsorption solution is continuously increased, so that nickel, cobalt and manganese are precipitated. In addition, the impurity removal effect is remarkable when the pH is adjusted to 5 in the high-temperature precipitation process, so that the pH of the nickel-cobalt-manganese-lithium-rich filtrate before adsorption does not need to be adjusted.
Example 7
Sucrose is adopted to replace glucose as an organic reducing agent in step 1 of the embodiment 1, the rest of the processes are operated in the embodiment 1, filter residues are obviously more in the leaching process, the leaching process is incomplete, a large amount of valuable metals can be presumed to remain in a solid phase, and the leaching rate of metal ions in the obtained filtrate is Al 81.65%, fe 88.2%, cu78.5%, li 88.9%, ni 79.1%, co 79.1% and Mn 82.2%. The monosaccharide is used as the reducing agent in the leaching process, and the leaching effect is obviously better than that of disaccharide.
Example 8
The pH of the leachate was adjusted to 5 by using a 1:1 dilute aqueous ammonia solution instead of a 1mol/L dilute aqueous sodium hydroxide solution in step 2 of example 2, and the rest of the procedure was carried out in accordance with example 2, wherein the precipitation rates of the respective metal ions were respectively Al6.5%, fe 0.22%, cu 1.47%, li 1.36%, ni 5.19%, co 1.9% and Mn 3.86%. In the process of precipitation impurity removal, no impurities are basically separated out, the precipitation effect is poor, the combination capability of ammonia water and metal ions is strong, and the actual precipitation pH value can be higher.
Example 9
100mL of the nickel-cobalt-manganese-lithium-rich solution was adsorbed by using a strongly acidic cationic resin D001 instead of the D113 resin in step 3 of example 1, and the rest of the procedure was carried out in example 1, and it was found that the concentration of Li was significantly reduced in the adsorption process compared with the impurity-removed solution, and the adsorption rate of Li was 41.8%. D113 is a cation exchange resin having the best effect of adsorbing nickel ions, manganese ions and cobalt ions from an acidic solution containing an organic substance.
The foregoing is a description of the embodiments of the present invention, but the scope of the present invention is not limited thereto, and any technical field of the present invention is within the scope of the present invention, and the technical solution according to the present invention and the inventive concept thereof are equivalent or changed and should be covered by the scope of the present invention.
Claims (9)
1. A method for efficiently separating and recycling valuable metals in waste ternary anode materials is characterized by comprising the following steps of: the method comprises the following steps:
1) Reducing and leaching the waste ternary anode material by adopting inorganic dilute acid and an organic reducing agent to obtain a metal mixed solution;
2) The pH value of the metal mixed solution is adjusted to 3-5, precipitation and impurity removal are carried out for 30-150 min at the temperature of 30-95 ℃ to obtain iron-rich aluminum slag and nickel-cobalt-manganese-lithium enrichment solution;
3) And (3) adsorbing nickel ions, cobalt ions and manganese ions in the nickel-cobalt-manganese-lithium enriched liquid by adopting cation exchange resin, and then analyzing to obtain the nickel-cobalt-manganese enriched liquid, wherein the adsorption residual liquid is the lithium enriched liquid.
2. The method for efficiently separating and recovering valuable metals in waste ternary cathode materials according to claim 1, which is characterized in that:
the inorganic dilute acid comprises at least one of dilute phosphoric acid, dilute sulfuric acid and dilute nitric acid;
the organic reducing agent comprises at least one of monosaccharide, disaccharide and polysaccharide.
3. The method for efficiently separating and recovering valuable metals in waste ternary cathode materials according to claim 2, which is characterized in that:
the concentration of the inorganic dilute acid is 1.0-4.0 mol/L;
the consumption of the organic reducing agent is 4-24% of the mass of the waste ternary cathode material.
4. The method for efficiently separating and recovering valuable metals in waste ternary cathode materials according to any one of claims 1 to 3, which is characterized by comprising the following steps: the conditions of the reduction leaching are as follows: the solid ratio of the leaching solution is 6-14 mL/g, the leaching temperature is 333K-363K, and the leaching time is 30-240 min.
5. The method for efficiently separating and recovering valuable metals in waste ternary cathode materials according to claim 1, which is characterized in that: the cation exchange resin comprises at least one of D001, D732 and D113.
6. The method for efficiently separating and recovering valuable metals in waste ternary cathode materials according to claim 1, which is characterized in that: the conditions of the adsorption are as follows: the pH value is 3-5, the temperature is room temperature, and the time is 30-180 min.
7. The method for efficiently separating and recovering valuable metals in waste ternary cathode materials according to claim 1, which is characterized in that: the desorption adopts dilute sulfuric acid and/or dilute hydrochloric acid as an analytical solution; the concentration of the desorption solution is 1-3 mol/L.
8. The method for efficiently separating and recovering valuable metals in waste ternary cathode materials according to claim 1, which is characterized in that: the pH adjustment is performed by adopting sodium hydroxide solution.
9. The method for efficiently separating and recovering valuable metals in waste ternary anode materials according to claims 1, 2, 3, 5, 6, 7 or 8, which is characterized in that: the conditions for precipitation and impurity removal are as follows: the pH value of the metal mixed solution is adjusted to 4.75-5, the temperature is 75-90 ℃ and the time is 120-150 min.
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