CN107017444A - A kind of method of metal recovery in waste lithium iron phosphate battery - Google Patents
A kind of method of metal recovery in waste lithium iron phosphate battery Download PDFInfo
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- CN107017444A CN107017444A CN201710251704.XA CN201710251704A CN107017444A CN 107017444 A CN107017444 A CN 107017444A CN 201710251704 A CN201710251704 A CN 201710251704A CN 107017444 A CN107017444 A CN 107017444A
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- lithium
- iron
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- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000002699 waste material Substances 0.000 title claims abstract description 24
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 15
- 239000002184 metal Substances 0.000 title claims abstract description 15
- 238000011084 recovery Methods 0.000 title claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 121
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 117
- 239000000843 powder Substances 0.000 claims abstract description 62
- 239000000243 solution Substances 0.000 claims abstract description 38
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 36
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 30
- 238000002386 leaching Methods 0.000 claims abstract description 27
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 26
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 25
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 25
- 238000001556 precipitation Methods 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 21
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 18
- 230000001590 oxidative effect Effects 0.000 claims abstract description 13
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 10
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 111
- 229910052742 iron Inorganic materials 0.000 claims description 54
- 239000004411 aluminium Substances 0.000 claims description 37
- 229910052782 aluminium Inorganic materials 0.000 claims description 37
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000498 ball milling Methods 0.000 claims description 13
- 238000000605 extraction Methods 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 9
- 239000002893 slag Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 239000001527 calcium lactate Substances 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- 239000012141 concentrate Substances 0.000 claims description 6
- 239000012634 fragment Substances 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- 229910014813 CaC2 Inorganic materials 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- 230000008719 thickening Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 239000002028 Biomass Substances 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 230000005484 gravity Effects 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000007654 immersion Methods 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000002787 reinforcement Effects 0.000 abstract description 2
- 239000013043 chemical agent Substances 0.000 abstract 1
- 239000011575 calcium Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 239000005955 Ferric phosphate Substances 0.000 description 6
- 229940032958 ferric phosphate Drugs 0.000 description 6
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 6
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 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
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000007780 powder milling Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
Classifications
-
- 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
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- 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
- 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
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- Processing Of Solid Wastes (AREA)
- Primary Cells (AREA)
Abstract
The invention provides a kind of method of waste lithium iron phosphate battery metal recovery, waste lithium iron phosphate battery is calcined and sorted by this method, obtain positive mix containing lithium, the powder containing lithium Strengthen education in the mixed solution of ammonium salt and/or ammonia, is converted to ferric iron, and form precipitation in oxidative environment by ferrous iron, so as to obtain lithium-containing solution, filtering, for the preparation of high purity lithium product, obtains the high-value product such as lithium hydroxide or lithium carbonate；The invention is different from traditional wet method acid immersion, acid lixiviant is not used, avoid the generation of a large amount of high-salt wastewaters, elemental lithium is leached by selective reinforcement, leaching efficiency is high, leachate consumption is small, high-purity lithium-containing solution can be obtained, the lithium product purity finally obtained is high, and flow is short, chemical agent wide material sources, process conditions are simple, alternative Strengthen education elemental lithium, reclaim and obtain high purity lithium product, the recovery benefit of waste lithium iron phosphate battery is improved, with good prospects for commercial application.
Description
Technical field
Recycled the invention belongs to secondary resource and recycling economy technical field, more particularly to a kind of waste lithium iron phosphate
The method of metal recovery in battery.
Background technology
Under energy-conservation and the dual-pressure of emission reduction, new-energy automobile turns into the direction of future automobile industrial development.With
Government widelys popularize, and new-energy automobile industry will enter Rapid development stage by the starting stage.Electrokinetic cell is used as new energy
One of parts of source automobile most critical, demand rapidly increases.Wherein, ferric phosphate lithium cell is because with higher theoretical appearance
Amount, good discharge platform, outstanding cyclical stability and it is cheap the advantages of, be widely used in new-energy automobile.It is waste and old
The reasonable recycling of LiFePO 4 material will promote the development of new-energy automobile industry, realize the comprehensive utilization of resource.
In the recent period, principle of the domestic and international researcher based on hydrometallurgy, is developed in a series of waste lithium iron phosphate batteries
The technique for reclaiming high level element, its main flow be by old and useless battery it is fired, it is broken obtain batch mixing, then removed using alkaline process
Aluminium, obtains iron, lithium mixing slag, then leaches iron, elemental lithium simultaneously, and selective precipitation obtains lithium product afterwards.Such as
CN103280610A obtains iron content lithium-containing solution by alkaline process dissolving, and iron is removed with ferric phosphate precipitation form, and gained contains lithium
Solution is further used for the recovery of elemental lithium.CN101847763A is then using organic solvent dissolving and acidolysis, then auxiliary addition
Vulcanized sodium obtains elemental lithium.CN102956936A discloses a kind of method for recycling valuable metal based on acidleach and alkali leaching,
Positive electrode after roasting is after 0.5 ~ 2.0 time acidleach of pH value, and acidleach filtrate readjustment pH value precipitation of aluminium, iron, copper, alkali lixivium enter
One step readjustment pH value is used to recycle lithium.Above-mentioned wet-leaching technique, iron elemental lithium is not separated before leaching,
Also Selectively leaching is not used in leaching process, causes to leach acid consumption greatly.Leachate contains substantial amounts of iron tramp, causes removal of impurities
Complex process, reclaims the lithium carbonate product taste obtained low, it is impossible to real to be used for the reproduction of battery.In addition existing process is related to
And to removal of impurities and cleaning procedure, it will usually a large amount of high-salt wastewaters are produced, such as deals with improperly and may result in secondary pollution, increase environment
Cost；Such as extra increase wastewater treatment link, then it can increase cost for wastewater treatment, not meet recycling economy development theory, also not
Possesses the value that large-scale promotion is used.
At present, the research of high-temperature calcination is concentrated mainly on the regeneration of lithium iron phosphate positive material, such as CN102280673A,
CN102583297A, CN102751548A, CN104362408A disclose the high-temperature calcination under oxidative conditions and prepare ferric phosphate
The technological parameter of lithium product.Based on current hydrometallurgy or pyrometallurgical recovery process, although phosphorus can be recycled
Sour lithium iron battery, and the multiple products such as lithium iron phosphate positive material or lithium carbonate are obtained, but temperature calcining directly prepares phosphoric acid
Often technological process is long for iron lithium anode material, it is desirable to strictly controls reaction condition, and needs the auxiliary production of high energy consumption process, therefore
Practical application is extremely limited.
The content of the invention
In order to improve old and useless battery organic efficiency, products obtained therefrom quality is improved, it is to avoid wastewater treatment derived from existing process
Problem, the present invention is intended to provide in a kind of waste lithium iron phosphate battery metal recovery method.The invention selective reinforcement is leached
Elemental lithium, leaching efficiency is high, leachate consumption is small, can obtain high-purity lithium-containing solution, therefore the lithium product purity obtained
It is high.Waste lithium iron phosphate battery is calcined and sorted, positive mix containing lithium is obtained.Powder containing lithium is molten in the mixing of ammonium salt and/or ammonia
Strengthen education in liquid, ferric iron is converted in oxidative environment by ferrous iron, and forms precipitation, obtains lithium-containing solution, filtering
It can be used for the preparation of high purity lithium product afterwards, obtain the high-value product such as lithium hydroxide or lithium carbonate.The invention has been different from biography
The wet method acid immersion of system, does not use acid lixiviant, it is to avoid the generations of a large amount of high-salt wastewaters.Because flow of the present invention is short, work
Simple, the alternative Strengthen education elemental lithium of skill, reclaims and obtains high purity lithium product, improve the recovery of waste lithium iron phosphate battery
Benefit, with good prospects for commercial application.
For up to this purpose, the present invention uses following technical scheme：
A kind of method that waste lithium iron phosphate battery Strengthen education reclaims metal, comprises the following steps：
（1）By old and useless battery be calcined sorting obtain containing aluminium, iron, lithium battery material powder；
（2）Step（1）Gained carries out alkaline process containing aluminium, iron, lithium powder and removes aluminium, obtains iron content residue containing lithium；
（3）Step（2）Gained iron content residue containing lithium, ball milling obtains iron content powder containing lithium；
（4）Step（3）Gained powder containing lithium is in ammonium salt and/or the mixed solution Strengthen education of ammonia, while in an oxidizing environment, inciting somebody to action
Ferrous iron is converted to ferric iron, forms water insoluble iron containing compoundses, Selectively leaching elemental lithium；
（5）Step（4）After leachate/slag separation, lithium-containing solution is concentrated, reclaims and obtains ammonium salt and/or ammonia；
（6）Step（5）Gained concentrate obtains Lithium hydroxide or lithium carbonate for reclaiming lithium resource.
Step（1）LiFePO4 old and useless battery is broken and be calcined sorting, obtain containing aluminium, iron, lithium battery material powder；
It is preferred that, cell positive material is broken for 1 ~ 20mm × 1 ~ 20mm fragment by Mechanical Crushing；
It is preferred that, sintering temperature is 200 ~ 1200 DEG C, and roasting time is 1 ~ 6h.
Step（1）Calcic powder can be sprayed into roasting process to absorb the fluoro-gas of generation, the battery waste is with containing
The quality proportioning of calcium powder body is 20 ~ 300:1；
It is preferred that, the calcic powder is a kind of in calcic inorganic matter, calcic organic matter and calcic biomass or any several
Combination；
It is preferred that, the calcic powder is preferably CaC2、CaCl2、CaCO3、Ca(NO3)2、CaO、Ca(OH)2、Ca5(PO4)3
(OH)、C36H70CaO4、C6H10CaO6、C6H10CaO6、Ca(HCO2)2、Ca(CH3COO)2、CaC2O4In one or more of groups
Close；
Method removing aluminium, the copper metal of gravity separation, eddy flow or screening can be used after roasting, powder containing lithium is obtained.
Step（2）Gained carries out alkaline process containing aluminium, iron, lithium powder and removes aluminium, obtains iron content residue containing lithium；
It is preferred that, old and useless battery powder is added in aqueous slkali, the oxide of dissolving aluminium and aluminium obtains iron content residue containing lithium；
It is preferred that, aqueous slkali is NaOH solution, KOH solution, Ca (OH)2One or more combination in solution or ammoniacal liquor；
It is preferred that, concentration of lye is 2 ~ 4mol/L.
Step（3）The gained iron content ball milling of residue containing lithium obtains powder, and Ball-milling Time is 0.1 ~ 20h；
It is preferred that, the mesh of iron content powder containing lithium size 30 ~ 1000；
Further, preferably 200 ~ 500 mesh.
Step（4）Gained powder containing lithium is in ammonium salt and/or the mixed solution Strengthen education of ammonia, while in oxidative environment
Under, ferrous iron is converted into ferric iron, water insoluble iron containing compoundses, Selectively leaching elemental lithium are formed；
Ammonium salt and/or ammonia density used are 0.1 ~ 15mol/L, and leaching S/L is 1 ~ 500g/L, and extraction temperature is 5 ~ 100 DEG C, is leached
Time is 5 ~ 480min, and mixing speed is 0 ~ 2000rpm, and Strengthen education pressure is 1 ~ 5atm；
Ammonium salt and/or the ammonia solution concentration is preferably 2 ~ 4mol/L；
The leaching S/L is preferably 80 ~ 150g/L；
The Strengthen education temperature is preferably 30 ~ 120 DEG C；The Strengthen education pressure is preferably 1 ~ 1.5atm；The stirring speed
Degree is preferably 100 ~ 500rpm；
The oxidative environment adds H to add or being passed through in the solution2O2、MnO2、KMnO4, air or O2One kind of oxidant
Or several combinations are aoxidized.
Step（5）Gained lithium-containing solution, is concentrated into lithium concentration for 2 ~ 500g/L, is reclaimed in concentration process and obtains ammonium salt
And/or ammonia, thickening temperature is 40 ~ 100 DEG C；
It is preferred that, thickening temperature is 70 ~ 100 DEG C；
It is preferred that, concentration lithium concentration is 200 ~ 500g/L.
Step（6）Lithium ion solution after concentration prepares lithium hydroxide through removal of impurities extraction, and cleaning obtains Lithium hydroxide；
Or saturated sodium carbonate solution precipitation lithium carbonate is added, separate and clean and obtain pure Lithium Carbonate；
It is preferred that, lithium carbonate precipitation temperature is 20 ~ 100 DEG C；
More preferably 60 ~ 100 DEG C；
It is preferred that, lithium carbonate precipitation mixing speed is 0 ~ 2000rpm；
More preferably 100 ~ 500rpm；
It is preferred that, the lithium carbonate precipitation stirring and adjusting time is 0.5 ~ 72h；
More preferably 2 ~ 12h；
It is preferred that, the molar ratio of lithium ion is 1 ~ 3 in carbanion and solution that lithium carbonate precipitation is added:2；
It is preferred that, the temperature of washing water used is 10 ~ 100 DEG C；
More preferably 40 ~ 100 DEG C.
Compared with prior art, beneficial effects of the present invention are：
（1）The present invention obtains elemental lithium by one-step method, has abandoned traditional wet method acid immersion technique, has simplified recovery process stream
Journey, the generation for avoiding a large amount of high-salt wastewaters, environment secondary pollution problems in old and useless battery removal process are efficiently solved, dropped
Low cost recovery；
（2）The present invention combines Strengthen education and Selectively leaching, the compound of water insoluble iron and calcium phosphate by producing
Mode, Strengthen education has selectively obtained comprising only the aqueous solution of elemental lithium, and impurity content is low, and leaching efficiency is increased substantially,
The lithium-containing solution of gained can be directly used for the recovery of elemental lithium；
（3）The process flow is short, efficiency high, medicament wide material sources used and do not produce a large amount of high-salt wastewaters, can obtain
The elemental lithium of high-purity, with great market promotion prospect.
For up to this purpose, the present invention uses the technical scheme of following optimization：
（1）Positive material of waste lithium iron phosphate is broken for 1 ~ 20mm × 1 ~ 20mm fragment, in 200 ~ 1200 °C of high temperature
It can spray into calcic powder to absorb the generation of fluoro-gas, wherein calcic powder CaC in 1 ~ 6h of lower roasting, roasting process2、
CaCl2、CaCO3、Ca(NO3)2、CaO、Ca(OH)2、Ca5(PO4)3(OH)、C36H70CaO4、C6H10CaO6、C6H10CaO6、Ca
(HCO2)2、Ca(CH3COO)2、CaC2O4Deng in calcic inorganic matter, calcic organic matter and calcic biomass it is a kind of or any several
Combination, the mass ratio of battery waste and calcic powder is controlled 20 ~ 300:1.Roasting uses gravity separation, eddy flow, sieve after terminating
Method of grading is gone out the metals such as aluminium, copper, obtains the battery material powder of aluminium, iron, lithium.
（2）Obtained by old and useless battery roasting sorting containing aluminium, iron, lithium battery material powder, by by old and useless battery powder
Material is added in aqueous slkali, the oxide of dissolving aluminium and aluminium, obtains iron content residue containing lithium.Aqueous slkali is NaOH, KOH, Ca
(OH)2, the one or more combination in ammoniacal liquor, concentration of lye is 2 ~ 4mol/L.
（3）The gained iron content ball milling of residue containing lithium obtain after iron content powder containing lithium, ball milling iron content powder containing lithium size be 200 ~
500 mesh.
（4）Gained powder containing lithium is in ammonium salt and/or the mixed solution Strengthen education of ammonia, and the ammonium salt and/or ammonia solution are dense
Spend for 2 ~ 4mol/L, leaching S/L is 80 ~ 150g/L, extraction temperature is 30 ~ 80 DEG C, and extraction time is 5 ~ 480min, leaches stirring
Speed is 100 ~ 500rpm, and leaching pressure is 1 ~ 1.5atm.Under simultaneous oxidation environment, ferrous iron is converted into ferric iron, shape
Into water insoluble iron containing compoundses, Selectively leaching elemental lithium.The oxidation environment refers to adds or is passed through H in the solution2O2、
MnO2、KMnO4, air, O2One or several kinds of combinations Deng oxidant are aoxidized.
（5）After leachate/slag separation, lithium-containing solution is obtained, lithium concentration is concentrated into for 200 ~ 500g/L, reclaims and obtain
Ammonium salt or ammonia, thickening temperature are 70 ~ 100 DEG C.Concentrate prepares Lithium hydroxide through removal of impurities extraction.Or add unsaturated carbonate
Sodium solution precipitates lithium carbonate, separates and clean obtained pure Lithium Carbonate（Purity 99.99%）.Lithium carbonate precipitation temperature be 60 ~
100 DEG C, precipitation mixing speed is 100 ~ 500rpm, and the stirring and adjusting time is 2 ~ 12h, carbanion and lithium ion in solution
Molar ratio is 1 ~ 3:2, the temperature of washing water used is 40 ~ 100 DEG C.
Brief description of the drawings
Fig. 1 is the method process chart that a kind of waste lithium iron phosphate battery Strengthen education reclaims metal.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.The skill of this area
Understanding is of the invention it will be clearly understood that described embodiment is only to aid in by art personnel, is not construed as the concrete restriction to the present invention.
Embodiment
A part of embodiment of the present invention, rather than whole embodiments, based on the embodiment in the present invention, art technology
The every other embodiment that personnel are obtained under the premise of innovative labor is not made, belongs to protection scope of the present invention.
Embodiment 1
（1）Positive material of waste lithium iron phosphate is broken for be calcined under 1 ~ 20mm × 1 ~ 20mm fragment, 800 DEG C of high temperature
CaO can be sprayed into 2h, roasting process prevents the generation of fluoro-gas, and the mass ratio of battery waste and calcic powder is controlled 300:
1.Roasting removes the metal such as aluminium and copper after terminating using screening, obtains powder containing lithium.
The ferric phosphate lithium cell of the table 1 roasting sorting gained composition of powder containing lithium（wt%）
| Fe | P | Li |
| 23.2 | 12.4 | 2.1 |
（2）Old and useless battery roasting sorting obtained by containing aluminium, iron, lithium battery material powder, by the way that old and useless battery powder is added
Enter into NaOH aqueous slkalis, the oxide of dissolving aluminium and aluminium obtains iron content residue containing lithium.NaOH concentration of lye is 2mol/L.
（3）The gained iron content ball milling of residue containing lithium obtained the iron content powder containing lithium of 200 mesh sieves, and Ball-milling Time is 2h.
（4）Gained powder containing lithium Strengthen education in ammonium salt solution, ammonium salt concentration is 2mol/L, and leaching S/L is 80g/L,
Extraction temperature is 60 DEG C, and extraction time is 30min, and leaching mixing speed is 500rpm, and leaching pressure is 1.2atm.Simultaneously to molten
O is passed through in liquid2, ferrous iron is converted into ferric iron, water insoluble iron containing compoundses, Selectively leaching elemental lithium, leaching is formed
Go out liquid/oxygen volume ratio 0.1.
（5）After leachate/slag separation, lithium-containing solution is obtained, lithium concentration is concentrated at 95 DEG C for 200g/L, simultaneously
Reclaim and obtain ammonium salt or ammonia.Concentrate prepares Lithium hydroxide through removal of impurities extraction（Purity is to 99.9%）.
Embodiment 2
（1）Positive material of waste lithium iron phosphate is broken for be calcined under 1 ~ 20mm × 1 ~ 20mm fragment, 800 DEG C of high temperature
CaCO can be sprayed into 2h, roasting process3The generation of fluoro-gas is prevented, the mass ratio control of battery waste and calcic powder exists
300:1.Roasting removes the metal such as aluminium and copper after terminating using screening, obtains powder containing lithium.
The ferric phosphate lithium cell of the table 2 roasting sorting gained composition of powder containing lithium（wt%）
| Fe | P | Li |
| 27.2 | 14.4 | 3.1 |
（2）Old and useless battery roasting sorting obtained by containing aluminium, iron, lithium battery material powder, by the way that old and useless battery powder is added
Enter to Ca (OH)2In aqueous slkali, the oxide of dissolving aluminium and aluminium obtains iron content residue containing lithium.Ca(OH)2Concentration of lye is 2mol/
L。
（3）The gained iron content ball milling of residue containing lithium obtained the iron content powder containing lithium of 200 mesh sieves, and Ball-milling Time is 2h.
（4）Gained powder containing lithium Strengthen education in the mixed solution of ammonium salt and ammonia, ammonium salt concentration is 3mol/L, leaches S/
L is 80g/L, and extraction temperature is 40 DEG C, and extraction time is 20min, and leaching mixing speed is 500rpm, leaches pressure and is
1.4atm.Air is passed through into solution simultaneously, ferrous iron is converted into ferric iron, water insoluble iron containing compoundses, choosing are formed
Selecting property leaches elemental lithium, leachate/volume of air 0.5.
（5）After leachate/slag separation, lithium-containing solution is obtained, lithium concentration is concentrated at 95 DEG C for 300g/L, simultaneously
Reclaim and obtain ammonium salt or ammonia.Concentrate adds saturated sodium carbonate solution precipitation lithium carbonate, separates and clean obtained high-purity carbon
Sour lithium（Purity 99.99%）.Lithium carbonate precipitation temperature is 95 DEG C, and precipitation mixing speed is 500rpm, and the stirring and adjusting time is 2h,
The molar ratio of carbanion and lithium ion in solution is 3:2, the temperature of washing water used is 90 DEG C.
Embodiment 3
（1）Positive material of waste lithium iron phosphate is broken for be calcined under 1 ~ 20mm × 1 ~ 20mm fragment, 800 DEG C of high temperature
CaCO can be sprayed into 2h, roasting process3The generation of fluoro-gas is prevented, the mass ratio control of battery waste and calcic powder exists
300:1.Roasting removes the metal such as aluminium and copper after terminating using screening, obtains powder containing lithium.
The ferric phosphate lithium cell of the table 3 roasting sorting gained composition of powder containing lithium（wt%）
| Fe | P | Li |
| 23.5 | 10.1 | 1.7 |
（2）Old and useless battery roasting sorting obtained by containing aluminium, iron, lithium battery material powder, by the way that old and useless battery powder is added
Enter to Ca (OH)2In aqueous slkali, the oxide of dissolving aluminium and aluminium obtains iron content residue containing lithium.Ca(OH)2Concentration of lye is 2mol/
L。
（3）The gained iron content ball milling of residue containing lithium obtained the iron content powder containing lithium of 400 mesh sieves, and Ball-milling Time is 2h.
（4）Gained powder containing lithium Strengthen education in the mixed solution of ammonium salt and ammonia, ammonium salt concentration is 3mol/L, leaches S/
L is 100g/L, and extraction temperature is 50 DEG C, and extraction time is 5min, and leaching mixing speed is 500rpm, leaches pressure and is
1.5atm.H is passed through into solution simultaneously2O2, ferrous iron is converted into ferric iron, water insoluble iron containing compoundses, selection are formed
Property leach elemental lithium, mixing slag/oxidant mass ratio 200.
（5）After leachate/slag separation, lithium-containing solution is obtained, lithium concentration is concentrated at 95 DEG C for 300g/L, simultaneously
Reclaim and obtain ammonium salt or ammonia.Concentrate adds saturated sodium carbonate solution precipitation lithium carbonate, separates and clean obtained high-purity carbon
Sour lithium（Purity 99.99%）.Lithium carbonate precipitation temperature is 95 DEG C, and precipitation mixing speed is 500rpm, and the stirring and adjusting time is 2h,
The molar ratio of carbanion and lithium ion in solution is 3:2, the temperature of washing water used is 90 DEG C.
Applicant states that the present invention illustrates the process of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned processing step, that is, does not mean that the present invention has to rely on above-mentioned processing step and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to raw material selected by the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and being open.
Claims (10)
1. a kind of method of metal recovery in waste lithium iron phosphate battery, it is characterised in that comprise the following steps：
（1）By old and useless battery be calcined sorting obtain containing aluminium, iron, lithium battery material powder；
（2）Step（1）Gained carries out alkaline process containing aluminium, iron, lithium powder and removes aluminium, obtains iron content residue containing lithium；
（3）Step（2）Gained iron content residue containing lithium, ball milling obtains iron content powder containing lithium；
（4）Step（3）Gained powder containing lithium is in ammonium salt and/or the mixed solution Strengthen education of ammonia, while in an oxidizing environment, inciting somebody to action
Ferrous iron is converted to ferric iron, forms water insoluble iron containing compoundses, Selectively leaching elemental lithium；
（5）Step（4）After leachate/slag separation, lithium-containing solution is concentrated, reclaims and obtains ammonium salt and/or ammonia；
（6）Step（5）Gained concentrate obtains Lithium hydroxide or lithium carbonate for reclaiming lithium resource.
2. method according to claim 1, it is characterised in that step（1）LiFePO4 old and useless battery is crushed and is calcined and is divided
Choosing, obtain containing aluminium, iron, lithium battery material powder；
It is preferred that, cell positive material is broken for 1 ~ 20mm × 1 ~ 20mm fragment by Mechanical Crushing；
It is preferred that, sintering temperature is 200 ~ 1200 DEG C, and roasting time is 1 ~ 6h.
3. method according to claim 2, it is characterised in that step（1）Calcic powder can be sprayed into roasting process to absorb
The quality proportioning of the fluoro-gas of generation, the battery waste and calcic powder is 20 ~ 300:1；
It is preferred that, the calcic powder is a kind of in calcic inorganic matter, calcic organic matter or calcic biomass or any several
Combination；
It is preferred that, the calcic powder is preferably CaC2、CaCl2、CaCO3、Ca(NO3)2、CaO、Ca(OH)2、Ca5(PO4)3
(OH)、C36H70CaO4、C6H10CaO6、C6H10CaO6、Ca(HCO2)2、Ca(CH3COO)2、CaC2O4In one or more of groups
Close.
4. method according to claim 3, it is characterised in that the method that can use gravity separation, eddy flow or screening after roasting
Aluminium, copper metal are removed, powder containing lithium is obtained.
5. method according to claim 1, it is characterised in that step（2）Gained carries out alkaline process containing aluminium, iron, lithium powder and removes aluminium,
Obtain iron content residue containing lithium；
It is preferred that, old and useless battery powder is added in aqueous slkali, the oxide of dissolving aluminium and aluminium obtains iron content residue containing lithium；
It is preferred that, aqueous slkali is NaOH solution, KOH solution, Ca (OH)2One or more combination in solution or ammoniacal liquor；
It is preferred that, concentration of lye is 2 ~ 4mol/L.
6. method according to claim 1, it is characterised in that step（3）The gained iron content ball milling of residue containing lithium obtains powder, ball
Consume time as 0.1 ~ 20h；
It is preferred that, the mesh of iron content powder containing lithium size 30 ~ 1000；
Further, preferably 200 ~ 500 mesh.
7. method according to claim 1, it is characterised in that step（4）Mixing of the gained powder containing lithium in ammonium salt and/or ammonia
Solution Strengthen education, while under oxidative environment, ferrous iron is converted into ferric iron, forms water insoluble iron content chemical combination
Thing, Selectively leaching elemental lithium；
Ammonium salt and/or ammonia density used are 0.1 ~ 15mol/L, and leaching S/L is 1 ~ 500g/L, and extraction temperature is 5 ~ 100 DEG C, is leached
Time is 5 ~ 480min, and mixing speed is 0 ~ 2000rpm, and Strengthen education pressure is 1 ~ 5atm.
8. method according to claim 7, it is characterised in that ammonium salt and/or the ammonia solution concentration is preferably 2 ~ 4mol/L；
The leaching S/L is preferably 80 ~ 150g/L；
The Strengthen education temperature is preferably 30 ~ 120 DEG C；The Strengthen education pressure is preferably 1 ~ 1.5atm；The stirring speed
Degree is preferably 100 ~ 500rpm；
The oxidative environment is to add or be passed through in the solution H2O2、MnO2、KMnO4, air or O2One kind of oxidant or
Several combinations are aoxidized.
9. method according to claim 1, it is characterised in that step（5）Gained lithium-containing solution, being concentrated into lithium concentration is
Reclaimed in 2 ~ 500g/L, concentration process and obtain ammonium salt and/or ammonia, thickening temperature is 40 ~ 100 DEG C；
It is preferred that, thickening temperature is 70 ~ 100 DEG C；
It is preferred that, concentration lithium concentration is 200 ~ 500g/L.
10. method according to claim 1, it is characterised in that step（6）Lithium ion solution after concentration is extracted through removal of impurities to be made
Standby lithium hydroxide, cleaning obtains Lithium hydroxide；
Or saturated sodium carbonate solution precipitation lithium carbonate is added, separate and clean and obtain pure Lithium Carbonate；
It is preferred that, lithium carbonate precipitation temperature is 20 ~ 100 DEG C；
More preferably 60 ~ 100 DEG C；
It is preferred that, lithium carbonate precipitation mixing speed is 0 ~ 2000rpm；
More preferably 100 ~ 500rpm；
It is preferred that, the lithium carbonate precipitation stirring and adjusting time is 0.5 ~ 72h；
More preferably 2 ~ 12h；
It is preferred that, the molar ratio of lithium ion is 1 ~ 3 in carbanion and solution that lithium carbonate precipitation is added:2；
It is preferred that, the temperature of washing water used is 10 ~ 100 DEG C；
More preferably 40 ~ 100 DEG C.
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