WO2023283685A1 - Process for recovering values from alkaline batteries - Google Patents
Process for recovering values from alkaline batteries Download PDFInfo
- Publication number
- WO2023283685A1 WO2023283685A1 PCT/AU2022/050732 AU2022050732W WO2023283685A1 WO 2023283685 A1 WO2023283685 A1 WO 2023283685A1 AU 2022050732 W AU2022050732 W AU 2022050732W WO 2023283685 A1 WO2023283685 A1 WO 2023283685A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alkaline
- particle fraction
- carbon
- mmd
- particles
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 132
- 230000008569 process Effects 0.000 title claims abstract description 109
- 239000002245 particle Substances 0.000 claims abstract description 405
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 188
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 187
- 239000010406 cathode material Substances 0.000 claims abstract description 135
- 239000010405 anode material Substances 0.000 claims abstract description 94
- 239000007772 electrode material Substances 0.000 claims abstract description 12
- 238000009291 froth flotation Methods 0.000 claims description 90
- 238000005188 flotation Methods 0.000 claims description 89
- 238000000926 separation method Methods 0.000 claims description 85
- 239000000463 material Substances 0.000 claims description 78
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 76
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 59
- 229910000831 Steel Inorganic materials 0.000 claims description 55
- 239000010959 steel Substances 0.000 claims description 55
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 51
- 229910052748 manganese Inorganic materials 0.000 claims description 51
- 239000011572 manganese Substances 0.000 claims description 51
- 239000011701 zinc Substances 0.000 claims description 49
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 48
- 229910052725 zinc Inorganic materials 0.000 claims description 48
- 239000012141 concentrate Substances 0.000 claims description 44
- 239000003337 fertilizer Substances 0.000 claims description 38
- 239000002002 slurry Substances 0.000 claims description 34
- 230000005484 gravity Effects 0.000 claims description 31
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 29
- 239000003575 carbonaceous material Substances 0.000 claims description 28
- 229910001385 heavy metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000011230 binding agent Substances 0.000 claims description 15
- 239000000428 dust Substances 0.000 claims description 15
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 15
- 239000011787 zinc oxide Substances 0.000 claims description 15
- 239000008396 flotation agent Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 11
- 239000003517 fume Substances 0.000 claims description 10
- 238000007885 magnetic separation Methods 0.000 claims description 9
- 239000011785 micronutrient Substances 0.000 claims description 9
- 235000013369 micronutrients Nutrition 0.000 claims description 9
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 8
- -1 a-terpinol Chemical compound 0.000 claims description 8
- 238000005273 aeration Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000012216 screening Methods 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 6
- 239000005696 Diammonium phosphate Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical group [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 6
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 6
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 6
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 6
- 239000006012 monoammonium phosphate Substances 0.000 claims description 6
- 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 claims description 6
- 230000000994 depressogenic effect Effects 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 239000003350 kerosene Substances 0.000 claims description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical group [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims description 3
- 239000001506 calcium phosphate Substances 0.000 claims description 3
- YYRMJZQKEFZXMX-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca+2].OP(O)(O)=O.OP(O)(O)=O YYRMJZQKEFZXMX-UHFFFAOYSA-N 0.000 claims description 3
- 230000001143 conditioned effect Effects 0.000 claims description 3
- 229930003836 cresol Natural products 0.000 claims description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 229910000150 monocalcium phosphate Inorganic materials 0.000 claims description 3
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 3
- 239000002426 superphosphate Substances 0.000 claims description 3
- 125000002256 xylenyl group Chemical class C1(C(C=CC=C1)C)(C)* 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 26
- 238000009826 distribution Methods 0.000 description 20
- 230000002209 hydrophobic effect Effects 0.000 description 18
- 238000011084 recovery Methods 0.000 description 12
- 238000000227 grinding Methods 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 238000004064 recycling Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000007769 metal material Substances 0.000 description 7
- 238000005549 size reduction Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000007717 exclusion Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 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 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000009837 dry grinding Methods 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 238000001493 electron microscopy Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(iii) oxide Chemical compound O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000399 optical microscopy Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012958 reprocessing Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000000184 acid digestion Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical compound [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000003019 stabilising effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/52—Reclaiming serviceable parts of waste cells or batteries, e.g. recycling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B9/00—General arrangement of separating plant, e.g. flow sheets
- B03B9/06—General arrangement of separating plant, e.g. flow sheets specially adapted for refuse
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/006—Hydrocarbons
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/02—Froth-flotation processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/08—Subsequent treatment of concentrated product
- B03D1/085—Subsequent treatment of concentrated product of the feed, e.g. conditioning, de-sliming
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B1/00—Superphosphates, i.e. fertilisers produced by reacting rock or bone phosphates with sulfuric or phosphoric acid in such amounts and concentrations as to yield solid products directly
- C05B1/02—Superphosphates
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
- C05D9/02—Other inorganic fertilisers containing trace elements
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G1/00—Mixtures of fertilisers belonging individually to different subclasses of C05
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
-
- 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
- C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B9/00—General arrangement of separating plant, e.g. flow sheets
- B03B9/06—General arrangement of separating plant, e.g. flow sheets specially adapted for refuse
- B03B2009/066—General arrangement of separating plant, e.g. flow sheets specially adapted for refuse the refuse being batteries
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B9/00—General arrangement of separating plant, e.g. flow sheets
- B03B9/06—General arrangement of separating plant, e.g. flow sheets specially adapted for refuse
- B03B9/061—General arrangement of separating plant, e.g. flow sheets specially adapted for refuse the refuse being industrial
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
-
- 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
- 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
Definitions
- the present disclosure relates generally to processes for recovering values from alkaline batteries. More specifically, the present disclosure relates to processes for recovering and separating electrode materials from alkaline batteries, such as cathode and/or anode materials. The present disclosure also relates to compositions and products comprising cathode and/or anode materials recovered from alkaline batteries, including for example fertilisers and repurposed electrodes.
- alkaline batteries have been used to power small consumer and electronic applications since development in the late 1950’s.
- alkaline batteries are used in personal devices, including toys, clocks, cameras and torches and other portable electronic devices.
- the present inventors have undertaken research and development into processes for recovering one or more values from alkaline batteries, including for example cathode and/or anode materials.
- the present disclosure described herein can also be scalable for industrial application for processing and recycling large quantities of alkaline batteries and the recovered cathode and/or anode materials can be reused or repurposed across a variety of industries, including as repurposed electrode materials for cathodes and/or anodes in alkaline batteries, or as micronutrients for fertilisers.
- Described herein is a process that can selectively separate and recover cathode material and carbon as a separate fraction to anode material from alkaline mixed metal dust (MMD).
- the alkaline MMD can be obtained from alkaline batteries, for example via physical separation (e.g. shredding).
- shredding physical separation
- the inventors have identified that comminuting alkaline MMD can advantageously result in the liberation of cathode material and carbon as a separate fraction to the anode material, including for example a concentrated manganese oxide and carbon product.
- the cathode material and carbon may be separated from the anode material by subjecting the alkaline MMD to a froth flotation separation.
- the inventors have surprisingly identified that cathode material and carbon report selectively report to the flotation concentrate as a separate fraction to the anode material. Comminution of alkaline MMD prior to froth flotation separation may also increase the recovery and concentration of the cathode material and carbon in the flotation concentrate.
- Another advantage of using froth flotation to separate the cathode material and carbon from the anode material according to some embodiments or examples described herein also include the preferential reporting of heavy metals to the anode material.
- the separated cathode material and carbon can be processed into a fertiliser.
- the comminuted alkaline MMD particles comprising both the cathode material and carbon fraction and the anode material fraction can also be processed into a fertiliser.
- the separated cathode material and carbon and/or anode material can also be processed into one or more electrodes for use in alkaline batteries.
- a process for obtaining cathode material and carbon from alkaline mixed metal dust (MMD) obtained from alkaline batteries comprising: a) comminuting alkaline MMD to reduce the average particle size of the alkaline MMD to liberate and obtain a first particle fraction comprising cathode material and carbon and a second particle fraction comprising anode material; and b) separating the first particle fraction comprising cathode material and carbon from the second particle fraction comprising anode material.
- MMD alkaline mixed metal dust
- 80% of the comminuted alkaline MMD particles have a particle size of between about 50 pm to about 500 pm.
- the first particle fraction comprises manganese oxide and carbon
- the second particle fraction comprises zinc/zinc oxide.
- the first particle fraction may be concentrated in manganese oxide and carbon and the second particle fraction may be concentrated in zinc/zinc oxide.
- the first particle fraction has a higher % w/w concentration of manganese compared to the concentration of manganese in the second particle fraction, based on the total weight of the particle fraction.
- the first particle fraction may comprise between about 25% w/w to about 60 % w/w manganese based on the total weight of the first particle fraction.
- the first particle fraction may comprise between about 5% w/w to about 15% w/w carbon based on the total weight of the first particle fraction.
- the second particle fraction has a higher % w/w concentration of zinc compared to the concentration of zinc in the first particle fraction, based on the total weight of the particle fraction.
- the second particle fraction may comprise between about 20% w/w to about 70% w/w zinc, based on the total weight of the second particle fraction.
- the carbon is physically or chemically associated with the manganese oxide as a mixed manganese oxide/carbon material.
- the mixed manganese oxide/carbon material is a mixed MnC /MmCb/carbon material.
- the separating of the particle fractions at step b) comprises a size screening of the comminuted alkaline MMD particles. In an alternative embodiment, the separating of the particle fractions at step b) comprises froth flotation of the comminuted alkaline MMD particles.
- the separating of the particle fractions at step b) comprises performing a froth flotation separation on the comminuted alkaline MMD particles in a froth flotation vessel, wherein the first particle fraction comprising cathode material and carbon reports to a flotation concentrate, and second particle fraction comprising anode material reports to a flotation tail, and removing the flotation concentrate from the froth flotation vessel to separate and obtain the first particle fraction comprising cathode material and carbon.
- the flotation separation comprises: bl) suspending the comminuted alkaline MMD particles in an aqueous solution comprising one or more froth flotation agents in the froth flotation vessel to create a slurry; b2) aerating the slurry to generate air bubbles which float to the surface of the slurry to form a froth, wherein the first particle fraction comprising cathode material and carbon attaches to at least some of the air bubbles and floats to the top of the froth flotation vessel to report to the flotation concentrate, and the second particle fraction comprising anode material remains in the slurry to report to the flotation tail.
- the one or more froth flotation agents is selected from the group consisting of a frother, collector, and/or depressant.
- the frother may be an alcohol selected from the group consisting of methyl isobutyl carbinol (MIBC), 2-ethyl hexanol, isoamyl alcohol, cyclohexanol, a-terpinol, cresol, xylenol, glycol ether, and a combination thereof.
- the collector may be provided in an amount of between about 100 g/t to about 8000 g/t.
- the collector may be hydrocarbon oil, fatty acid or hydroximate.
- the hydrocarbon oil may be kerosene.
- the slurry comprising the comminuted alkaline MMD particles is conditioned prior to froth flotation to clean or activate the particles prior to aeration.
- the flotation tail comprising the second particle fraction is removed from the froth flotation vessel and undergoes gravity separation to recover any manganese and carbon entrained within the second particle fraction following froth flotation separation.
- the manganese and carbon recovered from gravity separation is recycled into the froth flotation vessel or combined with the flotation concentrate.
- one or more heavy metals present in the comminuted alkaline MMD particles preferentially report to the flotation tail as part of the second particle fraction.
- the flotation tail has a higher ppm concentration of heavy metal compared to the concentration of heavy metal in the flotation concentrate, based on the total weight of the reported particles.
- the alkaline MMD is provided by the steps: al) physically separating alkaline batteries to obtain coarser particles comprising steel and/or ferrous material and finer particles comprising alkaline MMD; and a2) separating the coarser particles comprising steel and/or ferrous material from the finer particles comprising alkaline MMD.
- the finer particles comprising alkaline MMD is between about 30% to about 80% w/w based on the total weight of the alkaline battery.
- step a2) comprises screening the separated alkaline battery particles at between about 4 mm to about 6 mm to separate the coarser particles comprising steel and/or ferrous material from the finer particle of alkaline MMD.
- step a2) comprises subjecting the separated alkaline battery particles to magnetic separation to separate the coarser particles comprising steel and/or ferrous material from the finer particles comprising alkaline MMD.
- the physical separation of the alkaline batteries at step al) produces a dust and/or fume comprising electrolyte, wherein the dust and/or fume is optionally treated to recover the electrolyte.
- the separated alkaline battery particles comprising coarser particles comprising steel and/or ferrous material and finer particles comprising alkaline MMD are washed and/or attritioned prior to step a2).
- the separated coarser particles comprising steel and/or ferrous material may be subjected to crushing to liberate and obtain alkaline MMD trapped within the coarser particles.
- the separated first particle fraction comprising cathode material and carbon and/or separated second particle fraction comprising anode material is processed into one or more electrodes for alkaline batteries.
- the process further comprises assembling an alkaline battery comprising one or more electrodes prepared using the separated first particle fraction comprising cathode material and carbon and/or separated second particle fraction comprising anode material.
- the process further comprises mixing the separated first particle fraction comprising cathode material and carbon at step b) with a phosphorous source and optionally a binder to prepare a fertiliser.
- the phosphorous source is a calcium phosphate salt or ammonium phosphate salt, or a combination thereof.
- the calcium phosphate salt may be monocalcium phosphate (Super Phosphate).
- the ammonium phosphate salt may be monoammonium phosphate (MAP) or diammonium phosphate (DAP), or a combination thereof.
- the binder may be phosphoric acid.
- a fertiliser comprising comminuted alkaline MMD particles or separated cathode material and carbon obtained from alkaline batteries, a phosphorous source, and optionally a binder.
- an alkaline battery comprising one or more electrodes prepared using the separated cathode material and carbon and/or anode material obtained by the processes described above.
- the separated first particle fraction comprising cathode material and carbon and/or anode material obtained by the process described above, as an electrode material for preparing one or more electrodes for alkaline batteries.
- Figure 1 Process flow sheet depicting a process for liberating and obtaining cathode, carbon and anode materials from alkaline batteries using physical separation.
- Figure 2 Process flow sheet depicting a process for obtaining cathode, carbon and anode materials from alkaline batteries using physical separation, with dust and fume treatment for electrolyte recovery.
- Figure 3 Process flow sheet depicting a process for obtaining cathode, carbon and anode materials from alkaline batteries using flotation.
- Figures 4 Process flow sheet depicting a process for obtaining cathode, carbon and anode materials from alkaline batteries using gravity separation.
- Figure 5 Process flow sheet depicting a process for obtaining cathode, carbon and anode materials from alkaline batteries using comminution and froth flotation.
- Figure 6 and 7 Process flow sheets depicting a process for obtaining cathode, carbon and anode materials products from alkaline batteries using combinations of froth flotation and gravity separation.
- Figure 8 Process flow sheet depicting a process for preparing a fertiliser using separated cathode material and carbon as a micronutrient.
- the present disclosure describes the following various non-limiting embodiments, which relates to investigations undertaken to identify processes for recovering one or more values from alkaline batteries.
- the reference to “substantially free” generally refers to the absence of that compound or component in the material (e.g. absence of a particular impurity in the first or second particle fractions, cathode or anode materials, flotation concentrate or tail) other than any trace amounts or impurities that may be present, for example this may be an amount by weight % in the total composition of less than about 1%, 0.1%, 0.01%, 0.001%, or 0.0001%., or an amount as ppm in the total composition of less than about 10000, 1000, 100, 10 or 1 ppm.
- first Unless otherwise indicated, the terms “first,” “second,” etc. are used herein merely as labels, and are not intended to impose ordinal, positional, or hierarchical requirements on the items to which these terms refer. Moreover, reference to a “second” item does not require or preclude the existence of lower-numbered item (e.g., a “first” item) and/or a higher-numbered item (e.g., a “third” item).
- the phrase “at least one of’, when used with a list of items, means different combinations of one or more of the listed items may be used and only one of the items in the fist may be needed.
- the item may be a particular object, thing, or category.
- “at least one of’ means any combination of items or number of items may be used from the list, but not all of the items in the list may be required.
- “at least one of item A, item B, and item C” may mean item A; item A and item B; item B; item A, item B, and item C; or item B and item C.
- “at least one of item A, item B, and item C” may mean, for example and without limitation, two of item A, one of item B, and ten of item C; four of item B and seven of item C; or some other suitable combination.
- the term “electrode material” refers to a material comprising either anode material, cathode material or a mixture thereof.
- the electrode material is obtained from alkaline batteries, and comprise or consist of a mixed metal material.
- cathode material and “anode material” refers to the active material used to prepare the cathode and anode (i.e. electrodes) of an alkaline battery, respectively.
- Reference to active material means the material of the cathode and anode that react with each other during discharge of the alkaline battery, for example as outlined in the half reactions and overall reaction outlined below... Embodiments of the cathode and anode material and other metals are described herein.
- the term “mixed metal” includes a compound or mixture comprising at least two metals.
- the mixed metal material may comprise one or more metals that are present in alkaline batteries, such as those present in the electrodes, including cathode and anode materials.
- the metals in the mixed metal material may comprise manganese and zinc, for example as cathode and anode material.
- Other non-limiting examples of metals in the mixed metal material can include aluminium, carbon, copper, iron, potassium, sodium, and titanium.
- the mixed metal material may be a mixed metal dust (MMD) (also referred to as a mixed metal oxide dust and “black mass”).
- MMD mixed metal dust
- the MMD may be obtained during the recycling of alkaline batteries.
- the MMD may be a blend of one or more cathode and anode materials obtained from alkaline batteries along with one or more other metals described herein (e.g. carbon), also referred to herein as alkaline MMD.
- the mixed metal material may comprise a plurality of particles.
- a reference to “mg/kg” throughout the specification refers to the mass (in milligram) of a substance per kilogram of the total weight of a composition.
- a reference to w/w” throughout the specification refers to the percentage amount of a substance in a composition on a weight basis.
- the term “comminuting” and related terms such as “comminuted”, “comminution” etc. refers to the reduction of a solid material from one average particle size to a smaller average particle size, for example by crushing, grinding or milling.
- the process described herein can recover one or more values from alkaline batteries, namely materials that make up the cathode and anode of an alkaline battery.
- An alkaline battery is a type of primary battery which derives its energy from a chemical reaction between manganese oxide (i.e. cathode material) and zinc/zinc oxide (i.e. anode material) via an alkaline electrolyte.
- An alkaline battery comprises a cathode (e.g. positive terminal) and an anode (e.g. negative terminal).
- the cathode and anode comprise cathode material and anode material, respectively.
- the cathode material comprises a manganese oxide (e.g. MnCk and/or MmCb), often provided as a compressed paste to form the cathode.
- Carbon is often added to the cathode material (e.g. in the form of graphite) to increase the conductivity of the cathode, but does not take part in the half-reaction at the cathode or overall reaction on discharge (see below).
- the anode material comprises a mixture of zinc and zinc oxide (e.g. ZnO).
- the alkaline MMD described herein comprises a mixture of both the cathode material and anode material, and one or more other metal values obtained from alkaline batteries.
- the half-reactions at the anode and cathode comprising the anode material and cathode material, respectively, are:
- Alkaline batteries require an electrolyte which is dispersed with the anode material (and in some cases the cathode material).
- the electrolyte is alkaline and promotes the movement of electrons from the anode to the cathode on discharge.
- a typical alkaline electrolyte is potassium hydroxide (KOH).
- the cathode material and anode material independently form the reactive components of the cathode (i.e. positive electrode) and the anode (i.e. negative electrode), respectively, of the alkaline battery.
- the cathode and anode are separated by a separator which is a material located between the cathode and anode to keep the two electrodes apart to prevent electrical short circuits while also allowing the transport of ions therethrough.
- separator materials include polymers (e.g. polyolefins such as polyethylene, polypropylene and blends thereof).
- alkaline batteries include the outer casing and/or auxiliary components, including current collection or connection devices such as brass and aluminium, along with steel and ion conducting separator, typically woven cellulose or a synthetic polymer. Aluminium and/or plastics or cardboard are often used to house/encase alkaline batteries and for other auxiliary functions such as wiring.
- the alkaline batteries may be end of life batteries (e.g. dead/spent or faulty). It will be appreciated that such batteries present little economic value in their current form (e.g. cannot be sold). In light of the numerous materials making up alkaline batteries, there is a need to develop processes to recover a least some of these materials for re-use, recycling and/or commercial sale rather than disposing to landfill.
- the alkaline batteries have been physically separated to obtain alkaline MMD.
- the alkaline MMD may be subjected to a comminuting step as described herein.
- the present inventors have developed a process in which alkaline MMD obtained from alkaline batteries is subjected to a comminution step as described herein which results in the selective separation and recovery of cathode material and carbon as a separate fraction to the anode material, including for example a concentrated manganese oxide and carbon product.
- the cathode material and carbon can be separated from the anode material fraction (for example by froth flotation) and in some embodiments can be commercially sold as a carbon enriched manganese oxide product and/or subjected to further processing as a micronutrient for fertilisers.
- the anode material fraction can also be commercially sold.
- the process described herein does not require smelting, pyrometallurgical processing or acidic leaching to separate and obtain the cathode and anode material.
- the process for obtaining cathode material and carbon from alkaline MMD obtained from alkaline batteries comprises the steps of a) comminuting alkaline MMD to reduce the average particle size of the alkaline MMD to liberate and obtain a first particle fraction comprising cathode material and carbon and a second particle fraction comprising anode material.
- the alkaline MMD may be comminuted to reduce the average particle size of the alkaline MMD particles.
- the alkaline MMD may be comminuted by any conventional physical processing technique, including for example grinding, crushing, attritioning, shredding and/or milling.
- Any suitable apparatus capable of comminuting the alkaline MMD can be used, for example a grinding mill (either rod or ball), crusher, agitator (e.g. a high intensity agitator or an agitator tank), all of which are known to the person skilled in the art.
- the comminuting step may be performed in the presence of a liquid (e.g. wet comminution) or may be performed under dry conditions.
- the comminuting step comprises dry or wet grinding of the alkaline MMD, for example dry grinding.
- the comminuted alkaline MMD particles (comprising the first and second particle fractions described herein) have an average particle size.
- the average particle size is taken to be the cross-sectional diameter across a particle.
- the particle size is taken to be the distance corresponding to the longest cross- section dimension across the particle. It will be appreciated that the average particle size of the comminuted alkaline MMD is smaller than the average particle size of the alkaline MMD prior to the comminution step.
- the comminution step can result in a size reduced alkaline MMD.
- the comminution of alkaline MMD can result in 80% of the comminuted alkaline MMD particles (Pso) having a particle size of between about 50 pm to about 500 pm.
- the comminution of alkaline MMD can result in 80% of the comminuted alkaline MMD particles (Pso) having a particle size of less than about 500, 450, 400, 350. 300, 250, 150, 100 or 50 pm.
- the comminution of alkaline MMD can result in 80% of the comminuted alkaline MMD particles (Pso) having a particle size of at least about 50, 100, 150, 250, 300, 350, 400, 450 or 500 pm.
- the comminution of alkaline MMD can result in 80% of the comminuted alkaline MMD particles (Pso) having a particle size in a range provided by any two of these upper and/or lower amounts, for example between about 50 pm to about 500 pm.
- the alkaline MMD particles may be comminuted for any period of time effective to obtain one or more of the reduce particle sizes described herein, which may vary depending on the scale of the comminution (e.g. at laboratory scale or industrial scale) as understood by the skilled person when performing comminution.
- the comminution of the alkaline MMD is for a period of time of between about 1 minute to 120 minutes.
- the comminution of the alkaline MMD may be for a period of time (in minutes) of at least about 1, 2, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100 or 120.
- the comminution of the alkaline MMD may be for a period of time (in minutes) of less than about 120, 100, 90, 80, 70, 60, 50, 40, 30, 20, 15, 10, 5, 2 or 1.
- the comminution times can be a range provided by any two of these upper and/or lower times, for example between about 5 minutes to about 30 minutes, or about 5 minutes to about 15 minutes, or 30 minutes to about 60 minutes.
- the comminuted alkaline MMD particles may vary in morphology.
- the particles may take the form of flakes, fibres, agglomerates, granules, powders, spheres, pulverized materials or the like, as well as combinations thereof.
- the particles may have any desired shape including, but not limited to, cubic, rod like, polyhedral, spherical or semi- spherical, rounded or semi-rounded, angular, irregular, and so forth.
- the particle morphology and particle size can be measured by any conventional method, including laser diffraction, electron microscopy, dynamic light scattering, optical microscopy or size exclusion methods (such as wet or dry graduated mesh screens or filters).
- the comminution of alkaline MMD liberates and obtains a first particle fraction comprising cathode material and carbon and a second particle fraction comprising anode material. It will be appreciated that the first particle fraction and second particle fraction form part of the overall comminuted alkaline MMD particles described herein.
- the first particle fraction comprises cathode material and carbon.
- the cathode material comprises a manganese oxide.
- the manganese may exist in several oxidation states, including Mn(II) and Mn(III).
- the manganese oxide may be manganese (II) oxide (MnCh), manganese (III) oxide (MmCF) or a mixture thereof. It will be appreciated that any reference to manganese oxide, unless otherwise specified, can encompass one or more manganese oxide phases, including those recited above as well as mixtures thereof.
- the carbon may be associated with the manganese oxide (as opposed to discrete particles of carbon dispersed with the manganese oxide).
- the association may be physical or chemical.
- the carbon is physically or chemically associated with the manganese oxide.
- the carbon may be physically or chemically associated with the manganese oxide as a mixed manganese oxide/carbon material.
- the first particle fraction comprises a mixed manganese oxide/carbon material.
- the mixed manganese oxide/carbon material may be a mixed MnC /MmCF/carbon material. It will be appreciated that the mixed manganese oxide/carbon material is a compound comprising carbon physically associated with the manganese oxide as opposed to a mixture of discrete manganese oxide separate to carbon.
- the first particle fraction may be concentrated in manganese oxide and carbon.
- concentration refers to the enrichment of an element/compound in the particle fraction compared to the alkaline MMD prior to comminution.
- the first particle fraction has a higher % w/w concentration of manganese (e.g. elemental manganese derived from the manganese oxide present in the first particle fraction) compared to the concentration of manganese in the second particle fraction, based on the total weight of the particle fraction.
- manganese e.g. elemental manganese derived from the manganese oxide present in the first particle fraction
- the first particle fraction has a manganese % distribution of between about 40% to about 95% based on the amount of manganese in the alkaline MMD prior to comminution.
- the first particle fraction may have a manganese % distribution (based on the amount of manganese in the alkaline MMD prior to comminution) of at least about 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95.
- the first particle fraction may have a manganese % distribution (based on the amount of manganese in the alkaline MMD prior to comminution) of less than about 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, or 40.
- the first particle fraction may have a manganese % distribution in an amount in a range provided by any two of these upper and/or lower amounts, for example between about 80% to about 90% based on the amount of manganese in the alkaline MMD prior to comminution.
- the first particle fraction has a higher % w/w concentration of carbon (e.g. elemental carbon present in the first particle fraction) compared to the concentration of carbon in the second particle fraction, based on the total weight of the particle fraction.
- carbon e.g. elemental carbon present in the first particle fraction
- the first particle fraction has a carbon % distribution of between about 40% to about 95% based on the amount of carbon in the alkaline MMD prior to comminution.
- the first particle fraction may have a carbon % distribution (based on the amount of carbon in the alkaline MMD prior to comminution) of at least about 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95.
- the first particle fraction may have a carbon % distribution (based on the amount of carbon in the alkaline MMD prior to comminution) of less than about 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, or 40.
- the first particle fraction may have a carbon % distribution in an amount in a range provided by any two of these upper and/or lower amounts, for example between about 80% to about 90% based on the amount of carbon in the alkaline MMD prior to comminution.
- the first particle fraction comprises between about 10% w/w to about 60% w/w manganese based on the total weight of the first particle fraction.
- the first particle fraction may comprise manganese in an amount (as a % w/w based on the total weight of the first particle fraction) of at least about 10, 15, 20, 25,
- the first particle fraction may comprise manganese in an amount (as a % w/w based on the total weight of the first particle fraction) of less than about 60, 55, 50, 45, 40, 35, 30, 25, 20, 15 or 10.
- the first particle fraction may comprise manganese in an amount in a range provided by any two of these upper and/or lower amounts, for example between about 25% w/w to about 50% w/w, or about 35% w/w to about 45% w/w manganese based on the total weight of the first particle fraction.
- the first particle fraction comprises between about 1% w/w to about 30% w/w carbon based on the total weight of the first particle fraction.
- the first particle fraction may comprise carbon in an amount (as a % w/w based on the total weight of the first particle fraction) of at least about 1, 2, 3, 4, 5, 7, 10, 12, 15, 20, 25 or 30.
- the first particle fraction may comprise carbon in an amount (as a % w/w based on the total weight of the first particle fraction) of less than about 30, 25, 20, 15, 12, 10, 5, 2 or 1.
- the first particle fraction may comprise carbon in an amount in a range provided by any two of these upper and/or lower amounts, for example between about 5% w/w to about 15% w/w, or about 7% w/w to about 12% w/w carbon based on the total weight of the first particle fraction.
- the second particle fraction comprises anode material.
- the anode material comprises zinc metal and zinc oxide (ZnO), also referred to as zinc/zinc oxide.
- the second particle fraction may be concentrated in zinc/zinc oxide.
- the second particle fraction has a higher % w/w concentration of zinc (e.g. elemental zinc derived from the zinc metal and/or zinc oxide) compared to the concentration of zinc in the first particle fraction, based on the total weight of the particle fraction.
- zinc e.g. elemental zinc derived from the zinc metal and/or zinc oxide
- the second particle fraction has a zinc % distribution of between about 20% to about 60% based on the amount of zinc in the alkaline MMD prior to comminution.
- the second particle fraction may have a zinc % distribution (based on the amount of zinc in the alkaline MMD prior to comminution) of at least about 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58 or 60.
- the second particle fraction may have a zinc % distribution (based on the amount of zinc in the alkaline MMD prior to comminution) of less than about 60, 58, 56, 54, 52, 50, 48, 46, 44, 42, 40, 38, 36, 34, 32, 30, 28, 26, 24, 22 or 20.
- the second particle fraction may have a zinc % distribution in an amount in a range provided by any two of these upper and/or lower amounts, for example between about 30% to about 50% based on the amount of zinc in the alkaline MMD prior to comminution.
- the second particle fraction has a lower % w/w concentration of carbon compared to the concentration of carbon in the first particle fraction, based on the total weight of the particle fraction.
- the second particle fraction has a carbon % distribution of between about 1% to about 60% based on the amount of carbon in the alkaline MMD prior to comminution.
- the second particle fraction may have a carbon % distribution (based on the amount of carbon in the alkaline MMD prior to comminution) of at least about 1, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 or 60.
- the second particle fraction may have a carbon % distribution (based on the amount of carbon in the alkaline MMD prior to comminution) of less than about 60, 55, 50, 45,
- the second particle fraction may have a carbon % distribution in an amount in a range provided by any two of these upper and/or lower amounts, for example between about 5% to about 15% based on the amount of carbon in the alkaline MMD prior to comminution.
- the second particle fraction comprises between about 10% w/w to about 60 % w/w zinc based on the total weight of the second particle fraction.
- the second particle fraction may comprise zinc in an amount (as a % w/w based on the total weight of the second particle fraction) of at least about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 or 60.
- the second particle fraction may comprise zinc in an amount (as a % w/w based on the total weight of the second particle fraction) of less than about 60, 55, 50, 45, 40, 35, 30, 25, 20, 15 or 10.
- the second particle fraction may comprise zinc in an amount in a range provided by any two of these upper and/or lower amounts, for example between about 20% w/w to about 60% w/w, or about 25% w/w to about 40% w/w zinc based on the total weight of the second particle fraction.
- the amount of manganese, carbon and/or zinc, and other metals present in the alkaline MMD particles, including the first and second particle fractions may be determined using any suitable elemental compositional analysis technique, including for example one or more head assay analyses, including ashing, fusion, mixed acid digestion, Inductively coupled plasma - optical emission spectrometry (ICP-OES) , Inductively coupled plasma mass spectrometry (ICP-MS), X-ray fluorescence (XRF) or thermal analysis for carbon (such as Leco or CS2000).
- head assay analyses including ashing, fusion, mixed acid digestion, Inductively coupled plasma - optical emission spectrometry (ICP-OES) , Inductively coupled plasma mass spectrometry (ICP-MS), X-ray fluorescence (XRF) or thermal analysis for carbon (such as Leco or CS2000).
- the process may further comprise b) separating the first particle fraction comprising cathode material and carbon from the second particle fraction comprising anode material which are generated by the comminution of the alkaline MMD.
- the separating of the particle fractions at step b) may comprise a size screening or froth flotation of the comminuted alkaline MMD particles.
- the comminuted alkaline MMD particles may be size screened to separate the first particle fraction.
- the first particle fraction may be separated from the comminuted alkaline MMD particles via size-screening between about 30 pm to about 200 pm.
- the first particle fraction may be separated from the comminuted alkaline MMD particles via size screening below about 200, 180, 160, 140, 120, 100, 90, 80, 75, 70, 65, 60, 55, 40, 35 or 30 pm. Combination of these values can provide a range selection, for example between about 50 pm to about 100 pm.
- the separating of the particle fractions described herein comprise froth flotation of the alkaline MMD particles.
- Froth flotation involves the separation of the particle fractions based on their surface properties, namely their hydrophobic or hydrophilic properties. Generally speaking, hydrophilic surfaces will tend to associate with water (or another suitable aqueous phase) while hydrophobic surfaces will associate with a non-aqueous phase, for example air bubbles. Froth flotation separation exploits these surface properties to separate materials.
- Froth flotation processes are performed in a suitable froth flotation vessel (also called a cell or tank).
- the froth flotation vessel may be rectangular or cylindrical mechanically or naturally aerated vessels, flotation columns or cells.
- One or more froth flotation vessels/cells may be used, for example arranged in a series of cascading vessels/cells.
- the flotation concentrate comprises particles that are more hydrophobic compared to the particles which have reported to the flotation tail, which are generally more hydrophilic.
- the separating of the particle fractions at step b) comprises performing a froth flotation separation on the comminuted alkaline MMD particles in a froth flotation vessel.
- the first particle fraction comprising cathode material and carbon reports to a flotation concentrate
- second particle fraction comprising anode material reports to a flotation tail.
- the process further comprises removing the flotation concentrate from the froth flotation vessel to separate and obtain the first particle fraction comprising cathode material and carbon.
- the froth flotation separation comprises: bl) suspending the comminuted alkaline MMD particles in an aqueous solution comprising one or more froth flotation agents in the froth flotation vessel to create a slurry; t>2) aerating the slurry to generate air bubbles which float to the surface of the slurry to from a froth, wherein the first particle fraction comprising cathode material and carbon attaches to at least some of the air bubbles and floats to the top of the froth flotation vessel to report to the flotation concentrate, and the second particle fraction comprising anode material remains in the slurry to report to the flotation tail.
- the froth flotation processes described herein exploits carbons inherent hydrophobic properties to preferentially float manganese oxide (i.e. cathode material) separate to the zinc/zinc oxide (i.e. anode material), as opposed to recovering carbon as a separate material to the electrode material.
- cathode material preferentially float manganese oxide
- zinc/zinc oxide i.e. anode material
- carbon remains physically or chemically associated with the manganese oxide.
- the inventors have surprisingly identified that comminuting the alkaline MMD to a reduced particle size (for example to between about 50 pm to about 300 pm) increases the recovery of manganese oxide and carbon in the floatation concentrate separate to the anode material of zinc/zinc oxide.
- a reduced particle size for example to between about 50 pm to about 300 pm
- the flotation concentrate may comprise the first particle fraction as described herein. It will be appreciated that the manganese and carbon % distribution and % w/w concentration of the first particle fraction as described herein equally apply to the manganese and carbon % distribution and % w/w concentration of the flotation concentrate.
- the flotation concentrate is concentrated in manganese oxide and/or carbon.
- the flotation concentrate has a higher % w/w concentration of manganese and/or carbon compared to the concentration of manganese and/or carbon in the flotation tail, based on the total weight of the reported particles.
- the flotation concentrate may have a higher % w/w concentration of carbon compared to the concentration of carbon in the flotation tail, based on the total weight of the reported particles.
- the particles that do not attach to the air bubbles and float to the surface of the vessel are referred to as the flotation tail.
- the flotation tail comprises particles that are more hydrophilic compared to the particles which have reported to the flotation concentrate, which are generally more hydrophobic.
- the particles of the flotation tail may be subjected to further processing (i.e. attritioning) and further froth flotation steps to recover hydrophobic particles (e.g. cathode material and carbon) that did not initially float. This process is known as scavenging.
- the process further comprises one or more additional froth flotation separation steps to recover cathode material and carbon from the flotation tail.
- the flotation tail may comprise the second particle fraction as described herein. It will be appreciated that the zinc and carbon % distribution and % w/w concentration of the second particle fraction as described herein equally apply to the zinc and carbon % distribution and % w/w concentration of the flotation tail.
- the flotation tail is concentrated in zinc/zinc oxide.
- the flotation tail has a higher % w/w concentration of zinc compared to the concentration of zinc in the flotation concentrate, based on the total weight of the reported particles.
- the flotation tail has a lower % w/w concentration of carbon compared to the concentration of carbon in the particles of the flotation concentrate, based on the total weight of the reported particles.
- the alkaline MMD may comprise one or more heavy metals because of other battery types (e.g. lithium-ion, lead batteries etc.) misreporting to the alkaline battery feed which is then physically separated to obtain the alkaline MMD.
- the present inventors have surprisingly identified that, according to some embodiments or examples described herein, one or more heavy metals present in the comminuted alkaline MMD particles preferentially report to the flotation tail as part of the second particle fraction (i.e. with the anode material).
- the one or more heavy metals include for example lead (Pb), arsenic (As), cadmium (Cd), and mercury (Hg).
- the flotation tail has a higher ppm concentration of heavy metal (e.g. Cd, Pb etc.) compared to the concentration of heavy metal in the flotation concentrate, based on the total weight of the reported particles.
- heavy metal e.g. Cd, Pb etc.
- the flotation tail may comprise one or more heavy metals in an amount of between about 100 ppm to about 500 ppm based on the total weight of the reported particles.
- the flotation tail may have a heavy metal concentration (as ppm based on the total weight of the reported particles) of at least about 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 320, 340, 360, 380, 400, 420, 440, 460, 480 or 500.
- the flotation tail may have a heavy metal concentration in an amount in a range provided by any two of these amounts, for example between about 100 ppm to about 300 ppm, based on the total weight of the reported particles.
- the flotation concentrate may comprise one or more heavy metals in an amount of between about 1 ppm to about 200 ppm based on the total weight of the reported particles.
- the flotation concentrate may have a heavy metal concentration (as ppm based on the total weight of the reported particles) of less than about 200, 150,
- the flotation concentrate may have a heavy metal concentration in an amount in a range provided by any two of these amounts, for example between about 50 ppm to about 100 ppm, based on the total weight of the reported particles.
- the cathode material enriched with carbon can be readily processed into a fertiliser with higher % manganese and carbon content.
- the froth flotation separation comprises suspending the comminuted alkaline MMD particles in an aqueous solution, optionally comprising one or more froth flotation agents in the froth flotation vessel to create a slurry.
- Froth flotation agents comprise one or more materials that are suitable to manipulate the hydrophobic and/or hydrophilic properties of the suspended comminuted alkaline MMD particles to facilitate separation and/or assist in froth generation.
- the aqueous slurry and optional froth flotation agents may also be referred to as a “pulp”.
- any froth flotation agent that facilitates in the separation of the particle fractions by rendering the surfaces thereof more hydrophobic and/or more hydrophilic relative to each other so that the hydrophobic material attaches to air bubbles and floats to report to the flotation concentrate while the hydrophilic particles remain in the aqueous solution and report to the flotation tail can be used.
- the one or more froth flotation agents is selected from the group consisting of a frother, collector and/or depressant.
- a collector may be added to the aqueous solution comprising suspended alkaline MMD particles, which physically or chemically absorbs to the first particle fraction to increase the hydrophobicity of the particles and promote attachment to the air bubbles generated.
- a depressant may be added, which physically or chemically absorbs to the second particle fraction to increase the hydrophilicity of the particles.
- the aqueous solution comprising suspended comminuted alkaline MMD particles also comprises a frother and a collector, and optionally a depressant.
- the frother is an alcohol.
- the frother is an alcohol selected from the group consisting of methyl isobutyl carbinol (MIBC), 2- ethyl hexanol, isoamyl alcohol, cyclohexanol, a-terpinol, cresol, xylenol, glycol ether, and a combination thereof.
- the frother is methyl isobutyl carbinol (MIBC).
- MIBC methyl isobutyl carbinol
- the frother may be added in an amount effective to assist in stabilising the froth formed by the air bubbles at the surface of the slurry, as known to the skilled person.
- a collector may be added to enhance the hydrophobicity of the first particle fraction comprising carbon and cathode material.
- Suitable collectors include a hydrocarbon oil (e.g. kerosene), fatty acids (e.g. oleic acid) and hydroximates (e.g. hydroxamic acid).
- the collector is a hydrocarbon oil.
- the hydrocarbon oil is kerosene.
- the collector may be added in an amount effective to manipulate the surface of the first particle to be more hydrophobic, thereby promoting attachment to the air bubbles during aeration.
- the collector is provided in an amount of between about 100 g/t to about 8000 g/t.
- the collector may be provided in an amount (in g/t) of at least about 100, 200, 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000,
- the collector may be provided in an amount (in g/t) of less than about 8000, 7500, 7000, 6500, 6000, 5500, 5000, 4500, 4000, 3500, 3000, 2500, 2000, 1500, 1000, 500, 200 or 100.
- the collector may be provided in an amount in a range provided by any two of these upper and/or lower amounts, for example between about 500 g/t to about 2000 g/t.
- the carbon present in the first particle fraction little or no collector is required to manipulate the hydrophobic properties of the first particle fraction owing to the inherent hydrophobic nature of the carbon.
- any addition of a collector may be advantageous to further enhance the inherent hydrophobicity of the first particle fraction comprising carbon and cathode material to facilitate separation from the anode material via froth flotation.
- the aqueous slurry comprising comminuted alkaline MMD particles, and optionally one or more froth flotation agents, is then aerated (i.e. sparged with air) to generate air bubbles.
- aerated i.e. sparged with air
- hydrophobic particles attach to at least some of the air bubbles and float to the top of the froth flotation vessel to form a froth for removal versus the hydrophilic particles which remain in the aqueous slurry.
- particles having different surface properties are separated from one and other.
- the aqueous slurry may be aerated at flow rate effective to generate sufficient air bubbles and froth to separate the particle fraction.
- the flow rate may be at a rate suitable for industrial scale separation, as understood by the person skilled in the art.
- the aqueous slurry may be aerated for a period of time effective to generate sufficient air bubbles and froth to separate the particle fraction.
- the aeration of the aqueous slurry may be for a period of time of between 10 minutes to about 24 hours.
- the aeration of the aqueous slurry may be for a period of time of at least 1, 5, 10, 15, 20, 30, 45 (minutes), 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 18, or 24 hours.
- the aeration of the aqueous slurry may be for a period of time of less than 24,
- the aeration times may be provided by any two of these upper and/or lower amounts.
- the pH of the aqueous slurry may be any suitable pH.
- the pH of the aqueous slurry is the slurry’s natural pH (i.e. the pH of the slurry once the comminuted alkaline MMD particles and optional froth flotation agents are added).
- the pH of the aqueous slurry is between about 8 to about 14, for example between about 10 to about 13.
- the aqueous slurry comprising the comminuted alkaline MMD particles is conditioned prior to froth flotation to clean or activate the particles prior to aeration.
- Such conditioning may enhance the particles inherent hydrophobic/hydrophilic properties and facilitate in separation of the cathode and anode material.
- the flotation concentrate and/or tail can be removed from the flotation vessel by any conventional means to separate and obtain the first particle fraction of cathode material and carbon.
- the flotation concentrate can be removed by skimming off the froth using a mechanical propeller located at the slurry surface.
- the flotation tail can be removed via a suitable outlet valve or pump located below the surface of the slurry.
- the flotation tail comprising the second particle fraction is removed from the froth flotation vessel and undergoes gravity separation to recover any manganese and carbon entrained within the second particle fraction following froth flotation separation.
- the manganese and carbon recovered from gravity separation can be recycled into the froth flotation vessel or combined with the flotation concentrate.
- the comminuted alkaline MMD particles undergoes gravity separation to recover a light fraction comprising cathode material and carbon and a heavy fraction comprising anode material, wherein the light fraction comprising cathode material and carbon undergoes froth flotation separation.
- MMD Alkaline mixed metal dust
- the alkaline MMD may be obtained from alkaline batteries by any physical separation means, including for example conventional break operations to mechanically comminute the alkaline battery.
- the alkaline MMD may comprise one or more particulates (e.g. particles).
- the particles may take the form of flakes, fibres, agglomerates, granules, powders, spheres, pulverized materials or the like, as well as combinations thereof.
- the particles may have any desired shape including, but not hmited to, cubic, rod hke, polyhedral, spherical or semi- spherical, rounded or semi-rounded, angular, irregular, and so forth.
- the alkaline MMD may have an average particle size wherein 80% of the alkaline MMD particles (Pso) having a particle size of between about 500 pm to about 5000 pm for example about 1000 pm to 3000 pm.
- the alkaline MMD particle morphology and particle size can be measured by any conventional method, including laser diffraction, electron microscopy, dynamic light scattering, optical microscopy or size exclusion methods (such as wet or dry graduated mesh screens or filters).
- the alkaline MMD comprises cathode material, anode material and carbon.
- the alkaline MMD comprises between about 5% w/w to about 50% w/w manganese based on the total weight of the alkaline MMD.
- the alkaline MMD may comprise manganese in an amount (as a % w/w based on the total weight of alkaline MMD) of at least about 5, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28,
- the alkaline MMD may comprise manganese in an amount (as a % w/w based on the total weight of alkaline MMD) of less than about 50, 48, 46, 44, 42, 40, 38, 36, 34, 32, 30, 28, 26, 24, 22, 20, 18, 16, 14, 12, 10, 8 or 5.
- the alkaline MMD may comprise manganese in an amount in a range provided by any two of these upper and/or lower amounts, for example between about 10% w/w to about 40% w/w based on the total weight of alkaline MMD.
- the alkaline MMD comprises between about 5% w/w to about 50% w/w zinc based on the total weight of the alkaline MMD.
- the alkaline MMD may comprise zinc in an amount (as a % w/w based on the total weight of alkaline MMD) of at least about 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36,
- the alkaline MMD may comprise zinc in an amount (as a % w/w based on the total weight of alkaline MMD) of less than about 60, 58, 54, 52, 50, 48, 46, 44, 42, 40, 38, 36, 34, 32, 30, 28, 26, 24, 22, 20, 18,
- the alkaline MMD may comprise zinc in an amount in a range provided by any two of these upper and/or lower amounts, for example between about 20% w/w to about 50% w/w based on the total weight of alkaline MMD.
- the alkaline MMD comprises between about 0.1% w/w to about 20% w/w carbon based on the total weight of the alkaline MMD.
- the alkaline MMD may comprise carbon in an amount (as a % w/w based on the total weight of alkaline MMD) of at least about 0.1, 0.2, 0.5, 1, 2, 4, 6, 8, 10, 12, 14, 16, 18 or 20.
- the alkaline MMD may comprise carbon in an amount (as a % w/w based on the total weight of alkaline MMD) of less than about 20, 18, 16, 14, 12, 10, 8, 6, 4, 2, 1, 0.5, 0.2 or 0.1.
- the alkaline MMD may comprise carbon in an amount in a range provided by any two of these upper and/or lower amounts, for example between about 1% w/w to about 10% w/w based on the total weight of alkaline MMD.
- the alkaline MMD may comprise one or more additional metal values other than manganese, carbon or zinc (e.g. impurities). If present, the type and amount of impurity in the first particle fraction may depend on the alkaline battery feed used to obtain the MMD. Typical impurities present in the mixed in alkaline MMD may include aluminium (Al), arsenic (As), cadmium (Cd), copper (Cu), iron (Fe), potassium (K), sodium (Na) and titanium (Ti). In some embodiments, one or more additional metal values other than manganese, carbon or zinc (e.g.
- impurities including one or more of those metals recited above, may be present in the alkaline MMD in an amount of less than about 100000, 10000, 5000, 4000, 3000, 2000, 1000, 800, 600, 400, 200, 100, 50, or 10 ppm based on the total weight of the alkaline MMD.
- the alkaline MMD is provided by the steps: al) physically separating alkaline batteries to obtain coarser particles comprising steel and/or ferrous material and finer particles comprising alkaline MMD; and a2) separating the coarser particles comprising steel and/or ferrous material from the finer particles comprising alkaline MMD.
- the alkaline batteries may be physically separated using manual methods or conventional physical separation device/s such as a crusher, hammer mill or shredder.
- the physical separation may be performed in the presence of a liquid (e.g. wet shredding) or may be performed under dry conditions (e.g. dry- shredding).
- the weight split of the finer particles comprising alkaline MMD may be between about 30% to about 80% w/w based on the total weight of the alkaline battery.
- the weight split of the finer particles of the alkaline MMD (in % w/w based on the total weight of the alkaline battery) may be at least about 30, 35, 40, 45, 50, 55, 60, 65, 70, 75 or 80.
- the weight split of the finer particles of the alkaline MMD (in % w/w based on the total weight of the alkaline battery) may be less than about 80, 75, 70, 65, 60, 55, 50, 45, 40, 35 or 30.
- the weight split of the finer particles comprising alkaline MMD may be in a range provided by any two of these upper and/or lower amounts, for example between about 40% w/w to about 70% w/w based on the total weight of alkaline battery.
- the weight split of the coarser particles comprising steel and/or ferrous material may be between about 10% to about 50% w/w based on the total weight of the alkaline battery.
- the weight split of the coarser particles comprising steel and/or ferrous material (in % w/w based on the total weight of the alkaline battery) may be at least about 10, 15, 20, 25, 30, 35, 40, 45 or 50.
- the weight split of the coarser particles comprising steel and/or ferrous material (in % w/w based on the total weight of the alkaline battery) may be less than about 50, 45, 40, 35, 30, 25, 20, 15 or 10.
- the weight split of the coarser particles comprising steel and/or ferrous material may be in a range provided by any two of these upper and/or lower amounts, for example between about 10% w/w to about 40% w/w based on the total weight of alkaline battery.
- step a2) further comprises screening the separated alkaline battery particles at between about 4 mm to about 6 mm to separate the coarser particles comprising steel and/or ferrous material from the finer particle of alkaline MMD, for example at about 5 mm.
- step a2) may further comprise subjecting the separated alkaline battery particles to magnetic separation to separate the coarser particles comprising steel and/or ferrous material from the finer particles comprising alkaline MMD.
- the physical separation of the alkaline batteries at step al) produces a dust and/or fume comprising electrolyte, wherein the dust and/or fume is optionally treated to recover the electrolyte.
- the separated alkaline battery particles comprising coarser particles comprising steel and/or ferrous material and finer particles comprising alkaline MMD are washed and/or attritioned prior to step a2).
- the separated coarser particles comprising steel and/or ferrous material is subjected to crushing to liberate and obtain alkaline MMD trapped within the coarser particles.
- the liberated alkaline MMD may be combined with the finer particles comprising alkaline MMD.
- the separated first particle fraction comprising cathode material and carbon can be used as a micronutrient in fertilisers.
- the process further comprises mixing the separated first particle fraction comprising cathode material and carbon at step b) with a phosphorous source and optionally a binder to prepare a fertiliser.
- the comminuted alkaline MMD particles described herein can be used as a micronutrient for fertilisers.
- the process further comprises mixing comminuted alkaline MMD particles with a phosphorous source and optionally a binder to prepare a fertiliser.
- the fertiliser may be enriched in manganese and/or carbon.
- the fertiliser has a manganese concentration owing to the presence of manganese from the cathode material in the first particle fraction/comminuted particles.
- the fertiliser may have a manganese concentration (in mg/kg of fertiliser) of between about 1000 to about 20000.
- the fertiliser may have a manganese concentration (in mg/kg of fertiliser) of at least about 1000, 2000, 5000, 7000, 10000, 12000, 15000, 17000 or 20000.
- the fertiliser may have a manganese concentration (in mg/kg based on the total weight of fertiliser) of less than about 20000, 17000, 12000, 10000, 7000,
- the fertiliser may have a manganese concentration in an amount in a range provided by any two of these amounts, for example between about 1000 mg/kg to about 20000 mg/kg based on the total weight of fertiliser.
- the fertiliser has a carbon concentration owing to the presence of carbon in the first particle fraction/comminuted particles.
- any suitable phosphorous source may be used to prepare the fertiliser.
- the phosphorous source is a calcium phosphate salt or an ammonium phosphate salt, or a combination thereof.
- the calcium phosphate salt is monocalcium phosphate (Super Phosphate).
- the ammonium phosphate salt is monoammonium phosphate (MAP) or diammonium phosphate (DAP), or a combination thereof.
- any suitable binder may be used to bind, in one embodiment, the binder is phosphoric acid or formic acid, or a combination thereof.
- the fertiliser may be prepared using conventional blending/mixing techniques known to the person skilled in the art.
- the amount of phosphorous source and optional binder to be mixed with the separated first particle fraction comprising cathode material and carbon or comminuted alkaline MMD particles is sufficient to provide a fertiliser with a manganese concentration of about 1 % w/w based on the total weight of the fertiliser.
- the amount of heavy metals (if present in the separated first particle fraction comprising cathode material and carbon comminuted alkaline MMD particles) in the final fertiliser needs to be controlled.
- the amount of phosphorous source and optional binder to be mixed with the separated first particle fraction comprising cathode material and carbon or the comminuted alkaline MMD particles is sufficient to provide a fertiliser with a heavy metal concentration of less than 1000, 800, 600, 400, 200, 100, 50, 10, 5, or 1 ppm based on the total weight of the fertiliser.
- the fertiliser may comprise 10 ppm or less of cadmium and/or 100 ppm or less of lead.
- the preferential reporting of any heavy metal present in the alkaline MMD to the flotation tail with the anode material allows for the cathode material enriched with carbon to be recovered from the flotation concentrate and readily processed into a fertiliser having low amounts of heavy metal impurity. Additionally, a more enriched manganese fertiliser can be obtained owing to reduced ppm levels of heavy metal reporting to the flotation concentrate.
- a fertiliser comprising comminuted alkaline MMD particles obtained from alkaline batteries, a phosphorous source, and optionally a binder. In one embodiment, there is provided a fertiliser comprising separated cathode material and carbon obtained from alkaline batteries, a phosphorous source, and optionally a binder.
- the separated first particle cathode material and carbon and/or anode material can be recycled for use as electrode materials for alkaline batteries.
- the separated first particle fraction comprising cathode material and carbon and/or separated second particle fraction comprising anode material is processed into one or more electrodes for alkaline batteries.
- the process further comprises using the separated cathode material and carbon and/or anode material obtained by the process described herein as one or more electrodes for making an alkaline battery.
- the process further comprises assembling an alkaline battery comprising one or more electrodes prepared using the separated first particle fraction comprising cathode material and carbon and/or separated second particle fraction comprising anode material.
- an alkaline battery comprising one or more electrodes prepared using the separated cathode material and carbon and/or anode material obtained by the processes described herein.
- the separated first particle fraction comprising cathode material and carbon and/or anode material obtained by the processes described herein, as an electrode material (e.g. cathode and/or anode) for preparing one or more electrodes for alkaline batteries.
- an electrode material e.g. cathode and/or anode
- Example 1 Embodiment of process for recovering cathode material and carbon from alkaline batteries using physical separation
- sorted end of life alkaline batteries are physically separated, using a suitable device, using manual methods or conventional physical separation device/s such as a crusher, hammer mill or shredder (110).
- Coarser particles comprising steel and/or ferrous material are recovered by simple size separation at 500 pm or magnetic separation, to recover a steel/ferrous product (200).
- Finer particles comprising alkaline MMD comprising cathode material and carbon (113) and anode material (112) are also generated which in some embodiments are comminuted (not shown).
- coarse material from the size separation stage can be recycled to the physical separation stage, for further size reduction (not shown).
- Table 1 shows typical mass recovered to the steel or ferrous product (200).
- Table 1 Mass split of steel and/or ferrous product (200) and alkaline MMD (112) via the process described herein.
- the anode material (112) and cathode material and carbon (113) are separated into separate fractions, in this example by size separation at 75 pm to create a separated second particle fraction comprising anode material (300) and a first particle fraction comprising cathode material and carbon (400).
- Table 2 shows typical mass recovered and analysis of the separate anode material (300) and cathode material and carbon (400) fractions.
- Table 2 Composition of material separated and recovered via the simple physical separation process described in Figure 1.
- dust and fume (114) from physical alkaline battery separation (110), are recovered and treated (120), using conventional off gas treatment equipment such as bag filters/houses and wet gas/fume scrubbers, for example venturi or packed tower (120). Dust recovered is returned to the physical separation stage (110) and electrolyte material recovered (500) from the wet gas/fume scrubber.
- Example 2 Embodiment of process for recovering values from alkaline batteries using froth flotation separation
- end of life alkaline batteries are physically separated (120), using a suitable device, using a manual methods or a conventional physical separation device/s such as a crusher, hammer mill or shredder.
- Crushed or shredded end of life alkaline batteries (121) are subject to size based classification or magnetic separation methods (130) to recover coarser particles steel or ferrous material (131) and generate a steel and/or ferrous product (200). Mass recovery to the steel and/or ferrous product is as detailed in Table 1.
- coarse material (133) from the size separation stage can be recycled to the physical separation stage (120), for further size reduction.
- the alkaline MMD is comminuted prior to froth flotation separation (not shown).
- Anode concentrated material (151) reports preferentially to the flotation tail and is recovered as an anode material product (300).
- Cathode material and carbon (152) preferentially float and report to the froth fraction and is recovered as a cathode material and carbon flotation concentrate product (400).
- Froth flotation can be completed with flotation reagent such as depressants, collectors and frothers using equipment (cells) specifically designed for introduction of air to promote bubble formation and recover hydrophobic particles.
- Table 3 shows the impact of froth flotation (150) on the separation of cathode material and carbon (152) from anode material (151). Cathode material and carbon product (400) is recovered in the flotation concentrate from the froth flotation stage.
- Table 3 Composition of material recovered via the froth flotation process described in Figure 3.
- Example 3 Embodiment of process for recovering values from alkaline batteries using gravity separation
- end of life alkaline batteries are physically separated (120), using a suitable device, using manual methods or a conventional physical separation device/s such as a crusher, hammer mill or shredder.
- Crushed or shredded end of life alkaline batteries (121) are subject to size based classification or magnetic separation methods (130) to recover coarser particles comprising steel and/or ferrous material (131) and generate a steel and/or ferrous product (200). Mass recovery to the steel and/or ferrous product is as detailed in Table 1.
- the alkaline MMD may be comminuted prior to gravity separation (not shown).
- Anode concentrated material (161) reports preferentially to the heavy gravity fraction and is recovered as an anode material product (300).
- Concentrated cathode material and carbon (162) reports preferentially to the light gravity separation fraction and is recovered as a cathode material and carbon product (400).
- Gravity separation is often completed in separate stages as fine and coarse fractions and using devices such as, jigs, spirals, tables, high gravity concentrators or hydraulic / up flow classifiers.
- Table 4 Composition of material separated and recovered via the gravity separation process described in Figure 4.
- Example 4 Embodiment of process for recovering values from alkaline batteries using comminution and froth flotation
- end of life alkahne batteries are physically separated (120), using a suitable device, using a manual methods or a conventional physical separation device/s such as a crusher, hammer mill or shredder.
- Crushed or shredded end of life alkahne batteries (121) are subject to size based classification or magnetic separation methods (130) to recover coarser particles comprising steel and/or ferrous material (131) and generate a steel and/or ferrous product (200). Mass recovery to the steel and/or ferrous product is as detailed in Table 1. Optionally coarse material (133) from the size separation stage can be recycled to the physical separation stage (120), for further size reduction.
- a comminution step 140
- additional steel and/or ferrous material can be recovered (141) from the comminution stage (140). This material can be combined into the steel and/or ferrous product (200).
- Comminuted alkahne MMD particles (142) undergoes froth flotation (150).
- Anode concentrated material (151) report preferentially to the flotation tails fraction and is recovered as an anode material product (300).
- Cathode material and carbon (152) report preferentially to the froth fraction and is recovered as a cathode material and carbon flotation concentrate product (400).
- froth flotation is completed with flotation agents such as depressants, collectors and frothers in using equipment (cells) specifically designed for introduction of air to promote bubble formation and recovery hydrophobic particles.
- Table 5 shows the impact of grinding (140) on froth flotation (150) performance for separating cathode material and carbon (152) from anode material (151), present in the end of life alkaline batteries.
- a grind time of two minutes of the electrode material (132) leads to an improved liberation of cathode material and carbon.
- Further size reduction surprisingly leads to lower manganese grades in the cathode material product (400) due to disassociation of the carbon from the manganese oxide.
- Table 5 Composition of material separated and recovered via the froth flotation process described in Figure 5 at varying grind times.
- Example 5 Embodiment of process for recovering values from alkaline batteries using combination of froth flotation and gravity separation
- end of life alkaline batteries are physically separated (120), using a suitable device, using a manual methods or a conventional physical separation device/s such as a crusher, hammer mill or shredder.
- Crushed or shredded end of life alkaline batteries (121) are subject to size based classification or magnetic separation methods (130) to recover coarser particles comprising steel and/or ferrous material (131) and generate a steel and/or ferrous product (200). Mass recovery to the steel and/or ferrous product is as detailed in Table 1.
- coarse material (133) from the size separation stage can be recycled to the physical separation stage (120), for further size reduction.
- Finer particles comprising alkaline MMD, low in steel and/or ferrous (132) undergoes a comminution step (140) to reduce the average particle size using devices such as grinding mill (either rod or ball) or mixing or attritioning, using an agitated tank, attritioner or high intensity agitator.
- a comminution step 140
- additional steel and/or ferrous material can be recovered (141) from the comminution stage (140). This material can be combined into the steel and/or ferrous product (200).
- Comminuted alkaline MMD particles (142) undergoes froth flotation (150).
- Cathode material and carbon (154) floats preferentially and reports to the froth fraction and is recovered as a cathode material and carbon flotation concentrate product (400).
- Anode concentrated material (153) reports preferentially to the flotation tail is recovered, and undergoes gravity separation (160).
- Anode concentrated material (162) report preferentially to the heavy gravity fraction and is recovered as an anode material product (300).
- Table 6 shows the impact of grinding (140), froth flotation (150) and gravity separation (160) on the separation of cathode material and carbon (154) from anode material (162).
- Table 6 Composition of material separated and recovered via the combine froth flotation and gravity separation process described in Figure 6.
- Example 6 Embodiment of process for recovering values from alkaline batteries using combination of gravity separation and froth flotation
- Figure 7 demonstrates an alternative embodiment using combination of froth flotation and gravity where end of life alkaline batteries are physically separated (120), using a suitable device, using a manual methods or a conventional physical separation device/s such as a crusher, hammer mill or shredder
- Crushed or shredded end of life alkaline batteries (121) are subject to size based classification or magnetic separation methods (130) to recover coarser particles comprising steel and/or ferrous material (131) and generate a steel and/or ferrous product (200). Mass recovery to the steel and/or ferrous product is as detailed in Table 1.
- coarse material (133) from the size separation stage can be recycled to the physical separation stage (120), for further size reduction.
- Finer particles comprising alkaline MMD, low in steel and/or ferrous (132) undergoes a comminution step (140) to reduce the average particle size using devices such as grinding mill (either rod or ball) or mixing or attritioning, using an agitated tank, attritioner or high intensity agitator.
- a comminution step 140
- additional steel and/or ferrous material can be recovered (141) from the comminution stage (140). This material can be combined into the steel and/or ferrous product (200).
- the light gravity separation fraction optionally undergoes froth flotation (150).
- Cathode material and carbon (155) floats preferentially and reports to the froth fraction and is recovered as a cathode material and carbon flotation concentrate product (400).
- Example 7 Use of separated cathode material and carbon as micronutrients for fertilisers
- cathode material and carbon (400) is combined with a fertiliser (i.e. a phosphorous source) (500) and a binder (600) and blended (210). Blending can occur in a rotary drum, augmenter or other conventional mixing device. The blended product is recovered and optionally dried (213), before being used as a source of micronutrients (700) in agriculture.
- a fertiliser i.e. a phosphorous source
- binder i.e. phosphorous source
- Blending can occur in a rotary drum, augmenter or other conventional mixing device.
- the blended product is recovered and optionally dried (213), before being used as a source of micronutrients (700) in agriculture.
- Table 7 Composition of source fertiliser (500) and fertiliser product (700) after blending with cathode material (400) via the process described Figure 8.
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Abstract
The present disclosure generally relates to processes for recovering and separating electrode materials from alkaline batteries, such as cathode and/or anode materials. The process comprises comminuting alkaline MMD to reduce the average particle size of the alkaline MMD to liberate and obtain a first particle fraction comprising cathode material and carbon and a second particle fraction comprising anode material; and separating and obtaining the first particle fraction comprising cathode material and carbon from the second particle fraction comprising anode material.
Description
PROCESS FOR RECOVERING VALUES FROM ALKALINE BATTERIES TECHNICAL FIELD
[0001] The present disclosure relates generally to processes for recovering values from alkaline batteries. More specifically, the present disclosure relates to processes for recovering and separating electrode materials from alkaline batteries, such as cathode and/or anode materials. The present disclosure also relates to compositions and products comprising cathode and/or anode materials recovered from alkaline batteries, including for example fertilisers and repurposed electrodes.
BACKGROUND
[0002] Modern alkaline batteries have been used to power small consumer and electronic applications since development in the late 1950’s. For example, alkaline batteries are used in personal devices, including toys, clocks, cameras and torches and other portable electronic devices.
[0003] As alkaline batteries reach their end of life, other than disposal into landfill, it is often desirable to recycle and dispose of them whilst recovering one or more values for on-sale and/or re-use. Current alkaline battery recycling often requires smelting or pyrometallurgical processing to extract one or more values. However, such processes often extract values as complex alloys with steel while additional valuable components are trapped as part of the slag phase and/or decomposed at the high temperature. As such, further processing of the slag material/alloys to obtain values requires high cost and additional processing steps.
[0004] Other recycling process include leaching shredded alkaline batteries with sulfuric acid to produce separated manganese and zinc as sulfated compounds. However, such recycling processes require specialist process equipment and expensive reagents.
[0005] Accordingly, there is a need for an alkaline battery recycling process which overcomes one or more of these disadvantages and/or provides the public with a useful alternative.
SUMMARY
[0006] The present inventors have undertaken research and development into processes for recovering one or more values from alkaline batteries, including for example cathode and/or anode materials. The present disclosure described herein can also be scalable for industrial application for processing and recycling large quantities of alkaline batteries and the recovered cathode and/or anode materials can be reused or repurposed across a variety of industries, including as repurposed electrode materials for cathodes and/or anodes in alkaline batteries, or as micronutrients for fertilisers.
[0007] Described herein is a process that can selectively separate and recover cathode material and carbon as a separate fraction to anode material from alkaline mixed metal
dust (MMD). The alkaline MMD can be obtained from alkaline batteries, for example via physical separation (e.g. shredding). According to some examples or embodiments described herein, the inventors have identified that comminuting alkaline MMD can advantageously result in the liberation of cathode material and carbon as a separate fraction to the anode material, including for example a concentrated manganese oxide and carbon product.
[0008] In some embodiments, the cathode material and carbon may be separated from the anode material by subjecting the alkaline MMD to a froth flotation separation. In particular, according to some embodiments or examples, the inventors have surprisingly identified that cathode material and carbon report selectively report to the flotation concentrate as a separate fraction to the anode material. Comminution of alkaline MMD prior to froth flotation separation may also increase the recovery and concentration of the cathode material and carbon in the flotation concentrate. Another advantage of using froth flotation to separate the cathode material and carbon from the anode material according to some embodiments or examples described herein also include the preferential reporting of heavy metals to the anode material.
[0009] One or more downstream advantages associated with the processes described herein are also disclosed. For example, the separated cathode material and carbon can be processed into a fertiliser. Alternatively or additionally, the comminuted alkaline MMD particles comprising both the cathode material and carbon fraction and the anode material fraction can also be processed into a fertiliser. Alternatively, the separated cathode material and carbon and/or anode material can also be processed into one or more electrodes for use in alkaline batteries. Various advantages relating to the process, separated materials and products are described herein.
[0010] In one aspect, there is provided a process for obtaining cathode material and carbon from alkaline mixed metal dust (MMD) obtained from alkaline batteries, comprising: a) comminuting alkaline MMD to reduce the average particle size of the alkaline MMD to liberate and obtain a first particle fraction comprising cathode material and carbon and a second particle fraction comprising anode material; and b) separating the first particle fraction comprising cathode material and carbon from the second particle fraction comprising anode material.
[0011] In one embodiment, 80% of the comminuted alkaline MMD particles (Pso) have a particle size of between about 50 pm to about 500 pm.
[0012] In one embodiment, the first particle fraction comprises manganese oxide and carbon, and the second particle fraction comprises zinc/zinc oxide. The first particle fraction may be concentrated in manganese oxide and carbon and the second particle fraction may be concentrated in zinc/zinc oxide. In one embodiment, the first particle fraction has a higher % w/w concentration of manganese compared to the concentration of manganese in the second particle fraction, based on the total weight of the particle fraction. The first particle fraction may comprise between about 25% w/w to about 60 % w/w manganese based on the total weight of the first particle fraction. The first
particle fraction may comprise between about 5% w/w to about 15% w/w carbon based on the total weight of the first particle fraction.
[0013] In one embodiment, the second particle fraction has a higher % w/w concentration of zinc compared to the concentration of zinc in the first particle fraction, based on the total weight of the particle fraction. The second particle fraction may comprise between about 20% w/w to about 70% w/w zinc, based on the total weight of the second particle fraction. In one embodiment, the carbon is physically or chemically associated with the manganese oxide as a mixed manganese oxide/carbon material. In one embodiment, the mixed manganese oxide/carbon material is a mixed MnC /MmCb/carbon material.
[0014] In one embodiment, the separating of the particle fractions at step b) comprises a size screening of the comminuted alkaline MMD particles. In an alternative embodiment, the separating of the particle fractions at step b) comprises froth flotation of the comminuted alkaline MMD particles.
[0015] In one embodiment, the separating of the particle fractions at step b) comprises performing a froth flotation separation on the comminuted alkaline MMD particles in a froth flotation vessel, wherein the first particle fraction comprising cathode material and carbon reports to a flotation concentrate, and second particle fraction comprising anode material reports to a flotation tail, and removing the flotation concentrate from the froth flotation vessel to separate and obtain the first particle fraction comprising cathode material and carbon.
[0016] In one embodiment, the flotation separation comprises: bl) suspending the comminuted alkaline MMD particles in an aqueous solution comprising one or more froth flotation agents in the froth flotation vessel to create a slurry; b2) aerating the slurry to generate air bubbles which float to the surface of the slurry to form a froth, wherein the first particle fraction comprising cathode material and carbon attaches to at least some of the air bubbles and floats to the top of the froth flotation vessel to report to the flotation concentrate, and the second particle fraction comprising anode material remains in the slurry to report to the flotation tail.
[0017] In one embodiment, the one or more froth flotation agents is selected from the group consisting of a frother, collector, and/or depressant. The frother may be an alcohol selected from the group consisting of methyl isobutyl carbinol (MIBC), 2-ethyl hexanol, isoamyl alcohol, cyclohexanol, a-terpinol, cresol, xylenol, glycol ether, and a combination thereof. The collector may be provided in an amount of between about 100 g/t to about 8000 g/t. The collector may be hydrocarbon oil, fatty acid or hydroximate. The hydrocarbon oil may be kerosene.
[0018] In one embodiment, after step bl) and prior to step b2), the slurry comprising the comminuted alkaline MMD particles is conditioned prior to froth flotation to clean or activate the particles prior to aeration.
[0019] In one embodiment, the flotation tail comprising the second particle fraction is removed from the froth flotation vessel and undergoes gravity separation to recover any manganese and carbon entrained within the second particle fraction following froth flotation separation. In one embodiment, the manganese and carbon recovered from gravity separation is recycled into the froth flotation vessel or combined with the flotation concentrate.
[0020] In one embodiment, one or more heavy metals present in the comminuted alkaline MMD particles preferentially report to the flotation tail as part of the second particle fraction. In one embodiment, the flotation tail has a higher ppm concentration of heavy metal compared to the concentration of heavy metal in the flotation concentrate, based on the total weight of the reported particles.
[0021] In one embodiment, the alkaline MMD is provided by the steps: al) physically separating alkaline batteries to obtain coarser particles comprising steel and/or ferrous material and finer particles comprising alkaline MMD; and a2) separating the coarser particles comprising steel and/or ferrous material from the finer particles comprising alkaline MMD.
[0022] In one embodiment, the finer particles comprising alkaline MMD is between about 30% to about 80% w/w based on the total weight of the alkaline battery.
[0023] In one embodiment, step a2) comprises screening the separated alkaline battery particles at between about 4 mm to about 6 mm to separate the coarser particles comprising steel and/or ferrous material from the finer particle of alkaline MMD. In an alternative embodiment, step a2) comprises subjecting the separated alkaline battery particles to magnetic separation to separate the coarser particles comprising steel and/or ferrous material from the finer particles comprising alkaline MMD.
[0024] In one embodiment, the physical separation of the alkaline batteries at step al) produces a dust and/or fume comprising electrolyte, wherein the dust and/or fume is optionally treated to recover the electrolyte.
[0025] In one embodiment, the separated alkaline battery particles comprising coarser particles comprising steel and/or ferrous material and finer particles comprising alkaline MMD are washed and/or attritioned prior to step a2). Alternatively or additionally, the separated coarser particles comprising steel and/or ferrous material may be subjected to crushing to liberate and obtain alkaline MMD trapped within the coarser particles.
[0026] In one embodiment, the separated first particle fraction comprising cathode material and carbon and/or separated second particle fraction comprising anode material is processed into one or more electrodes for alkaline batteries.
[0027] In one embodiment, the process further comprises assembling an alkaline battery comprising one or more electrodes prepared using the separated first particle
fraction comprising cathode material and carbon and/or separated second particle fraction comprising anode material.
[0028] In one embodiment, the process further comprises mixing the separated first particle fraction comprising cathode material and carbon at step b) with a phosphorous source and optionally a binder to prepare a fertiliser.
[0029] In one embodiment, the phosphorous source is a calcium phosphate salt or ammonium phosphate salt, or a combination thereof. The calcium phosphate salt may be monocalcium phosphate (Super Phosphate). The ammonium phosphate salt may be monoammonium phosphate (MAP) or diammonium phosphate (DAP), or a combination thereof. The binder may be phosphoric acid.
[0030] In another aspect, there is provided use of the separated first particle fraction comprising cathode material and carbon obtained by the process as described above, as a micronutrient in fertiliser.
[0031] In another aspect, there is provided a fertiliser comprising comminuted alkaline MMD particles or separated cathode material and carbon obtained from alkaline batteries, a phosphorous source, and optionally a binder.
[0032] In another aspect, there is provided an alkaline battery comprising one or more electrodes prepared using the separated cathode material and carbon and/or anode material obtained by the processes described above.
[0033] In another aspect, there is provided use of the separated first particle fraction comprising cathode material and carbon and/or anode material obtained by the process described above, as an electrode material for preparing one or more electrodes for alkaline batteries.
[0034] It will be appreciated that other aspects, embodiments and examples of the processes and materials are described herein.
BRIEF DESCRIPTION OF FIGURES
[0035] Notwithstanding any other forms which may fall within the scope of the process described herein, specific embodiments will now be described, by way of example only, with reference to the accompanying figures in which:
[0036] Figure 1: Process flow sheet depicting a process for liberating and obtaining cathode, carbon and anode materials from alkaline batteries using physical separation.
[0037] Figure 2: Process flow sheet depicting a process for obtaining cathode, carbon and anode materials from alkaline batteries using physical separation, with dust and fume treatment for electrolyte recovery.
[0038] Figure 3: Process flow sheet depicting a process for obtaining cathode, carbon and anode materials from alkaline batteries using flotation.
[0039] Figures 4: Process flow sheet depicting a process for obtaining cathode, carbon and anode materials from alkaline batteries using gravity separation.
[0040] Figure 5: Process flow sheet depicting a process for obtaining cathode, carbon and anode materials from alkaline batteries using comminution and froth flotation.
[0041] Figure 6 and 7: Process flow sheets depicting a process for obtaining cathode, carbon and anode materials products from alkaline batteries using combinations of froth flotation and gravity separation.
[0042] Figure 8: Process flow sheet depicting a process for preparing a fertiliser using separated cathode material and carbon as a micronutrient.
DETAILED DESCRIPTION
[0043] The present disclosure describes the following various non-limiting embodiments, which relates to investigations undertaken to identify processes for recovering one or more values from alkaline batteries.
General terms
[0044] In the following description, reference is made to the accompanying drawings which form a part hereof, and which is shown, by way of illustration, several embodiments. It is understood that other embodiments may be utilized and structural changes may be made without departing from the scope of the present disclosure.
[0045] With regards to the definitions provided herein, unless stated otherwise, or implicit from context, the defined terms and phrases include the provided meanings. Unless explicitly stated otherwise, or apparent from context, the terms and phrases below do not exclude the meaning that the term or phrase has acquired by a person skilled in the relevant art. The definitions are provided to aid in describing particular embodiments, and are not intended to limit the claimed invention, because the scope of the invention is limited only by the claims. Furthermore, unless otherwise required by context, singular terms shall include pluralities and plural terms shall include the singular.
[0046] All publications discussed and/or referenced herein are incorporated herein in their entirety.
[0047] Any discussion of documents, acts, materials, devices, articles or the like which has been included in the present specification is solely for the purpose of providing a context for the present disclosure. It is not to be taken as an admission that any or all of these matters form part of the prior art base or were common general knowledge in the field relevant to the present disclosure as it existed before the priority date of each claim of this application.
[0048] Throughout this disclosure, unless specifically stated otherwise or the context requires otherwise, reference to a single step, composition of matter, group of steps or
group of compositions of matter shall be taken to encompass one and a plurality (i.e., one or more) of those steps, compositions of matter, groups of steps or groups of compositions of matter. Thus, as used herein, the singular forms “a”, “an” and “the” include plural aspects unless the context clearly dictates otherwise. For example, reference to “a” includes a single as well as two or more; reference to “an” includes a single as well as two or more; reference to “the” includes a single as well as two or more and so forth.
[0049] Those skilled in the art will appreciate that the disclosure herein is susceptible to variations and modifications other than those specifically described. It is to be understood that the disclosure includes all such variations and modifications. The disclosure also includes all of the examples, steps, features, methods, compositions, coatings, processes, and coated substrates, referred to or indicated in this specification, individually or collectively, and any and all combinations or any two or more of said steps or features.
[0050] Unless otherwise defined, all technical and scientific terms used herein have the same meaning commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.
[0051] The term “and/or”, e.g., “X and/or Y” shall be understood to mean either “X and Y” or “X or Y” and shall be taken to provide explicit support for both meanings or for either meaning.
[0052] The reference to “substantially free” generally refers to the absence of that compound or component in the material (e.g. absence of a particular impurity in the first or second particle fractions, cathode or anode materials, flotation concentrate or tail) other than any trace amounts or impurities that may be present, for example this may be an amount by weight % in the total composition of less than about 1%, 0.1%, 0.01%, 0.001%, or 0.0001%., or an amount as ppm in the total composition of less than about 10000, 1000, 100, 10 or 1 ppm.
[0053] Unless otherwise indicated, the terms “first,” “second,” etc. are used herein merely as labels, and are not intended to impose ordinal, positional, or hierarchical requirements on the items to which these terms refer. Moreover, reference to a “second” item does not require or preclude the existence of lower-numbered item (e.g., a “first” item) and/or a higher-numbered item (e.g., a “third” item).
[0054] As used herein, the phrase “at least one of’, when used with a list of items, means different combinations of one or more of the listed items may be used and only one of the items in the fist may be needed. The item may be a particular object, thing, or category. In other words, “at least one of’ means any combination of items or number of items may be used from the list, but not all of the items in the list may be required. For example, “at least one of item A, item B, and item C” may mean item A;
item A and item B; item B; item A, item B, and item C; or item B and item C. In some cases, “at least one of item A, item B, and item C” may mean, for example and without limitation, two of item A, one of item B, and ten of item C; four of item B and seven of item C; or some other suitable combination.
[0055] As used herein, the term “about”, unless stated to the contrary, typically refers to +/- 10%, for example +/- 5%, of the designated value.
[0056] It is to be appreciated that certain features that are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features that are, for brevity, described in the context of a single embodiment, may also be provided separately or in any sub combination.
[0057] Throughout the present specification, various aspects and components of the invention can be presented in a range format. The range format is included for convenience and should not be interpreted as an inflexible limitation on the scope of the invention. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range, unless specifically indicated. For example, description of a range such as from 1 to 5 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 5, from 3 to 5 etc., as well as individual and partial numbers within the recited range, for example, 1, 2, 3, 4,
5, 5.5 and 6, unless where integers are required or implicit from context. This applies regardless of the breadth of the disclosed range. Where specific values are required, these will be indicated in the specification.
[0058] Throughout this specification the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.
[0059] Each example of the present disclosure described herein is to be applied mutatis mutandis to each and every other example unless specifically stated otherwise. The present disclosure is not to be limited in scope by the specific examples described herein, which are intended for the purpose of exemplification only. Functionally equivalent products, compositions and methods are clearly within the scope of the disclosure as described herein.
Specific terms
[0060] As used herein, the term “electrode material” refers to a material comprising either anode material, cathode material or a mixture thereof. In the context of the present disclosure, the electrode material is obtained from alkaline batteries, and comprise or consist of a mixed metal material.
[0061] As used herein, the term “cathode material” and “anode material” refers to the active material used to prepare the cathode and anode (i.e. electrodes) of an alkaline
battery, respectively. Reference to active material means the material of the cathode and anode that react with each other during discharge of the alkaline battery, for example as outlined in the half reactions and overall reaction outlined below... Embodiments of the cathode and anode material and other metals are described herein.
[0062] As used herein, the term “mixed metal” includes a compound or mixture comprising at least two metals. By way of example, where the mixed metal material is obtained during the recycling of alkaline batteries, the mixed metal material may comprise one or more metals that are present in alkaline batteries, such as those present in the electrodes, including cathode and anode materials. As an example, the metals in the mixed metal material may comprise manganese and zinc, for example as cathode and anode material. Other non-limiting examples of metals in the mixed metal material can include aluminium, carbon, copper, iron, potassium, sodium, and titanium. The mixed metal material may be a mixed metal dust (MMD) (also referred to as a mixed metal oxide dust and “black mass”). In some embodiments, the MMD may be obtained during the recycling of alkaline batteries. The MMD may be a blend of one or more cathode and anode materials obtained from alkaline batteries along with one or more other metals described herein (e.g. carbon), also referred to herein as alkaline MMD. The mixed metal material may comprise a plurality of particles.
[0063] A reference to “mg/kg” throughout the specification refers to the mass (in milligram) of a substance per kilogram of the total weight of a composition. A reference to w/w” throughout the specification refers to the percentage amount of a substance in a composition on a weight basis.
[0064] As used herein, the term “comminuting” and related terms such as “comminuted”, “comminution” etc. refers to the reduction of a solid material from one average particle size to a smaller average particle size, for example by crushing, grinding or milling.
Process for recovering values from alkaline batteries
[0065] The process described herein can recover one or more values from alkaline batteries, namely materials that make up the cathode and anode of an alkaline battery. An alkaline battery is a type of primary battery which derives its energy from a chemical reaction between manganese oxide (i.e. cathode material) and zinc/zinc oxide (i.e. anode material) via an alkaline electrolyte.
[0066] An alkaline battery comprises a cathode (e.g. positive terminal) and an anode (e.g. negative terminal). The cathode and anode comprise cathode material and anode material, respectively. The cathode material comprises a manganese oxide (e.g. MnCk and/or MmCb), often provided as a compressed paste to form the cathode. Carbon is often added to the cathode material (e.g. in the form of graphite) to increase the conductivity of the cathode, but does not take part in the half-reaction at the cathode or overall reaction on discharge (see below). The anode material comprises a mixture of zinc and zinc oxide (e.g. ZnO). It will be appreciated that the alkaline MMD described herein comprises a mixture of both the cathode material and anode material, and one or more other metal values obtained from alkaline batteries.
[0067] The half-reactions at the anode and cathode comprising the anode material and cathode material, respectively, are:
Zii(s) + 2 OH (aq) ZnO(s) + EhOa) + 2e (anode)
2Mn02(S) + tbO® + 2e - dVhi203(S) + 20H (aq) (cathode)
[0068] Overall, the reaction is:
Zn(S) + 2Mn02(S) ^ ZnO(S> + M Chw
[0069] Alkaline batteries require an electrolyte which is dispersed with the anode material (and in some cases the cathode material). The electrolyte is alkaline and promotes the movement of electrons from the anode to the cathode on discharge. A typical alkaline electrolyte is potassium hydroxide (KOH).
[0070] The cathode material and anode material independently form the reactive components of the cathode (i.e. positive electrode) and the anode (i.e. negative electrode), respectively, of the alkaline battery. The cathode and anode are separated by a separator which is a material located between the cathode and anode to keep the two electrodes apart to prevent electrical short circuits while also allowing the transport of ions therethrough. Examples of separator materials include polymers (e.g. polyolefins such as polyethylene, polypropylene and blends thereof).
[0071] Other materials also present in alkaline batteries include the outer casing and/or auxiliary components, including current collection or connection devices such as brass and aluminium, along with steel and ion conducting separator, typically woven cellulose or a synthetic polymer. Aluminium and/or plastics or cardboard are often used to house/encase alkaline batteries and for other auxiliary functions such as wiring.
[0072] The alkaline batteries may be end of life batteries (e.g. dead/spent or faulty). It will be appreciated that such batteries present little economic value in their current form (e.g. cannot be sold). In light of the numerous materials making up alkaline batteries, there is a need to develop processes to recover a least some of these materials for re-use, recycling and/or commercial sale rather than disposing to landfill.
[0073] In one embodiment, the alkaline batteries have been physically separated to obtain alkaline MMD. The alkaline MMD may be subjected to a comminuting step as described herein.
[0074] In some aspects or embodiments, the present inventors have developed a process in which alkaline MMD obtained from alkaline batteries is subjected to a comminution step as described herein which results in the selective separation and recovery of cathode material and carbon as a separate fraction to the anode material, including for example a concentrated manganese oxide and carbon product. The cathode material and carbon can be separated from the anode material fraction (for example by froth flotation) and in some embodiments can be commercially sold as a carbon enriched manganese oxide product and/or subjected to further processing as a
micronutrient for fertilisers. The anode material fraction can also be commercially sold. Importantly, according to some embodiments or examples described herein, the process described herein does not require smelting, pyrometallurgical processing or acidic leaching to separate and obtain the cathode and anode material.
[0075] In some embodiments, the process for obtaining cathode material and carbon from alkaline MMD obtained from alkaline batteries, comprises the steps of a) comminuting alkaline MMD to reduce the average particle size of the alkaline MMD to liberate and obtain a first particle fraction comprising cathode material and carbon and a second particle fraction comprising anode material.
Comminuting alkaline MMD
[0076] The alkaline MMD may be comminuted to reduce the average particle size of the alkaline MMD particles. The alkaline MMD may be comminuted by any conventional physical processing technique, including for example grinding, crushing, attritioning, shredding and/or milling. Any suitable apparatus capable of comminuting the alkaline MMD can be used, for example a grinding mill (either rod or ball), crusher, agitator (e.g. a high intensity agitator or an agitator tank), all of which are known to the person skilled in the art.
[0077] The comminuting step may be performed in the presence of a liquid (e.g. wet comminution) or may be performed under dry conditions. In one embodiment, the comminuting step comprises dry or wet grinding of the alkaline MMD, for example dry grinding.
[0078] The comminuted alkaline MMD particles (comprising the first and second particle fractions described herein) have an average particle size. The average particle size is taken to be the cross-sectional diameter across a particle. For non-spherical particles, the particle size is taken to be the distance corresponding to the longest cross- section dimension across the particle. It will be appreciated that the average particle size of the comminuted alkaline MMD is smaller than the average particle size of the alkaline MMD prior to the comminution step.
[0079] The comminution step can result in a size reduced alkaline MMD. In one embodiment, the comminution of alkaline MMD can result in 80% of the comminuted alkaline MMD particles (Pso) having a particle size of between about 50 pm to about 500 pm. The comminution of alkaline MMD can result in 80% of the comminuted alkaline MMD particles (Pso) having a particle size of less than about 500, 450, 400, 350. 300, 250, 150, 100 or 50 pm. The comminution of alkaline MMD can result in 80% of the comminuted alkaline MMD particles (Pso) having a particle size of at least about 50, 100, 150, 250, 300, 350, 400, 450 or 500 pm. The comminution of alkaline MMD can result in 80% of the comminuted alkaline MMD particles (Pso) having a particle size in a range provided by any two of these upper and/or lower amounts, for example between about 50 pm to about 500 pm. By comminuting the alkaline MMD particles, one or more advantages may be provided according to at least some embodiments or examples described herein, including increased recovery of carbon into the first particle fraction comprising cathode material.
[0080] The alkaline MMD particles may be comminuted for any period of time effective to obtain one or more of the reduce particle sizes described herein, which may vary depending on the scale of the comminution (e.g. at laboratory scale or industrial scale) as understood by the skilled person when performing comminution. In some embodiments, the comminution of the alkaline MMD is for a period of time of between about 1 minute to 120 minutes. The comminution of the alkaline MMD may be for a period of time (in minutes) of at least about 1, 2, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100 or 120. The comminution of the alkaline MMD may be for a period of time (in minutes) of less than about 120, 100, 90, 80, 70, 60, 50, 40, 30, 20, 15, 10, 5, 2 or 1.
The comminution times can be a range provided by any two of these upper and/or lower times, for example between about 5 minutes to about 30 minutes, or about 5 minutes to about 15 minutes, or 30 minutes to about 60 minutes.
[0081] The comminuted alkaline MMD particles may vary in morphology. The particles may take the form of flakes, fibres, agglomerates, granules, powders, spheres, pulverized materials or the like, as well as combinations thereof. The particles may have any desired shape including, but not limited to, cubic, rod like, polyhedral, spherical or semi- spherical, rounded or semi-rounded, angular, irregular, and so forth.
[0082] The particle morphology and particle size can be measured by any conventional method, including laser diffraction, electron microscopy, dynamic light scattering, optical microscopy or size exclusion methods (such as wet or dry graduated mesh screens or filters).
[0083] The comminution of alkaline MMD liberates and obtains a first particle fraction comprising cathode material and carbon and a second particle fraction comprising anode material. It will be appreciated that the first particle fraction and second particle fraction form part of the overall comminuted alkaline MMD particles described herein.
First particle fraction
[0084] The first particle fraction comprises cathode material and carbon. The cathode material comprises a manganese oxide. The manganese may exist in several oxidation states, including Mn(II) and Mn(III). In some embodiments, the manganese oxide may be manganese (II) oxide (MnCh), manganese (III) oxide (MmCF) or a mixture thereof. It will be appreciated that any reference to manganese oxide, unless otherwise specified, can encompass one or more manganese oxide phases, including those recited above as well as mixtures thereof.
[0085] The carbon may be associated with the manganese oxide (as opposed to discrete particles of carbon dispersed with the manganese oxide). The association may be physical or chemical. In one embodiment, the carbon is physically or chemically associated with the manganese oxide. The carbon may be physically or chemically associated with the manganese oxide as a mixed manganese oxide/carbon material. In one embodiment, the first particle fraction comprises a mixed manganese oxide/carbon material. The mixed manganese oxide/carbon material may be a mixed MnC /MmCF/carbon material. It will be appreciated that the mixed manganese
oxide/carbon material is a compound comprising carbon physically associated with the manganese oxide as opposed to a mixture of discrete manganese oxide separate to carbon.
[0086] The first particle fraction may be concentrated in manganese oxide and carbon. As used herein, the term “concentrated” refers to the enrichment of an element/compound in the particle fraction compared to the alkaline MMD prior to comminution.
[0087] In some embodiments, the first particle fraction has a higher % w/w concentration of manganese (e.g. elemental manganese derived from the manganese oxide present in the first particle fraction) compared to the concentration of manganese in the second particle fraction, based on the total weight of the particle fraction.
[0088] In some embodiments, the first particle fraction has a manganese % distribution of between about 40% to about 95% based on the amount of manganese in the alkaline MMD prior to comminution. The first particle fraction may have a manganese % distribution (based on the amount of manganese in the alkaline MMD prior to comminution) of at least about 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90 or 95. The first particle fraction may have a manganese % distribution (based on the amount of manganese in the alkaline MMD prior to comminution) of less than about 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, or 40. The first particle fraction may have a manganese % distribution in an amount in a range provided by any two of these upper and/or lower amounts, for example between about 80% to about 90% based on the amount of manganese in the alkaline MMD prior to comminution.
[0089] In some embodiments, the first particle fraction has a higher % w/w concentration of carbon (e.g. elemental carbon present in the first particle fraction) compared to the concentration of carbon in the second particle fraction, based on the total weight of the particle fraction.
[0090] In some embodiments, the first particle fraction has a carbon % distribution of between about 40% to about 95% based on the amount of carbon in the alkaline MMD prior to comminution. The first particle fraction may have a carbon % distribution (based on the amount of carbon in the alkaline MMD prior to comminution) of at least about 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95. The first particle fraction may have a carbon % distribution (based on the amount of carbon in the alkaline MMD prior to comminution) of less than about 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, or 40. The first particle fraction may have a carbon % distribution in an amount in a range provided by any two of these upper and/or lower amounts, for example between about 80% to about 90% based on the amount of carbon in the alkaline MMD prior to comminution.
[0091] In some embodiments, the first particle fraction comprises between about 10% w/w to about 60% w/w manganese based on the total weight of the first particle fraction. The first particle fraction may comprise manganese in an amount (as a % w/w based on the total weight of the first particle fraction) of at least about 10, 15, 20, 25,
30, 35, 40, 45, 50, 55 or 60. The first particle fraction may comprise manganese in an
amount (as a % w/w based on the total weight of the first particle fraction) of less than about 60, 55, 50, 45, 40, 35, 30, 25, 20, 15 or 10. The first particle fraction may comprise manganese in an amount in a range provided by any two of these upper and/or lower amounts, for example between about 25% w/w to about 50% w/w, or about 35% w/w to about 45% w/w manganese based on the total weight of the first particle fraction.
[0092] In some embodiments, the first particle fraction comprises between about 1% w/w to about 30% w/w carbon based on the total weight of the first particle fraction. The first particle fraction may comprise carbon in an amount (as a % w/w based on the total weight of the first particle fraction) of at least about 1, 2, 3, 4, 5, 7, 10, 12, 15, 20, 25 or 30. The first particle fraction may comprise carbon in an amount (as a % w/w based on the total weight of the first particle fraction) of less than about 30, 25, 20, 15, 12, 10, 5, 2 or 1. The first particle fraction may comprise carbon in an amount in a range provided by any two of these upper and/or lower amounts, for example between about 5% w/w to about 15% w/w, or about 7% w/w to about 12% w/w carbon based on the total weight of the first particle fraction.
Second particle fraction
[0093] The second particle fraction comprises anode material. The anode material comprises zinc metal and zinc oxide (ZnO), also referred to as zinc/zinc oxide.
[0094] The second particle fraction may be concentrated in zinc/zinc oxide. In some embodiments, the second particle fraction has a higher % w/w concentration of zinc (e.g. elemental zinc derived from the zinc metal and/or zinc oxide) compared to the concentration of zinc in the first particle fraction, based on the total weight of the particle fraction.
[0095] In some embodiments, the second particle fraction has a zinc % distribution of between about 20% to about 60% based on the amount of zinc in the alkaline MMD prior to comminution. The second particle fraction may have a zinc % distribution (based on the amount of zinc in the alkaline MMD prior to comminution) of at least about 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58 or 60. The second particle fraction may have a zinc % distribution (based on the amount of zinc in the alkaline MMD prior to comminution) of less than about 60, 58, 56, 54, 52, 50, 48, 46, 44, 42, 40, 38, 36, 34, 32, 30, 28, 26, 24, 22 or 20. The second particle fraction may have a zinc % distribution in an amount in a range provided by any two of these upper and/or lower amounts, for example between about 30% to about 50% based on the amount of zinc in the alkaline MMD prior to comminution.
[0096] In some embodiments, the second particle fraction has a lower % w/w concentration of carbon compared to the concentration of carbon in the first particle fraction, based on the total weight of the particle fraction.
[0097] In some embodiments, the second particle fraction has a carbon % distribution of between about 1% to about 60% based on the amount of carbon in the alkaline MMD prior to comminution. The second particle fraction may have a carbon %
distribution (based on the amount of carbon in the alkaline MMD prior to comminution) of at least about 1, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 or 60. The second particle fraction may have a carbon % distribution (based on the amount of carbon in the alkaline MMD prior to comminution) of less than about 60, 55, 50, 45,
40, 35, 30, 25, 20, 15, 10, 5, 2, or 1. The second particle fraction may have a carbon % distribution in an amount in a range provided by any two of these upper and/or lower amounts, for example between about 5% to about 15% based on the amount of carbon in the alkaline MMD prior to comminution.
[0098] In some embodiments, the second particle fraction comprises between about 10% w/w to about 60 % w/w zinc based on the total weight of the second particle fraction. The second particle fraction may comprise zinc in an amount (as a % w/w based on the total weight of the second particle fraction) of at least about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 or 60. The second particle fraction may comprise zinc in an amount (as a % w/w based on the total weight of the second particle fraction) of less than about 60, 55, 50, 45, 40, 35, 30, 25, 20, 15 or 10. The second particle fraction may comprise zinc in an amount in a range provided by any two of these upper and/or lower amounts, for example between about 20% w/w to about 60% w/w, or about 25% w/w to about 40% w/w zinc based on the total weight of the second particle fraction.
[0099] The amount of manganese, carbon and/or zinc, and other metals present in the alkaline MMD particles, including the first and second particle fractions may be determined using any suitable elemental compositional analysis technique, including for example one or more head assay analyses, including ashing, fusion, mixed acid digestion, Inductively coupled plasma - optical emission spectrometry (ICP-OES) , Inductively coupled plasma mass spectrometry (ICP-MS), X-ray fluorescence (XRF) or thermal analysis for carbon (such as Leco or CS2000).
[0100] The process may further comprise b) separating the first particle fraction comprising cathode material and carbon from the second particle fraction comprising anode material which are generated by the comminution of the alkaline MMD. The separating of the particle fractions at step b) may comprise a size screening or froth flotation of the comminuted alkaline MMD particles.
[0101] The comminuted alkaline MMD particles may be size screened to separate the first particle fraction. The first particle fraction may be separated from the comminuted alkaline MMD particles via size-screening between about 30 pm to about 200 pm. The first particle fraction may be separated from the comminuted alkaline MMD particles via size screening below about 200, 180, 160, 140, 120, 100, 90, 80, 75, 70, 65, 60, 55, 40, 35 or 30 pm. Combination of these values can provide a range selection, for example between about 50 pm to about 100 pm.
Froth flotation separation
[0102] In one embodiment, the separating of the particle fractions described herein comprise froth flotation of the alkaline MMD particles.
[0103] Froth flotation involves the separation of the particle fractions based on their surface properties, namely their hydrophobic or hydrophilic properties. Generally speaking, hydrophilic surfaces will tend to associate with water (or another suitable aqueous phase) while hydrophobic surfaces will associate with a non-aqueous phase, for example air bubbles. Froth flotation separation exploits these surface properties to separate materials.
[0104] Froth flotation processes are performed in a suitable froth flotation vessel (also called a cell or tank). The froth flotation vessel may be rectangular or cylindrical mechanically or naturally aerated vessels, flotation columns or cells. One or more froth flotation vessels/cells may be used, for example arranged in a series of cascading vessels/cells.
[0105] Separation of the particle fractions is achieved as air bubbles float to the surface of the froth flotation vessel carrying away the hydrophobic cathode material and carbon while the anode material remains suspended in the aqueous solution. The particles that attach to the air bubbles and float to the surface of the vessel forming a froth are referred to as the flotation concentrate. Often, the flotation concentrate comprises particles that are more hydrophobic compared to the particles which have reported to the flotation tail, which are generally more hydrophilic.
[0106] When an aqueous slurry of alkaline MMD particles in the froth flotation vessel are aerated with bubbles, the hydrophobic particles attach to at least some of the air bubbles and floats to the top of the froth flotation vessel to report to a flotation concentrate, and the hydrophilic particles remains in the slurry to report to a flotation tail.
[0107] In one embodiment, the separating of the particle fractions at step b) comprises performing a froth flotation separation on the comminuted alkaline MMD particles in a froth flotation vessel. In one embodiment, the first particle fraction comprising cathode material and carbon reports to a flotation concentrate, and second particle fraction comprising anode material reports to a flotation tail. In one embodiment, the process further comprises removing the flotation concentrate from the froth flotation vessel to separate and obtain the first particle fraction comprising cathode material and carbon.
[0108] In one embodiment, the froth flotation separation comprises: bl) suspending the comminuted alkaline MMD particles in an aqueous solution comprising one or more froth flotation agents in the froth flotation vessel to create a slurry; t>2) aerating the slurry to generate air bubbles which float to the surface of the slurry to from a froth, wherein the first particle fraction comprising cathode material and carbon attaches to at least some of the air bubbles and floats to the top of the froth flotation vessel to report to the flotation concentrate, and the second particle fraction comprising anode material remains in the slurry to report to the flotation tail.
[0109] According to some embodiments or examples, the froth flotation processes described herein exploits carbons inherent hydrophobic properties to preferentially float manganese oxide (i.e. cathode material) separate to the zinc/zinc oxide (i.e. anode material), as opposed to recovering carbon as a separate material to the electrode
material. By carefully controlling the comminution of alkaline MMD particles, along with liberating particle fractions comprising the anode and cathode material, carbon remains physically or chemically associated with the manganese oxide. Owing to carbons inherent hydrophobicity, it attaches to the air bubbles and carries with it the cathode material to the surface thus greatly assisting in separation of the cathode material from the anode material which remains in the flotation tail. In some embodiments, a prolonged comminution of the alkaline MMD particles destroyed the manganese oxide and carbon association, thus allowing some of the liberated cathode material to migrate to the flotation tail along with the anode material owing to manganese oxide being inherently hydrophilic, thus reducing recovery of manganese in the flotation concentrate. Accordingly, in some embodiments or examples, the inventors have surprisingly identified that comminuting the alkaline MMD to a reduced particle size (for example to between about 50 pm to about 300 pm) increases the recovery of manganese oxide and carbon in the floatation concentrate separate to the anode material of zinc/zinc oxide. One or more downstream advantages of this effective separation are described herein.
[0110] The flotation concentrate may comprise the first particle fraction as described herein. It will be appreciated that the manganese and carbon % distribution and % w/w concentration of the first particle fraction as described herein equally apply to the manganese and carbon % distribution and % w/w concentration of the flotation concentrate. In some embodiments, owing to the presence of the first particle fraction, the flotation concentrate is concentrated in manganese oxide and/or carbon. In some embodiments, the flotation concentrate has a higher % w/w concentration of manganese and/or carbon compared to the concentration of manganese and/or carbon in the flotation tail, based on the total weight of the reported particles. In some embodiments, the flotation concentrate may have a higher % w/w concentration of carbon compared to the concentration of carbon in the flotation tail, based on the total weight of the reported particles.
[0111] The particles that do not attach to the air bubbles and float to the surface of the vessel are referred to as the flotation tail. Often, the flotation tail comprises particles that are more hydrophilic compared to the particles which have reported to the flotation concentrate, which are generally more hydrophobic. The particles of the flotation tail may be subjected to further processing (i.e. attritioning) and further froth flotation steps to recover hydrophobic particles (e.g. cathode material and carbon) that did not initially float. This process is known as scavenging. In one embodiment, the process further comprises one or more additional froth flotation separation steps to recover cathode material and carbon from the flotation tail.
[0112] The flotation tail may comprise the second particle fraction as described herein. It will be appreciated that the zinc and carbon % distribution and % w/w concentration of the second particle fraction as described herein equally apply to the zinc and carbon % distribution and % w/w concentration of the flotation tail. In some embodiments, owing to the presence of the second particle fraction, the flotation tail is concentrated in zinc/zinc oxide. In some embodiments, the flotation tail has a higher % w/w concentration of zinc compared to the concentration of zinc in the flotation
concentrate, based on the total weight of the reported particles. In some embodiments, the flotation tail has a lower % w/w concentration of carbon compared to the concentration of carbon in the particles of the flotation concentrate, based on the total weight of the reported particles.
[0113] Occasionally, the alkaline MMD may comprise one or more heavy metals because of other battery types (e.g. lithium-ion, lead batteries etc.) misreporting to the alkaline battery feed which is then physically separated to obtain the alkaline MMD. The present inventors have surprisingly identified that, according to some embodiments or examples described herein, one or more heavy metals present in the comminuted alkaline MMD particles preferentially report to the flotation tail as part of the second particle fraction (i.e. with the anode material). The one or more heavy metals include for example lead (Pb), arsenic (As), cadmium (Cd), and mercury (Hg).
[0114] In some embodiments, the flotation tail has a higher ppm concentration of heavy metal (e.g. Cd, Pb etc.) compared to the concentration of heavy metal in the flotation concentrate, based on the total weight of the reported particles.
[0115] The flotation tail may comprise one or more heavy metals in an amount of between about 100 ppm to about 500 ppm based on the total weight of the reported particles. The flotation tail may have a heavy metal concentration (as ppm based on the total weight of the reported particles) of at least about 100, 120, 140, 160, 180, 200, 220, 240, 260, 280, 300, 320, 340, 360, 380, 400, 420, 440, 460, 480 or 500. The flotation tail may have a heavy metal concentration in an amount in a range provided by any two of these amounts, for example between about 100 ppm to about 300 ppm, based on the total weight of the reported particles.
[0116] The flotation concentrate may comprise one or more heavy metals in an amount of between about 1 ppm to about 200 ppm based on the total weight of the reported particles. The flotation concentrate may have a heavy metal concentration (as ppm based on the total weight of the reported particles) of less than about 200, 150,
100, 80, 70, 60, 50, 40, 30, 20, 10, 5, or 1. The flotation concentrate may have a heavy metal concentration in an amount in a range provided by any two of these amounts, for example between about 50 ppm to about 100 ppm, based on the total weight of the reported particles.
[0117] By preferentially reporting any heavy metal present in the alkaline MMD to the flotation tail with the anode material, in some embodiments, the cathode material enriched with carbon can be readily processed into a fertiliser with higher % manganese and carbon content.
[0118] The froth flotation separation comprises suspending the comminuted alkaline MMD particles in an aqueous solution, optionally comprising one or more froth flotation agents in the froth flotation vessel to create a slurry. Froth flotation agents comprise one or more materials that are suitable to manipulate the hydrophobic and/or hydrophilic properties of the suspended comminuted alkaline MMD particles to facilitate separation and/or assist in froth generation. The aqueous slurry and optional froth flotation agents may also be referred to as a “pulp”.
[0119] Any froth flotation agent that facilitates in the separation of the particle fractions by rendering the surfaces thereof more hydrophobic and/or more hydrophilic relative to each other so that the hydrophobic material attaches to air bubbles and floats to report to the flotation concentrate while the hydrophilic particles remain in the aqueous solution and report to the flotation tail can be used. In some embodiments, the one or more froth flotation agents is selected from the group consisting of a frother, collector and/or depressant. For example, a collector may be added to the aqueous solution comprising suspended alkaline MMD particles, which physically or chemically absorbs to the first particle fraction to increase the hydrophobicity of the particles and promote attachment to the air bubbles generated. Alternatively or additionally a depressant may be added, which physically or chemically absorbs to the second particle fraction to increase the hydrophilicity of the particles.
[0120] In one embodiment, the aqueous solution comprising suspended comminuted alkaline MMD particles also comprises a frother and a collector, and optionally a depressant.
[0121] In one embodiment the frother is an alcohol. In one embodiment, the frother is an alcohol selected from the group consisting of methyl isobutyl carbinol (MIBC), 2- ethyl hexanol, isoamyl alcohol, cyclohexanol, a-terpinol, cresol, xylenol, glycol ether, and a combination thereof. In one embodiment, the frother is methyl isobutyl carbinol (MIBC). The frother may be added in an amount effective to assist in stabilising the froth formed by the air bubbles at the surface of the slurry, as known to the skilled person.
[0122] A collector may be added to enhance the hydrophobicity of the first particle fraction comprising carbon and cathode material. Suitable collectors include a hydrocarbon oil (e.g. kerosene), fatty acids (e.g. oleic acid) and hydroximates (e.g. hydroxamic acid). In one embodiment, the collector is a hydrocarbon oil. In one embodiment, the hydrocarbon oil is kerosene.
[0123] The collector may be added in an amount effective to manipulate the surface of the first particle to be more hydrophobic, thereby promoting attachment to the air bubbles during aeration. In some embodiment, the collector is provided in an amount of between about 100 g/t to about 8000 g/t. The collector may be provided in an amount (in g/t) of at least about 100, 200, 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000,
4500, 5000, 5500, 6000, 6500, 7000, 7500 or 8000. The collector may be provided in an amount (in g/t) of less than about 8000, 7500, 7000, 6500, 6000, 5500, 5000, 4500, 4000, 3500, 3000, 2500, 2000, 1500, 1000, 500, 200 or 100. The collector may be provided in an amount in a range provided by any two of these upper and/or lower amounts, for example between about 500 g/t to about 2000 g/t.
[0124] In some embodiments, owing to the carbon present in the first particle fraction, little or no collector is required to manipulate the hydrophobic properties of the first particle fraction owing to the inherent hydrophobic nature of the carbon. However, it will be appreciated that any addition of a collector may be advantageous to further enhance the inherent hydrophobicity of the first particle fraction comprising
carbon and cathode material to facilitate separation from the anode material via froth flotation.
[0125] The aqueous slurry comprising comminuted alkaline MMD particles, and optionally one or more froth flotation agents, is then aerated (i.e. sparged with air) to generate air bubbles. In the froth flotation vessel, hydrophobic particles attach to at least some of the air bubbles and float to the top of the froth flotation vessel to form a froth for removal versus the hydrophilic particles which remain in the aqueous slurry.
In this way, particles having different surface properties (e.g. hydrophobic vs hydrophilic) are separated from one and other.
[0126] The aqueous slurry may be aerated at flow rate effective to generate sufficient air bubbles and froth to separate the particle fraction. The flow rate may be at a rate suitable for industrial scale separation, as understood by the person skilled in the art.
[0127] The aqueous slurry may be aerated for a period of time effective to generate sufficient air bubbles and froth to separate the particle fraction. In some embodiments, the aeration of the aqueous slurry may be for a period of time of between 10 minutes to about 24 hours. The aeration of the aqueous slurry may be for a period of time of at least 1, 5, 10, 15, 20, 30, 45 (minutes), 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 18, or 24 hours. The aeration of the aqueous slurry may be for a period of time of less than 24,
18, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1.5, 1 (hours), 45, 30, 20, 15, 10, 5 or 1 (minutes). The aeration times may be provided by any two of these upper and/or lower amounts.
[0128] The pH of the aqueous slurry may be any suitable pH. In one embodiment, the pH of the aqueous slurry is the slurry’s natural pH (i.e. the pH of the slurry once the comminuted alkaline MMD particles and optional froth flotation agents are added). In some embodiments, the pH of the aqueous slurry is between about 8 to about 14, for example between about 10 to about 13.
[0129] In some embodiments, the aqueous slurry comprising the comminuted alkaline MMD particles is conditioned prior to froth flotation to clean or activate the particles prior to aeration. Such conditioning may enhance the particles inherent hydrophobic/hydrophilic properties and facilitate in separation of the cathode and anode material.
[0130] The flotation concentrate and/or tail can be removed from the flotation vessel by any conventional means to separate and obtain the first particle fraction of cathode material and carbon. For example, the flotation concentrate can be removed by skimming off the froth using a mechanical propeller located at the slurry surface. The flotation tail can be removed via a suitable outlet valve or pump located below the surface of the slurry.
[0131] In some embodiments, the flotation tail comprising the second particle fraction is removed from the froth flotation vessel and undergoes gravity separation to recover any manganese and carbon entrained within the second particle fraction following froth flotation separation. The manganese and carbon recovered from gravity separation can be recycled into the froth flotation vessel or combined with the flotation concentrate.
[0132] In some embodiments, the comminuted alkaline MMD particles undergoes gravity separation to recover a light fraction comprising cathode material and carbon and a heavy fraction comprising anode material, wherein the light fraction comprising cathode material and carbon undergoes froth flotation separation.
Alkaline mixed metal dust (MMD)
[0133] The alkaline MMD may be obtained from alkaline batteries by any physical separation means, including for example conventional break operations to mechanically comminute the alkaline battery.
[0134] The alkaline MMD may comprise one or more particulates (e.g. particles). The particles may take the form of flakes, fibres, agglomerates, granules, powders, spheres, pulverized materials or the like, as well as combinations thereof. The particles may have any desired shape including, but not hmited to, cubic, rod hke, polyhedral, spherical or semi- spherical, rounded or semi-rounded, angular, irregular, and so forth.
[0135] The alkaline MMD may have an average particle size wherein 80% of the alkaline MMD particles (Pso) having a particle size of between about 500 pm to about 5000 pm for example about 1000 pm to 3000 pm.
[0136] The alkaline MMD particle morphology and particle size can be measured by any conventional method, including laser diffraction, electron microscopy, dynamic light scattering, optical microscopy or size exclusion methods (such as wet or dry graduated mesh screens or filters).
[0137] The alkaline MMD comprises cathode material, anode material and carbon.
[0138] In some embodiments, the alkaline MMD comprises between about 5% w/w to about 50% w/w manganese based on the total weight of the alkaline MMD. The alkaline MMD may comprise manganese in an amount (as a % w/w based on the total weight of alkaline MMD) of at least about 5, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28,
30, 32, 34, 36, 38, 40, 42, 44, 46, 48 or 50. The alkaline MMD may comprise manganese in an amount (as a % w/w based on the total weight of alkaline MMD) of less than about 50, 48, 46, 44, 42, 40, 38, 36, 34, 32, 30, 28, 26, 24, 22, 20, 18, 16, 14, 12, 10, 8 or 5. The alkaline MMD may comprise manganese in an amount in a range provided by any two of these upper and/or lower amounts, for example between about 10% w/w to about 40% w/w based on the total weight of alkaline MMD.
[0139] In some embodiments, the alkaline MMD comprises between about 5% w/w to about 50% w/w zinc based on the total weight of the alkaline MMD. The alkaline MMD may comprise zinc in an amount (as a % w/w based on the total weight of alkaline MMD) of at least about 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36,
38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58 or 60. The alkaline MMD may comprise zinc in an amount (as a % w/w based on the total weight of alkaline MMD) of less than about 60, 58, 54, 52, 50, 48, 46, 44, 42, 40, 38, 36, 34, 32, 30, 28, 26, 24, 22, 20, 18,
16, 14, 12, or 10. The alkaline MMD may comprise zinc in an amount in a range
provided by any two of these upper and/or lower amounts, for example between about 20% w/w to about 50% w/w based on the total weight of alkaline MMD.
[0140] In some embodiments, the alkaline MMD comprises between about 0.1% w/w to about 20% w/w carbon based on the total weight of the alkaline MMD. The alkaline MMD may comprise carbon in an amount (as a % w/w based on the total weight of alkaline MMD) of at least about 0.1, 0.2, 0.5, 1, 2, 4, 6, 8, 10, 12, 14, 16, 18 or 20. The alkaline MMD may comprise carbon in an amount (as a % w/w based on the total weight of alkaline MMD) of less than about 20, 18, 16, 14, 12, 10, 8, 6, 4, 2, 1, 0.5, 0.2 or 0.1. The alkaline MMD may comprise carbon in an amount in a range provided by any two of these upper and/or lower amounts, for example between about 1% w/w to about 10% w/w based on the total weight of alkaline MMD.
[0141] The alkaline MMD may comprise one or more additional metal values other than manganese, carbon or zinc (e.g. impurities). If present, the type and amount of impurity in the first particle fraction may depend on the alkaline battery feed used to obtain the MMD. Typical impurities present in the mixed in alkaline MMD may include aluminium (Al), arsenic (As), cadmium (Cd), copper (Cu), iron (Fe), potassium (K), sodium (Na) and titanium (Ti). In some embodiments, one or more additional metal values other than manganese, carbon or zinc (e.g. impurities), including one or more of those metals recited above, may be present in the alkaline MMD in an amount of less than about 100000, 10000, 5000, 4000, 3000, 2000, 1000, 800, 600, 400, 200, 100, 50, or 10 ppm based on the total weight of the alkaline MMD.
[0142] In some embodiments, the alkaline MMD is provided by the steps: al) physically separating alkaline batteries to obtain coarser particles comprising steel and/or ferrous material and finer particles comprising alkaline MMD; and a2) separating the coarser particles comprising steel and/or ferrous material from the finer particles comprising alkaline MMD.
[0143] The alkaline batteries may be physically separated using manual methods or conventional physical separation device/s such as a crusher, hammer mill or shredder. The physical separation may be performed in the presence of a liquid (e.g. wet shredding) or may be performed under dry conditions (e.g. dry- shredding).
[0144] The weight split of the finer particles comprising alkaline MMD may be between about 30% to about 80% w/w based on the total weight of the alkaline battery. The weight split of the finer particles of the alkaline MMD (in % w/w based on the total weight of the alkaline battery) may be at least about 30, 35, 40, 45, 50, 55, 60, 65, 70, 75 or 80. The weight split of the finer particles of the alkaline MMD (in % w/w based on the total weight of the alkaline battery) may be less than about 80, 75, 70, 65, 60, 55, 50, 45, 40, 35 or 30. The weight split of the finer particles comprising alkaline MMD may be in a range provided by any two of these upper and/or lower amounts, for example between about 40% w/w to about 70% w/w based on the total weight of alkaline battery.
[0145] The weight split of the coarser particles comprising steel and/or ferrous material may be between about 10% to about 50% w/w based on the total weight of the
alkaline battery. The weight split of the coarser particles comprising steel and/or ferrous material (in % w/w based on the total weight of the alkaline battery) may be at least about 10, 15, 20, 25, 30, 35, 40, 45 or 50. The weight split of the coarser particles comprising steel and/or ferrous material (in % w/w based on the total weight of the alkaline battery) may be less than about 50, 45, 40, 35, 30, 25, 20, 15 or 10. The weight split of the coarser particles comprising steel and/or ferrous material may be in a range provided by any two of these upper and/or lower amounts, for example between about 10% w/w to about 40% w/w based on the total weight of alkaline battery.
[0146] In some embodiments, step a2) further comprises screening the separated alkaline battery particles at between about 4 mm to about 6 mm to separate the coarser particles comprising steel and/or ferrous material from the finer particle of alkaline MMD, for example at about 5 mm. Alternatively, step a2) may further comprise subjecting the separated alkaline battery particles to magnetic separation to separate the coarser particles comprising steel and/or ferrous material from the finer particles comprising alkaline MMD.
[0147] In some embodiments, the physical separation of the alkaline batteries at step al) produces a dust and/or fume comprising electrolyte, wherein the dust and/or fume is optionally treated to recover the electrolyte.
[0148] In some embodiments, the separated alkaline battery particles comprising coarser particles comprising steel and/or ferrous material and finer particles comprising alkaline MMD are washed and/or attritioned prior to step a2).
[0149] In some embodiments, the separated coarser particles comprising steel and/or ferrous material is subjected to crushing to liberate and obtain alkaline MMD trapped within the coarser particles. The liberated alkaline MMD may be combined with the finer particles comprising alkaline MMD.
Fertilisers
[0150] The separated first particle fraction comprising cathode material and carbon can be used as a micronutrient in fertilisers. In one embodiment, the process further comprises mixing the separated first particle fraction comprising cathode material and carbon at step b) with a phosphorous source and optionally a binder to prepare a fertiliser.
[0151] In another aspect, the comminuted alkaline MMD particles described herein can be used as a micronutrient for fertilisers. In one embodiment, the process further comprises mixing comminuted alkaline MMD particles with a phosphorous source and optionally a binder to prepare a fertiliser. The fertiliser may be enriched in manganese and/or carbon.
[0152] The fertiliser has a manganese concentration owing to the presence of manganese from the cathode material in the first particle fraction/comminuted particles. The fertiliser may have a manganese concentration (in mg/kg of fertiliser) of between about 1000 to about 20000. The fertiliser may have a manganese concentration (in
mg/kg of fertiliser) of at least about 1000, 2000, 5000, 7000, 10000, 12000, 15000, 17000 or 20000. The fertiliser may have a manganese concentration (in mg/kg based on the total weight of fertiliser) of less than about 20000, 17000, 12000, 10000, 7000,
5000, 2000 or 1000. The fertiliser may have a manganese concentration in an amount in a range provided by any two of these amounts, for example between about 1000 mg/kg to about 20000 mg/kg based on the total weight of fertiliser.
[0153] The fertiliser has a carbon concentration owing to the presence of carbon in the first particle fraction/comminuted particles.
[0154] Any suitable phosphorous source may be used to prepare the fertiliser. In some embodiments, the phosphorous source is a calcium phosphate salt or an ammonium phosphate salt, or a combination thereof. In one embodiment, the calcium phosphate salt is monocalcium phosphate (Super Phosphate). In one embodiment, the ammonium phosphate salt is monoammonium phosphate (MAP) or diammonium phosphate (DAP), or a combination thereof.
[0155] Any suitable binder may be used to bind, in one embodiment, the binder is phosphoric acid or formic acid, or a combination thereof.
[0156] The fertiliser may be prepared using conventional blending/mixing techniques known to the person skilled in the art.
[0157] In some embodiments, the amount of phosphorous source and optional binder to be mixed with the separated first particle fraction comprising cathode material and carbon or comminuted alkaline MMD particles is sufficient to provide a fertiliser with a manganese concentration of about 1 % w/w based on the total weight of the fertiliser.
[0158] In some embodiments, the amount of heavy metals (if present in the separated first particle fraction comprising cathode material and carbon comminuted alkaline MMD particles) in the final fertiliser needs to be controlled. In some embodiments, the amount of phosphorous source and optional binder to be mixed with the separated first particle fraction comprising cathode material and carbon or the comminuted alkaline MMD particles is sufficient to provide a fertiliser with a heavy metal concentration of less than 1000, 800, 600, 400, 200, 100, 50, 10, 5, or 1 ppm based on the total weight of the fertiliser. For example, in some embodiments, the fertiliser may comprise 10 ppm or less of cadmium and/or 100 ppm or less of lead.
[0159] According to some embodiments, the preferential reporting of any heavy metal present in the alkaline MMD to the flotation tail with the anode material allows for the cathode material enriched with carbon to be recovered from the flotation concentrate and readily processed into a fertiliser having low amounts of heavy metal impurity. Additionally, a more enriched manganese fertiliser can be obtained owing to reduced ppm levels of heavy metal reporting to the flotation concentrate.
[0160] In one embodiment, there is provided a fertiliser comprising comminuted alkaline MMD particles obtained from alkaline batteries, a phosphorous source, and optionally a binder. In one embodiment, there is provided a fertiliser comprising
separated cathode material and carbon obtained from alkaline batteries, a phosphorous source, and optionally a binder.
Electrode materials and batteries
[0161] The separated first particle cathode material and carbon and/or anode material can be recycled for use as electrode materials for alkaline batteries. In some embodiments, the separated first particle fraction comprising cathode material and carbon and/or separated second particle fraction comprising anode material is processed into one or more electrodes for alkaline batteries.
[0162] In some embodiments, the process further comprises using the separated cathode material and carbon and/or anode material obtained by the process described herein as one or more electrodes for making an alkaline battery. In some embodiments, the process further comprises assembling an alkaline battery comprising one or more electrodes prepared using the separated first particle fraction comprising cathode material and carbon and/or separated second particle fraction comprising anode material. In one embodiment, there is provided an alkaline battery comprising one or more electrodes prepared using the separated cathode material and carbon and/or anode material obtained by the processes described herein.
[0163] In another embodiment, there is provided use of the separated first particle fraction comprising cathode material and carbon and/or anode material obtained by the processes described herein, as an electrode material (e.g. cathode and/or anode) for preparing one or more electrodes for alkaline batteries.
[0164] The present application claims priority from Australian Provisional Patent Application No. 2021902192 filed on 16 July 2021, the entire contents of which are incorporated herein by reference.
EXAMPLES
[0165] In order that the disclosure may be more clearly understood, particular embodiments of the invention are described in further detail below by reference to the following non-limiting experimental materials, methodologies and examples.
Example 1: Embodiment of process for recovering cathode material and carbon from alkaline batteries using physical separation
[0166] Referring to Figure 1, sorted end of life alkaline batteries (100) are physically separated, using a suitable device, using manual methods or conventional physical separation device/s such as a crusher, hammer mill or shredder (110). Coarser particles comprising steel and/or ferrous material (111) are recovered by simple size separation at 500 pm or magnetic separation, to recover a steel/ferrous product (200). Finer particles comprising alkaline MMD comprising cathode material and carbon (113) and anode material (112) are also generated which in some embodiments are comminuted (not shown). Optionally coarse material from the size separation stage can be recycled to the physical separation stage, for further size reduction (not shown).
[0167] Table 1 shows typical mass recovered to the steel or ferrous product (200).
Table 1: Mass split of steel and/or ferrous product (200) and alkaline MMD (112) via the process described herein.
[0168] The anode material (112) and cathode material and carbon (113) are separated into separate fractions, in this example by size separation at 75 pm to create a separated second particle fraction comprising anode material (300) and a first particle fraction comprising cathode material and carbon (400).
[0169] Table 2 shows typical mass recovered and analysis of the separate anode material (300) and cathode material and carbon (400) fractions.
Table 2: Composition of material separated and recovered via the simple physical separation process described in Figure 1.
[0170] Referring to Figure 2, dust and fume (114) from physical alkaline battery separation (110), are recovered and treated (120), using conventional off gas treatment equipment such as bag filters/houses and wet gas/fume scrubbers, for example venturi or packed tower (120). Dust recovered is returned to the physical separation stage (110) and electrolyte material recovered (500) from the wet gas/fume scrubber.
Example 2: Embodiment of process for recovering values from alkaline batteries using froth flotation separation
[0171] Referring to Figure 3, end of life alkaline batteries are physically separated (120), using a suitable device, using a manual methods or a conventional physical separation device/s such as a crusher, hammer mill or shredder.
[0172] Crushed or shredded end of life alkaline batteries (121) are subject to size based classification or magnetic separation methods (130) to recover coarser particles steel or ferrous material (131) and generate a steel and/or ferrous product (200). Mass recovery to the steel and/or ferrous product is as detailed in Table 1. Optionally coarse
material (133) from the size separation stage can be recycled to the physical separation stage (120), for further size reduction.
[0173] Finer particles comprising alkaline MMD, low in steel and/or ferrous material (132) undergoes froth flotation (150). In some embodiments, the alkaline MMD is comminuted prior to froth flotation separation (not shown). Anode concentrated material (151) reports preferentially to the flotation tail and is recovered as an anode material product (300). Cathode material and carbon (152) preferentially float and report to the froth fraction and is recovered as a cathode material and carbon flotation concentrate product (400).
[0174] Froth flotation can be completed with flotation reagent such as depressants, collectors and frothers using equipment (cells) specifically designed for introduction of air to promote bubble formation and recover hydrophobic particles.
[0175] Table 3 shows the impact of froth flotation (150) on the separation of cathode material and carbon (152) from anode material (151). Cathode material and carbon product (400) is recovered in the flotation concentrate from the froth flotation stage.
Example 3: Embodiment of process for recovering values from alkaline batteries using gravity separation
[0176] Referring to Figure 4, end of life alkaline batteries are physically separated (120), using a suitable device, using manual methods or a conventional physical separation device/s such as a crusher, hammer mill or shredder.
[0177] Crushed or shredded end of life alkaline batteries (121) are subject to size based classification or magnetic separation methods (130) to recover coarser particles comprising steel and/or ferrous material (131) and generate a steel and/or ferrous product (200). Mass recovery to the steel and/or ferrous product is as detailed in Table 1.
[0178] Finer particles comprising alkaline MMD, low in steel and/or ferrous material (132) undergoes gravity separation (160). In some embodiments, the alkaline MMD
may be comminuted prior to gravity separation (not shown). Anode concentrated material (161) reports preferentially to the heavy gravity fraction and is recovered as an anode material product (300). Concentrated cathode material and carbon (162) reports preferentially to the light gravity separation fraction and is recovered as a cathode material and carbon product (400).
[0179] Gravity separation is often completed in separate stages as fine and coarse fractions and using devices such as, jigs, spirals, tables, high gravity concentrators or hydraulic / up flow classifiers.
Table 4: Composition of material separated and recovered via the gravity separation process described in Figure 4.
Example 4: Embodiment of process for recovering values from alkaline batteries using comminution and froth flotation
[0180] Referring to Figure 5, end of life alkahne batteries are physically separated (120), using a suitable device, using a manual methods or a conventional physical separation device/s such as a crusher, hammer mill or shredder.
[0181] Crushed or shredded end of life alkahne batteries (121) are subject to size based classification or magnetic separation methods (130) to recover coarser particles comprising steel and/or ferrous material (131) and generate a steel and/or ferrous product (200). Mass recovery to the steel and/or ferrous product is as detailed in Table 1. Optionally coarse material (133) from the size separation stage can be recycled to the physical separation stage (120), for further size reduction.
[0182] Finer particles comprising alkahne MMD, low in steel and/or ferrous material (132) undergoes a comminution step (140) to reduce the average particle size using devices such as grinding mill (either rod or ball) or mixing or attritioning, using an agitated tank, attritioner or high intensity agitator. Optionally additional steel and/or ferrous material can be recovered (141) from the comminution stage (140). This material can be combined into the steel and/or ferrous product (200).
[0183] Comminuted alkahne MMD particles (142) undergoes froth flotation (150). Anode concentrated material (151) report preferentially to the flotation tails fraction and is recovered as an anode material product (300). Cathode material and carbon (152) report preferentially to the froth fraction and is recovered as a cathode material and carbon flotation concentrate product (400).
[0184] It is understood that froth flotation is completed with flotation agents such as depressants, collectors and frothers in using equipment (cells) specifically designed for introduction of air to promote bubble formation and recovery hydrophobic particles.
[0185] Table 5 shows the impact of grinding (140) on froth flotation (150) performance for separating cathode material and carbon (152) from anode material (151), present in the end of life alkaline batteries. Advantageously, a grind time of two minutes of the electrode material (132), leads to an improved liberation of cathode material and carbon. Further size reduction surprisingly leads to lower manganese grades in the cathode material product (400) due to disassociation of the carbon from the manganese oxide.
Table 5: Composition of material separated and recovered via the froth flotation process described in Figure 5 at varying grind times.
Example 5: Embodiment of process for recovering values from alkaline batteries using combination of froth flotation and gravity separation
[0186] Referring to Figure 6, end of life alkaline batteries are physically separated (120), using a suitable device, using a manual methods or a conventional physical separation device/s such as a crusher, hammer mill or shredder.
[0187] Crushed or shredded end of life alkaline batteries (121) are subject to size based classification or magnetic separation methods (130) to recover coarser particles comprising steel and/or ferrous material (131) and generate a steel and/or ferrous product (200). Mass recovery to the steel and/or ferrous product is as detailed in Table 1. Optionally coarse material (133) from the size separation stage can be recycled to the physical separation stage (120), for further size reduction.
[0188] Finer particles comprising alkaline MMD, low in steel and/or ferrous (132) undergoes a comminution step (140) to reduce the average particle size using devices such as grinding mill (either rod or ball) or mixing or attritioning, using an agitated tank, attritioner or high intensity agitator. Optionally additional steel and/or ferrous material can be recovered (141) from the comminution stage (140). This material can be combined into the steel and/or ferrous product (200).
[0189] Comminuted alkaline MMD particles (142) undergoes froth flotation (150). Cathode material and carbon (154) floats preferentially and reports to the froth fraction and is recovered as a cathode material and carbon flotation concentrate product (400).
[0190] Anode concentrated material (153) reports preferentially to the flotation tail is recovered, and undergoes gravity separation (160). Anode concentrated material (162) report preferentially to the heavy gravity fraction and is recovered as an anode material product (300). Any cathode material and carbon recovered as a light gravity fraction (163) and is recycled to the froth flotation stage (150) for reprocessing or optionally added directly the cathode material and carbon product (400).
[0191] Table 6 shows the impact of grinding (140), froth flotation (150) and gravity separation (160) on the separation of cathode material and carbon (154) from anode material (162).
Table 6: Composition of material separated and recovered via the combine froth flotation and gravity separation process described in Figure 6.
Example 6: Embodiment of process for recovering values from alkaline batteries using combination of gravity separation and froth flotation
[0192] Figure 7 demonstrates an alternative embodiment using combination of froth flotation and gravity where end of life alkaline batteries are physically separated (120), using a suitable device, using a manual methods or a conventional physical separation device/s such as a crusher, hammer mill or shredder
[0193] Crushed or shredded end of life alkaline batteries (121) are subject to size based classification or magnetic separation methods (130) to recover coarser particles comprising steel and/or ferrous material (131) and generate a steel and/or ferrous product (200). Mass recovery to the steel and/or ferrous product is as detailed in Table 1. Optionally coarse material (133) from the size separation stage can be recycled to the physical separation stage (120), for further size reduction.
[0194] Finer particles comprising alkaline MMD, low in steel and/or ferrous (132) undergoes a comminution step (140) to reduce the average particle size using devices such as grinding mill (either rod or ball) or mixing or attritioning, using an agitated tank, attritioner or high intensity agitator. Optionally additional steel and/or ferrous material can be recovered (141) from the comminution stage (140). This material can be combined into the steel and/or ferrous product (200).
[0195] Comminuted alkaline MMD particles (142) low in steel and/or ferrous material (132) undergoes gravity separation (160). Anode concentrated material (165) reports preferentially to the heavy gravity fraction and is recovered as an anode material product (300). Concentrated cathode material and carbon (162) reports preferentially to the light gravity separation fraction and is recovered as a cathode material and carbon product (400).
[0196] The light gravity separation fraction optionally undergoes froth flotation (150). Cathode material and carbon (155) floats preferentially and reports to the froth fraction and is recovered as a cathode material and carbon flotation concentrate product (400).
[0197] Anode concentrated material (156) reports preferentially to the flotation tail is recovered and is recycled to the gravity separation stage (160) for reprocessing or optionally added directly the heavy gravity fraction and is recovered as an anode material product (300).
Example 7: Use of separated cathode material and carbon as micronutrients for fertilisers
[0198] Referring to Figure 8 cathode material and carbon (400) is combined with a fertiliser (i.e. a phosphorous source) (500) and a binder (600) and blended (210). Blending can occur in a rotary drum, augmenter or other conventional mixing device. The blended product is recovered and optionally dried (213), before being used as a source of micronutrients (700) in agriculture.
Claims
CLAIMS:
1. A process for obtaining cathode material and carbon from alkaline mixed metal dust (MMD) obtained from alkaline batteries, comprising: a) comminuting alkaline MMD to reduce the average particle size of the alkaline MMD to liberate and obtain a first particle fraction comprising cathode material and carbon and a second particle fraction comprising anode material; and b) separating and obtaining the first particle fraction comprising cathode material and carbon from the second particle fraction comprising anode material.
2. The process of claim 1, wherein 80% of the comminuted alkaline MMD particles (Pso) have a particle size of between about 50 pm to about 500 pm.
3. The process of any one of claims 1 to 2, wherein the first particle fraction comprises manganese oxide and carbon, and the second particle fraction comprises zinc/zinc oxide.
4. The process of any one of claims 1 to 3 , wherein the first particle fraction is concentrated in manganese oxide and carbon and the second particle fraction is concentrated in zinc/zinc oxide.
5. The process of claim 3 or claim 4, wherein the first particle fraction has a higher % w/w concentration of manganese compared to the concentration of manganese in the second particle fraction, based on the total weight of the particle fraction.
6. The process of any one of claims 3 to 5 , wherein the first particle fraction comprises between about 25% w/w to about 60% w/w manganese based on the total weight of the first particle fraction.
7. The process of any one of claims 3 to 6, wherein the first particle fraction comprises between about 5% w/w to about 15% w/w carbon based on the total weight of the first particle fraction.
8. The process of any one of claims 3 to 7, wherein the second particle fraction has a higher % w/w concentration of zinc compared to the concentration of zinc in the first particle fraction, based on the total weight of the particle fraction.
9. The process of any one of claims 3 to 8 , wherein the second particle fraction comprises between about 20% w/w to about 70% w/w zinc, based on the total weight of the second particle fraction.
10. The process of any one of claims 3 to 9, wherein the carbon is physically or chemically associated with the manganese oxide as a mixed manganese oxide/carbon material.
11. The process of claim 10, wherein the mixed manganese oxide/carbon material is a mixed MnC /MmOs/carbon material.
12. The process of any one of claims 1 to 11, wherein the separating of the particle fractions at step b) comprises a size screening of the comminuted alkaline MMD particles.
13. The process of any one of claims 1 to 11, wherein the separating of the particle fractions at step b) comprises froth flotation of the comminuted alkaline MMD particles.
14. The process of claim 12, wherein the separating of the particle fractions at step b) comprises performing a froth flotation separation on the comminuted alkaline MMD particles in a froth flotation vessel, wherein the first particle fraction comprising cathode material and carbon reports to a flotation concentrate, and second particle fraction comprising anode material reports to a flotation tail, and removing the flotation concentrate from the froth flotation vessel to separate and obtain the first particle fraction comprising cathode material and carbon.
15. The process of claim 14, wherein the froth flotation separation comprises: bl) suspending the comminuted alkaline MMD particles in an aqueous solution comprising one or more froth flotation agents in the froth flotation vessel to create a slurry; t>2) aerating the slurry to generate air bubbles which float to the surface of the slurry to form a froth, wherein the first particle fraction comprising cathode material and carbon attaches to at least some of the air bubbles and floats to the top of the froth flotation vessel to report to the flotation concentrate, and the second particle fraction comprising anode material remains in the slurry to report to the flotation tail.
16. The process of claim 15 or 16, wherein the one or more froth flotation agents is selected from the group consisting of a frother, collector, and/or depressant.
17. The process of claim 15 or 16, wherein the frother is an alcohol selected from the group consisting of methyl isobutyl carbinol (MIBC), 2-ethyl hexanol, isoamyl alcohol, cyclohexanol, a-terpinol, cresol, xylenol, glycol ether, and a combination thereof.
18. The process of any one of claims 15 to 17, wherein the collector is provided in an amount of between about 100 g/t to about 8000 g/t.
19. The process of any one of claims 15 to 18, wherein the collector is a hydrocarbon oil, fatty acid or hydroximate.
20. The process of claim 19, wherein the hydrocarbon oil is kerosene.
21. The process of any one of claims 15 to 20, wherein after step bl) and prior to step t>2), the slurry comprising the comminuted alkaline MMD particles is conditioned prior to froth flotation to clean or activate the particles prior to aeration.
22. The process of any one of claims 14 to 21 , wherein the flotation tail comprising the second particle fraction is removed from the froth flotation vessel and undergoes gravity separation to recover any manganese and carbon entrained within the second particle fraction following froth flotation separation.
23. The process of claim 22, wherein the manganese and carbon recovered from gravity separation is recycled into the froth flotation vessel or combined with the flotation concentrate.
24. The process of any one of claims 14 to 23, wherein one or more heavy metals present in the comminuted alkaline MMD particles preferentially report to the flotation tail as part of the second particle fraction.
25. The process of claim 24, wherein the flotation tail has a higher ppm concentration of heavy metal compared to the concentration of heavy metal in the flotation concentrate, based on the total weight of the reported particles.
26. The process of any one of claims 1 to 25, wherein the alkaline MMD is provided by the steps: al) physically separating alkaline batteries to obtain coarser particles comprising steel and/or ferrous material and finer particles comprising alkaline MMD; and a2) separating the coarser particles comprising steel and/or ferrous material from the finer particles comprising alkaline MMD.
27. The process of claim 26, wherein the finer particles comprising alkaline MMD is between about 30% to about 80% w/w based on the total weight of the alkaline battery.
28. The process of claim 26 or claim 27, wherein step a2) comprises screening the separated alkaline battery particles at between about 4 mm to about 6 mm to separate the coarser particles comprising steel and/or ferrous material from the finer particle of alkaline MMD.
29. The process of claim 26 or claim 27, wherein step a2) comprises subjecting the separated alkaline battery particles to magnetic separation to separate the coarser particles comprising steel and/or ferrous material from the finer particles comprising alkaline MMD.
30. The process of any one of claims 26 to 29, wherein the physical separation of the alkaline batteries at step al) produces a dust and/or fume comprising electrolyte, wherein the dust and/or fume is optionally treated to recover the electrolyte.
31. The process of any one of claims 26 to 30, wherein the separated alkaline battery particles comprising coarser particles comprising steel and/or ferrous material and finer particles comprising alkaline MMD are washed and/or attritioned prior to step a2).
32. The process of any one of claims 26 to 31, wherein the separated coarser particles comprising steel and/or ferrous material is subjected to crushing to liberate and obtain alkaline MMD trapped within the coarser particles.
33. The process of any one of claims 1 to 32, wherein the separated first particle fraction comprising cathode material and carbon and/or separated second particle fraction comprising anode material is processed into one or more electrodes for alkaline batteries.
34. The process of claim 33, further comprising assembling an alkaline battery comprising one or more electrodes prepared using the separated first particle fraction comprising cathode material and carbon and/or separated second particle fraction comprising anode material.
35. The process of any one of claims 1 to 32, further comprising mixing the separated first particle fraction comprising cathode material and carbon at step b) with a phosphorous source and optionally a binder to prepare a fertiliser.
36. The process of claim 35, wherein the phosphorous source is a calcium phosphate salt or ammonium phosphate salt, or a combination thereof.
37. The process of claim 36, wherein the calcium phosphate salt is monocalcium phosphate (Super Phosphate).
38. The process of claim 36, wherein the ammonium phosphate salt is monoammonium phosphate (MAP) or diammonium phosphate (DAP), or a combination thereof.
39. The process of any one of claims 35 to 38, wherein the binder is phosphoric acid.
40. Use of the separated first particle fraction comprising cathode material and carbon obtained by the process of any one of claims 1 to 32, as a micronutrient in fertiliser.
42. A fertiliser comprising comminuted alkaline MMD particles or separated cathode material and carbon obtained from alkaline batteries, a phosphorous source, and optionally a binder.
43. An alkaline battery comprising one or more electrodes prepared using the separated cathode material and carbon and/or anode material obtained by the process of any one of claims 1 to 32.
44. Use of the separated first particle fraction comprising cathode material and carbon and/or anode material obtained by the process of any one of claims 1 to 32, as an electrode material for preparing one or more electrodes for alkaline batteries.
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Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1363963A (en) * | 2001-01-01 | 2002-08-14 | 刘序达 | Process for reclaiming used dry batteries |
JP2010253432A (en) * | 2009-04-28 | 2010-11-11 | Jfe Steel Corp | Method of recovering manganese oxide from dry cell |
WO2011056548A2 (en) * | 2009-10-27 | 2011-05-12 | Akridge James R | Oxygen torch waste reclamation system and acid recovery |
JP2011131195A (en) * | 2009-12-25 | 2011-07-07 | Jfe Steel Corp | Method for recovering manganese oxide from dry cell |
WO2011143061A1 (en) * | 2010-05-10 | 2011-11-17 | Rsr Technologies, Inc. | Separation of materials from recycled electrochemical cells and batteries by froth flotation |
US20120305684A1 (en) * | 2011-06-06 | 2012-12-06 | Ashish Bhandari | Method and system for reclamation of battery constituents |
CN103227337A (en) * | 2013-04-11 | 2013-07-31 | 安徽理工大学 | Waste zinc-manganese dry battery recovery system based on jigger sorting |
US20160045841A1 (en) * | 2013-03-15 | 2016-02-18 | Transtar Group, Ltd. | New and improved system for processing various chemicals and materials |
WO2017041185A1 (en) * | 2015-09-11 | 2017-03-16 | Marlie Inc | Battery recycling |
CN113058733A (en) * | 2021-04-24 | 2021-07-02 | 江西铭鑫冶金设备有限公司 | Environment-friendly recovery flow production line for waste lithium batteries |
-
2022
- 2022-07-13 WO PCT/AU2022/050732 patent/WO2023283685A1/en unknown
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1363963A (en) * | 2001-01-01 | 2002-08-14 | 刘序达 | Process for reclaiming used dry batteries |
JP2010253432A (en) * | 2009-04-28 | 2010-11-11 | Jfe Steel Corp | Method of recovering manganese oxide from dry cell |
WO2011056548A2 (en) * | 2009-10-27 | 2011-05-12 | Akridge James R | Oxygen torch waste reclamation system and acid recovery |
JP2011131195A (en) * | 2009-12-25 | 2011-07-07 | Jfe Steel Corp | Method for recovering manganese oxide from dry cell |
WO2011143061A1 (en) * | 2010-05-10 | 2011-11-17 | Rsr Technologies, Inc. | Separation of materials from recycled electrochemical cells and batteries by froth flotation |
US20120305684A1 (en) * | 2011-06-06 | 2012-12-06 | Ashish Bhandari | Method and system for reclamation of battery constituents |
US20160045841A1 (en) * | 2013-03-15 | 2016-02-18 | Transtar Group, Ltd. | New and improved system for processing various chemicals and materials |
CN103227337A (en) * | 2013-04-11 | 2013-07-31 | 安徽理工大学 | Waste zinc-manganese dry battery recovery system based on jigger sorting |
WO2017041185A1 (en) * | 2015-09-11 | 2017-03-16 | Marlie Inc | Battery recycling |
CN113058733A (en) * | 2021-04-24 | 2021-07-02 | 江西铭鑫冶金设备有限公司 | Environment-friendly recovery flow production line for waste lithium batteries |
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