WO2021075136A1 - 廃乾電池からのマンガン回収方法および回収設備 - Google Patents
廃乾電池からのマンガン回収方法および回収設備 Download PDFInfo
- Publication number
- WO2021075136A1 WO2021075136A1 PCT/JP2020/030638 JP2020030638W WO2021075136A1 WO 2021075136 A1 WO2021075136 A1 WO 2021075136A1 JP 2020030638 W JP2020030638 W JP 2020030638W WO 2021075136 A1 WO2021075136 A1 WO 2021075136A1
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- WO
- WIPO (PCT)
- Prior art keywords
- manganese
- zinc
- iron
- ions
- solution
- Prior art date
Links
- 239000011572 manganese Substances 0.000 title claims abstract description 306
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 296
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 294
- 238000000034 method Methods 0.000 title claims abstract description 127
- 239000002699 waste material Substances 0.000 title claims abstract description 51
- 238000011084 recovery Methods 0.000 title claims description 53
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 432
- 229910052742 iron Inorganic materials 0.000 claims abstract description 239
- 239000011701 zinc Substances 0.000 claims abstract description 224
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 217
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 216
- 239000002253 acid Substances 0.000 claims abstract description 117
- 238000000926 separation method Methods 0.000 claims abstract description 112
- 238000002386 leaching Methods 0.000 claims abstract description 93
- 239000007788 liquid Substances 0.000 claims abstract description 90
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 42
- 238000000605 extraction Methods 0.000 claims abstract description 25
- 150000002500 ions Chemical class 0.000 claims abstract description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 130
- 239000008187 granular material Substances 0.000 claims description 128
- 239000000843 powder Substances 0.000 claims description 128
- 238000010438 heat treatment Methods 0.000 claims description 92
- 238000001556 precipitation Methods 0.000 claims description 80
- 238000007254 oxidation reaction Methods 0.000 claims description 76
- 230000003647 oxidation Effects 0.000 claims description 74
- 239000002244 precipitate Substances 0.000 claims description 67
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 55
- -1 iron ions Chemical class 0.000 claims description 54
- 239000010926 waste battery Substances 0.000 claims description 54
- 239000003638 chemical reducing agent Substances 0.000 claims description 50
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 46
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 38
- 238000007873 sieving Methods 0.000 claims description 36
- 238000005273 aeration Methods 0.000 claims description 31
- 239000012298 atmosphere Substances 0.000 claims description 29
- 230000001590 oxidative effect Effects 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 21
- 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 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 15
- 239000003575 carbonaceous material Substances 0.000 claims description 11
- 239000007800 oxidant agent Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 230000001376 precipitating effect Effects 0.000 claims description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 6
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 6
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 207
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 40
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 24
- 239000000203 mixture Substances 0.000 description 24
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 22
- 229910002804 graphite Inorganic materials 0.000 description 21
- 239000010439 graphite Substances 0.000 description 21
- 238000004458 analytical method Methods 0.000 description 18
- 229910052799 carbon Inorganic materials 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- 239000011787 zinc oxide Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 12
- 239000011148 porous material Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 235000005074 zinc chloride Nutrition 0.000 description 11
- 239000011592 zinc chloride Substances 0.000 description 11
- 239000003002 pH adjusting agent Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- 150000002739 metals Chemical class 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 239000007772 electrode material Substances 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- 239000011593 sulfur Substances 0.000 description 8
- 238000004993 emission spectroscopy Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- 229910052984 zinc sulfide Inorganic materials 0.000 description 6
- 239000005083 Zinc sulfide Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 description 4
- 150000004692 metal hydroxides Chemical class 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000005022 packaging material Substances 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 150000004763 sulfides Chemical class 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000002440 industrial waste Substances 0.000 description 3
- 235000014413 iron hydroxide Nutrition 0.000 description 3
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 3
- 235000002867 manganese chloride Nutrition 0.000 description 3
- 239000011565 manganese chloride Substances 0.000 description 3
- 229940099607 manganese chloride Drugs 0.000 description 3
- 238000009628 steelmaking Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910000616 Ferromanganese Inorganic materials 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 210000000416 exudates and transudate Anatomy 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical class [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- LNGNZSMIUVQZOX-UHFFFAOYSA-L disodium;dioxido(sulfanylidene)-$l^{4}-sulfane Chemical compound [Na+].[Na+].[O-]S([O-])=S LNGNZSMIUVQZOX-UHFFFAOYSA-L 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910021404 metallic carbon Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/02—Apparatus therefor
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B2101/00—Type of solid waste
- B09B2101/15—Electronic waste
- B09B2101/16—Batteries
-
- 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 invention relates to a method and equipment for recovering valuable metals from waste batteries.
- manganese which is a main valuable component of a discarded manganese dry battery and / or an alkaline manganese dry battery, can be separated as a valuable metal and recovered as high-purity manganese that can be used for various batteries.
- Manganese recovery method and recovery equipment can be used for various batteries.
- manganese which is one of the valuable metals, is regarded as an essential metal in various fields of industry, and there is concern that its demand will exceed its reserves in the future.
- steelworks have traditionally consumed a large amount of manganese as a raw material for steelmaking, and securing a manganese source is an extremely important issue in the steelmaking field.
- the consumption of manganese for secondary batteries such as lithium ion batteries has been increasing, and securing a manganese source has become an extremely serious problem in this secondary battery field as well.
- a huge amount of dry batteries are produced, consumed, and disposed of as industrial waste.
- Some of the dry batteries (waste dry batteries) that are discarded as industrial waste have a high manganese content.
- a manganese dry battery and an alkaline manganese dry battery which are typical as primary batteries, use manganese dioxide as a positive electrode material and zinc as a negative electrode material.
- manganese dry batteries zinc chloride may be used as the electrolytic solution.
- iron is used for the outer cylinder of these dry batteries.
- manganese batteries and alkaline manganese batteries are selected from waste dry batteries, crushed and screened to obtain powders and granules, and the obtained powders and granules are dissolved with dilute hydrochloric acid or dilute sulfuric acid for acid treatment.
- a method for recovering a metallurgical raw material from a waste battery has been proposed in which manganese dioxide and a carbon-containing mixture are separated and recovered.
- the manganese dioxide and carbon-containing mixture recovered by the technique described in Patent Document 1 can be used as a starting material for ferromanganese production or as a material directly used in a smelting furnace instead of ferromanganese.
- Patent Document 2 proposes a technique for separating and recovering manganese dioxide and zinc chloride from a waste battery.
- a material containing a large amount of manganese and zinc is obtained from a waste dry battery, and this material is washed with water, dissolved in hydrochloric acid, and insoluble matter (carbon powder, etc.) is removed.
- a mixed aqueous solution of manganese chloride and zinc chloride is prepared, the solution is purified by purification to remove impurities, then concentrated by heating, and perchloric acid is added to the concentrate to heat the solution, and manganese chloride in the solution is oxidized to manganese dioxide.
- Patent Documents 3 to 5 an acid or an acid and a reducing agent are allowed to act on manganese-containing powders and granules obtained by crushing and sieving a waste dry battery, and ozone is further allowed to act on the obtained manganese solution.
- a technique for recovering manganese, which is a valuable component, from a waste battery by precipitating only manganese as an oxide is described.
- Patent Document 3 proposes a method for recovering valuable components from waste batteries.
- a step of sorting a manganese dry battery and / or an alkali manganese dry battery from a waste dry battery and a crushing / sieving step of crushing and sieving the dry battery selected in the sorting step to obtain powders and granules.
- An acid leaching step in which manganese and zinc are leached from the powder and granules by mixing the powder and granules obtained in the crushing and sieving step, an acid solution, and a reducing agent, and an leaching solution obtained in the acid leaching step.
- Manganese ions contained in the leachate are oxidized and precipitated by allowing ozone to act on the leachate separated in the first solid-liquid separation step of solid-liquid separation and the first solid-liquid separation step.
- a second solid-liquid separation step of solid-liquid separation of the manganese-containing precipitate obtained in the ozone treatment step and the zinc ion-containing solution is performed in sequence through an ozone treatment step of obtaining a manganese-containing precipitate and a zinc ion-containing solution.
- the manganese component contained in the waste dry battery is recovered as a manganese-containing precipitate.
- Patent Document 3 an alkaline agent is added to the zinc ion-containing solution, and an alkaline precipitation treatment step is performed in which zinc ions in the zinc ion-containing solution are used as a zinc-containing precipitate to remove the zinc component contained in the waste dry battery. It is being collected.
- Patent Document 4 proposes a method for separating resources from waste batteries.
- Manganese-containing precipitates are formed by allowing ozone to act on the leachate separated in the first solid-liquid separation step and the first solid-liquid separation step to oxidize and precipitate manganese ions contained in the leachate.
- a waste dry battery is sequentially subjected to an ozone treatment step of obtaining a product and a zinc ion-containing solution and a second solid-liquid separation step of solid-liquid separation of the manganese-containing precipitate obtained in the ozone treatment step and the zinc ion-containing solution.
- the manganese component contained in is separated as a leachate residue and a manganese-containing precipitate, and the zinc component contained in the waste dry battery is separated as a zinc ion-containing solution.
- Patent Document 5 describes a method for producing high-grade metallic manganese.
- a manganese-containing substance and a reducing agent and a flux are charged into an arc melting furnace, and the manganese-containing substance is reduced by energization and / or the reaction heat of the reducing agent to reduce the metal.
- This is a method for producing high-grade metallic manganese, which is manganese.
- manganese contained in a waste dry battery is subjected to acid leaching treatment as a manganese-containing substance, the obtained acid leaching solution is subjected to ozone treatment, and only manganese is precipitated as an oxide and then separated.
- a manganese-containing substance obtained by treatment is used.
- Patent Documents 6 to 7 manganese is recovered by leaching manganese from a metal oxide or a metal hydroxide by using divalent iron obtained by reacting ferric iron with iron-reducing bacteria. The technology to be used is described.
- Patent Document 6 proposes a metal recovery method.
- iron-reducing bacteria are allowed to act on a group consisting of a metal oxide and a metal hydroxide to reduce trivalent iron to divalent iron, and the obtained divalent iron is used.
- Metals such as cobalt, nickel, and manganese contained in the group consisting of metal oxides and metal hydroxides are leached to generate leachate and residue, and the obtained leachate and residue are separated to recover the desired metal. How to do it.
- low-grade metals contained in metal oxides and metal hydroxides can be recovered at high speed and with high efficiency.
- Patent Document 7 proposes a manganese recovery method.
- a manganese-containing object to be treated and iron-reducing bacteria are mixed with a treatment liquid containing trivalent iron ions, and trivalent iron ions are reduced to divalent iron ions.
- It is a technique having an insolubilization step of oxidizing ions to insolubilize them and a step of precipitating and separating and recovering the obtained manganese component.
- manganese can be concentrated and recovered at a high concentration rate under relatively mild conditions, and manganese can be recovered inexpensively and easily from a large amount of object to be treated.
- the zinc refining maker recovers a part of zinc contained in the waste battery, or a part of the electric furnace maker. Is only recovering some of the iron and carbon contained in the waste batteries. Most of the valuable metals contained in waste batteries are not recovered and are sent to landfills as waste materials. This is due to the fact that it is technically difficult to separate various valuable metals contained in waste batteries, and that there are still problems such as disadvantages in terms of economy.
- Patent Document 2 describes that the recovered manganese can be used for manufacturing a new manganese dry battery.
- the technique described in Patent Document 2 has a problem that the procedure is complicated and a problem that the manufacturing cost rises because it includes a process that consumes a large amount of energy such as heating and concentrating.
- all manganese recovered from waste batteries by the techniques described in the above-mentioned patent documents other than Patent Document 2 have a problem of low purity as a raw material for an electrode material of a secondary battery.
- the recovered manganese When the recovered manganese is used as a raw material for an electrode material of a secondary battery, its purity is required to be high. This is because impurities mixed in the electrode material of the secondary battery have a significant effect on the performance of the secondary battery such as discharge capacity and repeatability, and cause a significant deterioration in the performance of the secondary battery. .. Furthermore, in recent years, it has become clear that the presence of impurities mixed in the electrode material of a secondary battery may cause ignition of the battery due to a short circuit. Therefore, manganese used as a raw material for an electrode material of a secondary battery is required to strictly reduce impurities.
- the present invention has been made in view of the above-mentioned problems of the prior art, and manganese contained in a waste dry battery can be recovered as a high-purity manganese-containing solution containing extremely little contamination of impurities such as zinc, iron, and carbon. , Aim to provide a method and equipment for recovering manganese from waste batteries.
- high-purity manganese-containing solution refers to an analytical method in which zinc (Zn), iron (Fe), carbon (C), etc. are commonly used as impurities in the solution. All of the analyzes used refer to manganese-containing solutions that are below the analytical limit, for example, less than 0.1 mg / L.
- the materials constituting the dry batteries are separated into solids on the sieve and powders and granules under the sieve.
- the materials constituting the dry battery mainly iron-skin-like packaging materials, zinc cans, brass rods, paper materials, plastics and the like become foil-like or piece-like solids after crushing and are separated on a sieve.
- manganese dioxide, carbon, zinc chloride, ammon chloride, caustic potash, or MnO (OH), Zn (OH) 2 , Mn (OH) 2 , ZnO, etc. generated by discharge become powders and granules under the sieve. Be separated. Normally, a small amount of iron is inevitably mixed in the powder or granular material.
- the present inventors have diligently studied a means for separating impurities, which is effective for recovering manganese contained in a waste dry cell as a high-purity manganese-containing solution containing few impurities.
- the present inventors have selected unintended components (impurities) from powders and granules obtained by selecting one or both of manganese dry batteries and alkaline manganese dry batteries from waste batteries, and further crushing and sieving them. Diligently examined whether to remove.
- the present inventors have come up with the idea of first subjecting the powder or granular material obtained as described above to a predetermined heat treatment.
- the zinc contained in the powder or granular material is highly efficient and highly efficient. It was found that it can be easily removed as pure zinc. Further, the present inventors apply an acid and a reducing agent to the heat-treated powders and granules to obtain a leachate in which manganese, iron, and residual zinc are leached, and then, from this leachate, If the remaining zinc component and the iron component are selectively precipitated and separated according to a predetermined procedure, a high-purity manganese solution can be easily and inexpensively obtained regardless of the order of the precipitation / separation steps. Was found.
- the present inventors first act as a sulfide (zinc-containing sulfide) in the leachate by allowing a sulfide such as sodium hydrosulfide NaHS to act on the leachate. It was found that the zinc component can be further removed from the leachate by performing a sulfide precipitation treatment step of selectively precipitating and a zinc separation step of separating the obtained zinc-containing precipitate (zinc removal step in procedure A). .. Then, the present inventors have found that the zinc ion concentration in the solution (first solution) left after the zinc removal step can be easily reduced to less than the analysis limit of 0.1 mg / L.
- a sulfide such as sodium hydrosulfide NaHS
- the present inventors have also found that by adjusting the amount of sulfide to act on, the concentration of sulfide ions, and the pH of the leachate, the zinc component remaining from the leachate can be better separated. Then, if the first solution in which zinc is separated to less than the analysis limit is further subjected to an oxidation treatment step and iron ions are further separated as an iron-containing precipitate (iron separation step), it is left after the iron component is separated. It was found that a high-purity manganese solution can be easily and inexpensively obtained as a solution (second solution) (iron removal step in procedure A).
- the present inventors when the iron component is removed prior to the remaining zinc component, the present inventors oxidize the obtained leachate to form an iron-containing precipitate. I came up with the idea of performing an iron separation step to separate the obtained iron-containing precipitate (procedure B).
- the present inventors selectively precipitate iron ions contained in the leachate, for example, as hydroxides by oxidizing the leachate with air, for example, and preferentially separate only the iron component from the leachate. , It was found that the iron ion concentration in the solution (first solution) left after the separation of the iron component can be significantly reduced.
- the present inventors have also found that by adjusting the pH of the leachate, only the iron component can be better separated from the leachate. Then, the first solution after separating the iron component is subsequently subjected to a sulfide precipitation treatment in which a sulfide such as sodium hydrosulfide NaHS acts, and the remaining zinc ions are further separated as a zinc-containing precipitate. It has been found that a high-purity manganese solution can be easily and inexpensively obtained as a solution (second solution) left after separation.
- the weight and zinc content of the powder and granules before and after the heat treatment are measured, and the zinc removal rate by the heat treatment is determined according to the following formula from the difference in the zinc content contained in the powder and granules before and after the heat treatment. Calculated.
- Zinc removal rate [%] (Zn content in powder or granular material before heat treatment [kg] -Zn content in powder or granular material after heat treatment [kg]) x 100 / Powder or granular material before heat treatment Zn content in [kg]
- FIG. 4 a graph showing the relationship between the blending ratio of the reducing agent (graphite) and the zinc removal rate in the heat treatment step.
- the zinc removal rate is 84% even when the graphite blending ratio is 0 (that is, when graphite as a reducing agent is not blended in the heat treatment step).
- ZnO is first reduced to Zn (zinc) by the reaction between the graphite contained in the powder or granular material derived from the dry battery and ZnO. Since the boiling point of zinc is around 900 ° C., when the heating temperature is 1000 ° C., the produced zinc is volatilized and removed from the powder or granular material as zinc vapor. Further, from FIG.
- the heat treatment of the powder or granular material is performed in a non-oxidizing atmosphere having an inert atmosphere or a reducing atmosphere.
- an oxidizing atmosphere such as an air atmosphere
- a part of graphite contained in the powder or granular material or added to the powder or granular material reacts with oxygen in the air instead of ZnO and burns. Therefore, the reduction of ZnO to zinc is inhibited.
- most of the zinc contained in the powder or granular material is volatilized and removed by the heat treatment, but as can be seen from FIG. 4, a small amount of zinc component usually remains in the heat-treated powder or granular material. To do.
- the acid solution and the reducing agent are allowed to act on the heat-treated powder or granular material to leach the manganese component, iron component, and the remaining zinc component contained in the powder or granular material into the leachate.
- the effect of the amount of the reducing agent added on the leaching rate of the manganese component in this acid leaching step was investigated.
- Manganese dry batteries and alkaline manganese dry batteries are selected from the waste batteries, and the powders and granules obtained by further crushing and sieving are subjected to a nitrogen atmosphere (inert atmosphere) without adding a reducing agent such as graphite.
- Heating temperature Heat treatment was performed at 1000 ° C. for 30 minutes.
- An acid leaching step of mixing an acid solution and a reducing agent was carried out on the obtained heat-treated powders and granules.
- the acid leaching treatment conditions were as follows. By this acid leaching step, a mixture of a leachate containing at least manganese ions, residual zinc ions, iron ions, and other leaching residues was obtained.
- Acid solution Sulfuric acid 50 mL Sulfuric acid concentration: 1.5 mol / L (mass% concentration about 13.2%)
- Reducing agent 35% hydrogen peroxide solution H 2 O 2 Reducing agent addition amount: 0g (0g / L), 0.56g (11g / L), 1.1g (22g / L), 1.7g (33g / L), 2.2g (45g / L)
- Acid leaching treatment time 1 hour (stirring treatment) Solid-liquid ratio of powder and acid solution: 100 g / L
- the obtained mixture was filtered through a filter paper having a pore size of 1 ⁇ m, and the leachate and the leachate residue were solid-liquid separated (solid-liquid separation step).
- the manganese concentration in the separated leachate was quantified by ICP emission spectrometry.
- the mass of manganese in the leachate was determined, and the ratio of the mass of manganese in the leachate to the mass of manganese contained in the powder or granular material after the heat treatment (in terms of manganese element) was calculated. , Manganese leaching rate.
- the obtained results are shown in FIG.
- the manganese leaching rate is approximately 100% regardless of the amount of the reducing agent (hydrogen peroxide solution) added, and the manganese component contained in the powder or granular material after the heat treatment is leached by the acid leaching step. It can be seen that the entire amount has been leached out.
- the form of manganese contained in the powder or granular material after the heat treatment step is mainly MnO. MnO dissolves only in acid. Therefore, the present inventors have found that if the powder or granular material is subjected to a heat treatment step, almost all of the manganese component contained in the powder or granular material can be leached without adding a reducing agent in the acid leaching step.
- the heating temperature, and the heating time MnO 2 , Mn 2 O 3 , and Mn 3 O 4 even after the heat treatment.
- the Mn form remains, and the entire amount of manganese is not leached only by the acid.
- a reducing agent hydrogen peroxide solution
- manganese existing as MnO 2 , Mn 2 O 3 , and Mn 3 O 4 can also be leached as Mn 2+.
- the powder or granular material after the heat treatment is subjected to an acid leaching treatment in which an acid and, if necessary, a reducing agent are further acted to leach the remaining zinc component, and then sulfide is further added to the obtained leachate. If the precipitation treatment is performed, the remaining zinc component can be selectively and sufficiently precipitated as will be described in detail later. As a result, we have come up with the idea that the zinc component can be removed reliably, easily, and inexpensively.
- the heat-treated powders and granules that have been heat-treated without blending graphite are subjected to acid leaching treatment in which only an acid solution acts (acid leaching step), and then the leachate and the precipitate are filtered through a filter paper having a pore size of 1 ⁇ m.
- a solid-liquid separation step was performed to obtain a leachate.
- the acid concentration of the acid solution was 1.5 mol / L (mass% concentration: about 13.2%), and the acid leaching treatment time was 1 hour for stirring.
- the manganese concentration was 66198 mg / L
- the zinc concentration was 5031 mg / L
- the iron concentration was 1131 mg / L.
- the obtained leachate was subjected to a sulfide precipitation treatment step in which sodium hydrosulfide NaHS was added as a sulfide under various conditions.
- Sodium hydrosulfide (NaHS) was dissolved in distilled water and added in the form of a solution.
- the conditions for the sulfide precipitation treatment were as follows.
- Leachate 100 mL Sulfide type: Sodium hydrosulfide (NaHS)
- Addition amount of sulfide 1 to 3 equivalents of sulfur with respect to dissolved zinc pH of leachate during reaction: 0.5 to 5
- Acidity regulator 3M sulfuric acid or 100g / L sodium hydroxide
- Treatment time 0.5 hours after addition of sodium hydrosulfide (stirring treatment)
- suction filtration is performed with a filter paper having a pore size of 1 ⁇ m to perform solid-liquid separation (zinc separation step), and the components (zinc, iron, manganese) of the separated first solution are quantified by the ICP emission analysis method.
- the analytical values obtained were corrected for the effect of being diluted by the addition of a sodium hydrosulfide solution and a pH adjuster. The obtained results are shown in FIG.
- the analysis result of manganese is not shown in FIG. 7.
- iron precipitation is also removed by the zinc removal step.
- the amount of sulfide added is 2 equivalents (NaHS: 2 equivalents)
- iron is precipitated and removed under the condition that the pH is 3 or more, and when the pH is about 5, iron is precipitated and removed.
- the Fe concentration is reduced to about 1 to 10 mg / L.
- the manganese concentration also began to decrease to about 55000 mg / L, although not shown. That is, it can be seen that under the condition that the amount of sulfide added is 2 equivalents and the pH is 3 or more, a part of manganese is precipitated and removed at the same time as zinc and iron.
- the zinc component can be precipitated / separated and removed to less than the analysis limit.
- iron (Fe) may be partially precipitated together with zinc (Zn). If the iron (Fe) concentration has been precipitated and removed to some extent, the treatment may be terminated at this stage.
- the present inventors have set iron ions contained in the first solution separated after the zinc removal step as an iron-containing precipitate such as hydroxide (iron removal step). I came up with the need to perform additional oxidation treatment steps and iron separation steps).
- Experiment (B) According to the same method as in Experiment (A), the manganese concentration, zinc concentration, and iron concentration in the leachate separated by the solid-liquid separation step were measured by ICP luminescence analysis, and the manganese concentration was 66198 mg / L and the zinc concentration was 5031 mg. The iron concentration was 1131 mg / L.
- the obtained leachate was aerated with air as an oxidation treatment (oxidation treatment step).
- the conditions for air aeration were as follows. Blow-in amount: (same volume as leachate volume) / min Aeration time: 30 minutes pH of leachate during reaction: 4-6 pH adjuster: 3M sulfuric acid or 100g / L sodium hydroxide
- the aeration amount and aeration time are under normal practical conditions (aeration amount: 0.1 to 1 times the amount / minute of the solution amount, aeration time. : 15-60 minutes).
- the total amount of the leachate after air aeration is suction-filtered with a filter paper having a pore size of 1 ⁇ m and solid-liquid separated (iron separation step), and the component concentrations (zinc, iron, manganese) of the separated first solution are determined by ICP emission spectrometry. Measured at. The obtained measured values were corrected for the effect of dilution with a pH adjuster. The obtained results are shown in FIG. Since precipitation of manganese and zinc by the oxidation treatment step was hardly confirmed, FIG. 8 shows only the iron concentration in the first solution after the iron removal step (oxidation treatment step and iron separation step).
- the leachate adjusted to pH: 5 was subjected to air aeration (oxidation treatment) to reduce the iron concentration to less than 0.5 mg / L, and then the iron separation step by solid-liquid separation was performed to obtain the first solution. Further, a sulfide precipitation treatment step was performed under various conditions. The conditions for the sulfide precipitation treatment were as follows.
- First solution 100 mL Sulfide type: Sodium hydrosulfide (NaHS)
- Addition amount of sulfide 1 to 3 equivalents of sulfur with respect to dissolved zinc pH of the first solution during the reaction: 0.5 to 5
- Acidity regulator 3M sulfuric acid or 100g / L sodium hydroxide
- Treatment time 0.5 hours after addition of sodium hydrosulfide (stirring treatment)
- suction filtration was performed with a filter paper having a pore size of 1 ⁇ m to perform solid-liquid separation (zinc separation step), and the components of the separated second solution were analyzed by ICP emission spectrometry.
- manganese obtained by subjecting the powders and granules of the waste dry battery to heat treatment and then mixing the heat-treated powders and granules with an acid solution or a reducing agent If the leachate from which zinc and iron have been leached is first subjected to an oxidation treatment, a solution in which most of the iron components are precipitated, separated and removed can be obtained by simply performing a simple oxidation treatment called air aeration (iron removal step). ). Then, if the first solution is subjected to a sulfide precipitation treatment step of allowing sulfide to act, the zinc component can be precipitated and removed below the analysis limit (zinc removal step).
- iron is subjected to the zinc removing step and the iron removing step in addition to the heat treatment step, regardless of the step sequence of the zinc removing step and the iron removing step. It was found that a high-purity manganese-containing solution in which both iron and iron were reliably precipitated, separated and removed can be easily produced by simply performing a simple process.
- the present invention has been completed by further studying based on such findings. That is, the gist of the present invention is as follows. (1) A sorting step for selecting manganese dry batteries and / or alkaline manganese dry batteries from waste batteries, and A crushing / sieving step of crushing and sieving the manganese dry battery and / or the alkaline manganese dry battery sorted in the sorting step to obtain powders and granules. A heat treatment step in which the powder or granular material obtained in the crushing / sieving step is heat-treated in a non-oxidizing atmosphere, and a heat treatment step.
- An acid solution or a reducing agent is mixed with the powder or granular material subjected to the heat treatment step, and manganese, zinc and iron contained in the powder or granular material are leached from the powder or granular material to cause manganese ions.
- An acid leaching step to obtain a leachate containing zinc ions and iron ions
- a solid-liquid separation step for separating the leachate obtained in the acid leaching step and other leaching residues
- a solid-liquid separation step for separating the leachate obtained in the acid leaching step and other leaching residues
- a manganese extraction step of removing the zinc ions and iron ions from the leachate separated in the solid-liquid separation step to obtain a solution containing the manganese ions. Is a method of recovering manganese from waste batteries in this order.
- the manganese extraction step A zinc removal step including a sulfide precipitation treatment step of allowing sulfide to act on the zinc ions to precipitate the zinc ions, and a zinc separation step of separating the obtained zinc-containing precipitate;
- An iron removal step including an oxidation treatment step of oxidizing the iron ions to precipitate the iron ions, and an iron separation step of separating the obtained iron-containing precipitate;
- a method for recovering manganese from a waste battery which comprises obtaining a high-purity manganese-containing solution by containing the following in no particular order.
- the manganese extraction step is performed in the order of the zinc removing step and then the iron removing step.
- a sulfide precipitation treatment step is performed in which a sulfide is allowed to act on the leachate to precipitate zinc ions in the leachate, and then the zinc-containing precipitate and manganese obtained in the sulfide precipitation treatment step are performed.
- iron obtained in the oxidation treatment step is performed after performing an oxidation treatment step of oxidizing the first solution obtained in the zinc removal step to precipitate iron ions in the first solution.
- a method for recovering manganese from a waste dry cell which comprises solid-liquid separation of the contained precipitate and a second solution containing manganese ions.
- a method for recovering manganese from a waste dry cell which comprises adding the first solution and adjusting the pH of the first solution to 3 or more and 7 or less.
- the manganese extraction step is performed in the order of the iron removing step and then the zinc removing step.
- the iron removing step after performing an oxidation treatment step of oxidizing the leachate and precipitating iron ions in the leachate, the iron-containing precipitate obtained in the oxidation treatment step and manganese ions and zinc ions are contained.
- a sulfide precipitation treatment step is performed in which a sulfide is allowed to act on the first solution obtained in the iron removal step to precipitate zinc ions in the first solution, and then the sulfide precipitation.
- a method for recovering manganese from a waste battery which comprises solid-liquid separation of a zinc-containing precipitate obtained in the treatment step and a second solution containing manganese ions.
- manganese recovery from a waste battery is characterized in that the first solution containing manganese ions and zinc ions is adjusted to pH: 2 or more and 6 or less.
- the heat treatment in the heat treatment step is a treatment of heating to a temperature in the range of 800 ° C. or higher and 1200 ° C. or lower, from a waste dry battery. Manganese recovery method.
- the carbon material is further added to the powder or granular material in a mass ratio of 0.5 or less with respect to the total amount of the powder or granular material.
- the acid solution in the acid leaching step is made of dilute sulfuric acid having a mass% concentration of 1.4% or more and 45% or less or dilute hydrochloric acid having a mass% concentration of 1% or more and 14% or less.
- the solid-liquid ratio of the powder or granular material to the acid solution in the acid leaching step is 50 g / L or more, from a waste dry battery. Manganese recovery method.
- the reducing agent in the acid leaching step is any one of hydrogen peroxide, sodium sulfide, sodium bisulfite, sodium thiosulfate, and iron sulfate.
- the sulfide used in the sulfide precipitation treatment step is any one of sodium hydrosulfide, sodium sulfide, and hydrogen sulfide. Manganese recovery method from waste batteries.
- An acid solution or a reducing agent is mixed with the powder or granular material heat-treated by the heating device, and manganese, zinc and iron contained in the powder or granular material are leached from the powder or granular material to leach manganese ions.
- An acid leaching tank to obtain a leachate containing zinc ions and iron ions
- a solid-liquid separator that separates the leaching liquid and the leaching residue obtained in the acid leaching tank
- a group of manganese extractors that remove the zinc ions and iron ions from the leachate separated by the solid-liquid separator to obtain a solution containing the manganese ions.
- Manganese recovery equipment from waste batteries which is equipped in this order.
- the manganese extraction device group A group of zinc removing devices including a sulfide precipitation treatment tank for allowing sulfide to act on the zinc ions to precipitate the zinc ions, and a zinc separator for solid-liquid separation of the obtained zinc-containing precipitate.
- An iron removing device group including an oxidation treatment tank for oxidizing the iron ions to precipitate the iron ions, and an iron separating device for solid-liquid separating the obtained iron-containing precipitate;
- Manganese recovery equipment from waste batteries which is characterized by recovering valuable components from waste batteries by including them in no particular order.
- the manganese component contained in the waste dry battery is almost completely separated from the carbon component, the zinc component, and the iron component, and the purity is high enough to be used as a raw material for the electrode material of the secondary battery, and the yield is high. , It can be collected at low cost, and it has a great effect on the industry.
- the present invention targets a waste dry battery, and separates the manganese component contained in the waste dry cell from the carbon component, the zinc component and the iron component contained in the waste dry battery together, and recovers the manganese component as a high-purity manganese-containing solution from the waste dry battery.
- the present invention relates to a method for recovering manganese and a recovery facility for manganese.
- the method for recovering manganese of the present invention includes a sorting step, a crushing / sieving step, a heat treatment step, an acid leaching step, a solid-liquid separation step, and a manganese extraction step in this order.
- the manganese extraction step includes a predetermined zinc removing step and an iron removing step in no particular order.
- Sorting process Waste batteries are generally collected in a mixed form of various types. Therefore, in the present invention, manganese dry batteries and / or alkaline manganese dry batteries are selected from the recovered waste batteries. In order to efficiently extract the manganese component in a later step, only the manganese dry battery may be selected, only the alkaline manganese dry battery may be selected, or both the manganese dry battery and the alkaline manganese dry battery may be selected. ..
- the sorting method any method such as manual sorting or machine sorting using equipment may be used.
- the manganese dry cell and / or alkaline manganese dry cell selected in the sorting step is crushed.
- the purpose of crushing is to eliminate as much as possible materials containing components other than manganese, zinc, and carbon from the constituent materials of manganese dry batteries and / or alkaline manganese batteries sorted in the sorting step.
- packaging materials iron, plastic, paper, etc.
- zinc cans which are the negative material of manganese batteries
- brass rods which are collectors of alkaline manganese batteries
- manganese dioxide which is a positive electrode material
- carbon rod which is a current collector for manganese dry batteries
- zinc powder which is a negative electrode material for alkaline manganese dry batteries
- MnO (OH), Zn (OH) 2 which is a negative electrode material for alkaline manganese dry batteries
- Compounds such as ZnO and various electrolytic solutions become finer powders than foil-like or piece-like solids.
- a crusher is usually used to crush the waste batteries.
- the type of the crusher is not particularly limited, and for example, a type in which solid matter such as a packaging material constituting a dry battery and powder or granular material are well separated after crushing is preferable.
- Examples of such a crusher include a biaxial rotary type crusher.
- the mesh size of the sieve used for sieving the above-mentioned crushed material is preferably about 1 mm or more, preferably 20 mm or less, and 10 mm or less. More preferably, 3 mm or less is further preferable.
- the mesh size of the sieve is preferably about 1 to 20 mm, more preferably about 1 to 10 mm, and even more preferably about 1 to 3 mm.
- the mesh size of the sieve is at least the above lower limit, more powders and granules containing a manganese component can be secured.
- the mesh opening of the sieve is not more than the above upper limit, solid matter containing an unintended component other than manganese can be more eliminated, and the subsequent steps can be performed more efficiently.
- the powders and granules obtained through the crushing and sieving steps are the main constituent materials of the manganese dry battery and / or the alkaline manganese dry battery, such as manganese dioxide, carbon, zinc chloride or ammon chloride, caustic potash, and further. It is a powder and granules in which MnO (OH), Zn (OH) 2 , Mn (OH) 2, ZnO, etc. generated by discharge are mixed. Normally, an iron component is inevitably mixed in the powder or granular material.
- Heat treatment step The powder or granular material obtained through the crushing / sieving step is heat-treated in a non-oxidizing atmosphere such as an inert atmosphere or a reducing atmosphere as a heat treatment step.
- Zinc (Zn) in the powder or granular material mainly exists as ZnO, and by performing heat treatment, graphite in the powder or granular material reacts with ZnO and is reduced from ZnO to zinc (Zn).
- the heat treatment is performed in an oxidizing atmosphere, the graphite in the powder or granules or a part of the graphite mixed as a reducing agent reacts with oxygen in the atmosphere and burns instead of ZnO, so from ZnO to zinc.
- the reduction reaction of zinc oxide is inhibited, and the removal rate of zinc from the powder and granules is reduced. Therefore, the heat treatment may be performed in a non-oxidizing atmosphere, in an inert atmosphere, or in a reducing atmosphere.
- the powder or granular material is preferably heated to 800 ° C. or higher, more preferably 850 ° C. or higher, further preferably 900 ° C. or higher, and preferably 1200 ° C. or lower. It is preferable to heat to a temperature in the range of 800 ° C. or higher and 1200 ° C. or lower.
- the temperature of the heat treatment is 800 ° C. or higher, zinc starts to volatilize substantially and becomes zinc vapor and is removed from the powder or granular material.
- the temperature of the heat treatment exceeds 1200 ° C., the heating furnace that can be used is limited. From this point of view, it is preferable that the heat treatment is a treatment of heating to a temperature within the above-mentioned preferable range.
- the reduction reaction from ZnO to zinc can be caused only by the graphite in the powder or granular material.
- a non-metallic carbon material such as graphite as a reducing agent
- carbon material blending ratio carbon material / powders and granules
- the bulk density of the carbon material is smaller than that of the powder or granular material, if a large amount of carbon material with a carbon material mixing ratio of more than 0.5 is mixed, a large heating facility is required, which is economically disadvantageous. is there.
- the reducing agent used is a non-metal-based reducing agent. It is preferably a carbon material.
- Acid leaching step In the acid leaching step, the heat-treated powder or granular material obtained through the heat treatment step is mixed with an acid solution or a reducing agent, and the powder or granular material is subjected to acid leaching treatment.
- acid leaching treatment a leachate in which the manganese component, the iron component, and the remaining zinc component are leached into the acid solution can be obtained from the powder or granular material.
- the carbon component remains as a solid state leaching residue.
- the acid used in the acid solution may be a general acid, and sulfuric acid, nitric acid, hydrochloric acid or other acids can be used. Although it can be appropriately selected depending on the price and purpose, it is preferable to use sulfuric acid or hydrochloric acid as the acid solution in consideration of cost and ease of procurement.
- sulfuric acid it is preferable to use dilute sulfuric acid having a sulfuric acid concentration of 1.4% or more and 45% or less in terms of mass% concentration. More specifically, the sulfuric acid concentration is preferably 1.4% or more, more preferably 2% or more, further preferably 5% or more, preferably 45% or less, more preferably 30% or less, still more preferably 25% or less.
- the sulfuric acid is more preferably dilute sulfuric acid having a concentration of 2% or more and 30% or less, and further preferably dilute sulfuric acid having a concentration of 5% or more and 25% or less.
- hydrochloric acid it is preferable to use dilute hydrochloric acid having a hydrochloric acid concentration of 1% or more and 14% or less in terms of mass% concentration. More specifically, the hydrochloric acid concentration is preferably 1% or more, more preferably 2% or more, preferably 14% or less, and more preferably 8% or less.
- the hydrochloric acid is more preferably dilute hydrochloric acid having a concentration of 2% or more and 8% or less.
- the "mass% concentration” here is a value obtained by dividing the mass of the acid in the acid solution by the mass of the entire solution and multiplying it by 100.
- the acid concentration required for leaching the manganese component, iron component and residual zinc component is the solid-liquid ratio of the powder or granular material to the acid solution, the amount of the powder or granular material, and the powder or granular material. It varies depending on the content of manganese, zinc and iron in the granules, the form of manganese and zinc in the granular material, and the like. Therefore, it is preferable to determine the optimum acid concentration by conducting a preliminary experiment assuming an actual machine in advance.
- an acid solution or a reducing agent is mixed with the powder or granular material that has undergone the heat treatment step. If the acid alone is not sufficient for leaching, a reducing agent is further added as needed to almost completely leaching the manganese component contained in the powder or granular material. Most of the manganese contained in the heat-treated granules is MnO, but a small amount of MnO 2 , Mn 2 O 3 , Mn 3 O 4, etc. may be contained. Of these, only a part of Mn O and Mn 3 O 4 dissolves only with acid.
- Manganese dissolves in an acid when it has a divalent valence, and in order to dissolve manganese, which has a valence such as trivalent or tetravalent, in an acid, it has a divalent valence. It needs to be reduced. Therefore, a reducing agent is required as a substance that supplies electrons for reduction.
- the amount of the reducing agent added is not particularly limited, but since it depends on the form of manganese contained in the powder or granular material, about 1 to 500 g / L with respect to the acid solution is sufficient.
- any of various commonly used reducing agents can be applied.
- the reducing agent include hydrogen peroxide H 2 O 2 , sodium sulfide Na 2 S ⁇ 9H 2 O, sodium bisulfite Na HSO 3 , sodium thiosulfite Na 2 S 2 O 3 , and iron sulfate FeSO 4 ⁇ 7H 2 O. ..
- Sulfur-based reducing agents may generate corrosive gases such as sulfurous acid gas and hydrogen sulfide gas, so caution is required from the viewpoint of safety and the like.
- the reducing agent is preferably hydrogen peroxide H 2 O 2.
- the zinc component contained in the powder or granular material almost the entire amount is dissolved (leached) if the acid concentration is increased regardless of the presence or absence of the reducing agent.
- the solid-liquid ratio (powder / granular material (g) / acid solution (L)) of the powder or granular material to the acid solution in the acid leaching step should be 50 g / L or more. Is preferable. On the other hand, if the solid-liquid ratio exceeds 800 g / L, the viscosity may increase and handling problems may occur, or the yield during the solid-liquid separation process may deteriorate. Therefore, the solid-liquid ratio is preferably 800 g / L or less.
- the treatment temperature of the acid leaching treatment is sufficient even at room temperature (around 15 to 25 ° C.), but heating may be performed. By heating, the reaction efficiency can be expected to improve as the temperature is raised within the range where the treatment solution does not boil.
- the treatment time of the acid leaching treatment is preferably 5 minutes or more, preferably 6 hours or less.
- Solid-liquid separation step In the solid-liquid separation step, the leachate obtained in the acid leaching step and the leaching residue are solid-liquid separated.
- the separated leachate contains manganese ions, iron ions, and residual zinc ions.
- the leaching residue of the separated solid is mainly the result of carbon remaining.
- the solid-liquid separation means is not particularly limited.
- a commonly used means for example, a means selected from gravity sedimentation separation, filtration, centrifugation, filter press, membrane separation and the like.
- the manganese extraction step includes a predetermined zinc removing step and an iron removing step in no particular order.
- the zinc removal step included in the manganese extraction step includes a sulfide precipitation treatment step in which sulfide is allowed to act on zinc ions to precipitate zinc ions, and a zinc separation step in which the obtained zinc-containing precipitate is separated. And include.
- the iron removal step included in the manganese extraction step includes an oxidation treatment step of oxidizing iron ions to precipitate iron ions and an iron separation step of separating the obtained iron-containing precipitate.
- an oxidation treatment step of oxidizing iron ions to precipitate iron ions and an iron separation step of separating the obtained iron-containing precipitate.
- zinc ions and iron ions are selectively precipitated to surely remove zinc ions and iron ions from the leachate, whereby the manganese component, which is the target component, is finally obtained with high purity. Can be obtained at.
- a zinc removal step including a sulfide precipitation treatment step for preferentially precipitating zinc ions and a zinc separation step may be performed first (procedure A), or oxidation for preferentially precipitating iron ions.
- the iron removing step including the treatment step and the iron separation step may be performed first (procedure B). From the viewpoint of facilitating the simplification of the process, it is preferable to perform the iron removing step first (procedure B).
- procedure A a mixture of a zinc-containing precipitate and a first solution containing manganese ions and iron ions is obtained from the leachate, and then these are separated. Further, in step B, after obtaining a mixture of the iron-containing precipitate and the first solution containing manganese ions and zinc ions from the leachate, these are separated.
- Zinc removal step (procedure A)
- a sulfide precipitation treatment step is first applied to the solid-liquid separated leachate.
- sulfide precipitation treatment step sulfide is allowed to act on the leachate, and the remaining zinc ions among the ions contained in the leachate are precipitated as zinc sulfide so that they can be removed from the leachate.
- a mixture of a first solution containing manganese ions and iron ions and a zinc-containing precipitate is obtained from the leachate.
- the leachate separated in the solid-liquid separation step contains manganese ions, iron ions, and residual zinc ions.
- the divalent metal ions contained are sulfide ions S. Reacts with 2- to form sulfide and precipitate.
- K SP solubility product
- MnS: K SP 2.5 x 10 -10
- ZnS: K SP 1.6 ⁇ 10 -24
- FeS: K SP 6.3 ⁇ 10 -18 (Lange, NA: Lange's Handbook of Chemistry.
- Examples of the sulfide to act include sodium hydrosulfide NaHS, sodium sulfide NaS, hydrogen sulfide H 2 S and the like. Since hydrogen sulfide is a gas, it needs to be aerated.
- the amount of sulfide to act is preferably 1.1 equivalents or more and 5 equivalents or less as sulfur S with respect to dissolved zinc.
- the amount of sulfide is preferably 1.1 equivalents or more, more preferably 2 equivalents or more, preferably 5 equivalents or less, more preferably 3 equivalents or less, still more preferably less than 3 equivalents, as sulfur S with respect to dissolved zinc.
- zinc ions can be reliably precipitated.
- the amount of sulfide is not more than the above lower limit, unintended precipitation of manganese ions can be suppressed, and the amount of sulfide acting can be prevented from becoming excessive, which is economically disadvantageous.
- the pH of the leachate in the sulfide precipitation treatment step is preferably 2 or more, more preferably 3 or more, preferably 6 or less, more preferably 5 or less, and even more preferably less than 5.
- the pH of the leachate is preferably pH 2 or more and 5 or less, more preferably pH 3 or more and 5 or less, and even more preferably pH 3 or more and less than 5.
- the mixture obtained in the above-mentioned sulfide precipitation treatment step is separated into a first solution and a zinc-containing precipitate (zinc separation step) to remove the zinc component.
- a zinc-containing precipitate zinc separation step
- the first solution containing manganese ions and iron ions obtained in the sulfide precipitation treatment step and the zinc-containing precipitate in which the remaining zinc sulfide is mainly precipitated are separated.
- the zinc component can be easily separated from the mixture after the sulfide precipitation treatment step, and a first solution containing manganese ions and iron ions can be obtained.
- the separation means is not particularly limited, and the solid-liquid separation step described above may be followed.
- Iron removal step (procedure A) In the procedure (A), an iron removing step is performed following the zinc removing step described above.
- the iron removal step in the procedure (A) first, the first solution containing manganese ions and iron ions obtained in the previous zinc removal step is subjected to an oxidation treatment step, and the iron ions in the first solution are precipitated with iron. As a product, the iron component can also be separated and removed.
- a mixture of a second solution (manganese-containing solution) containing manganese ions with high purity and an iron-containing precipitate can be obtained from the first solution.
- the oxidation treatment method in the procedure (B) described later may be followed, including the suitable pH of the first solution.
- the iron component in the first solution may not be completely separated and removed.
- this reducing agent consumes oxygen supplied by air aeration, the amount of oxygen is insufficient depending on the amount of air aeration, and iron content that cannot be separated and removed remains in the treated solution.
- air aeration is continued, the sulfide becomes sulfate ions, and finally the solution becomes oxidative and the iron component also precipitates.
- the aeration time becomes long and it is not practical.
- the oxidation treatment step in the procedure (A) it is preferable to apply air aeration and then add an oxidizing agent as a finish oxidation treatment.
- the amount of the oxidizing agent added is preferably adjusted so that the redox potential (vs. SHE) is measured and the redox potential is 550 mV or more.
- the oxidizing agent include hydrogen peroxide and potassium permanganate.
- the iron component is left for an appropriate period of time, and then the oxidation treatment step is performed, the iron component can be sufficiently precipitated by the treatment of only air aeration without performing the finish oxidation treatment.
- hydrogen sulfide which is a reducing substance
- the first solution generated in the sulfide precipitation treatment step in the previous stage is released into the air, and the first solution is easily oxidized, that is, the oxidation-reduction potential is likely to increase. It is thought that this is due to the fact that The appropriate period here depends on the storage condition such as whether it is a closed system or an open system, so it cannot be said unconditionally, but it is estimated to be about several days to one week.
- the mixture obtained in the above-mentioned oxidation treatment step is separated into a second solution and an iron-containing precipitate (iron separation step) to remove the iron component.
- iron separation step iron-containing precipitate
- Iron removal step (procedure B) In the iron removing step in the procedure (B), the leachate obtained in the solid-liquid separation step is first subjected to an oxidation treatment. In this oxidation treatment, the leachate is oxidized to precipitate iron ions among the ions contained in the leachate as an iron-containing precipitate, so that the iron component can be removed from the leachate first. By this treatment, a mixture of a first solution containing manganese ions and zinc ions and an iron-containing precipitate is obtained from the leachate.
- any of the usual oxidation treatment methods can be applied, but in the oxidation treatment step of the present embodiment, only air aeration, which is an inexpensive oxidation treatment method, is sufficient.
- air aeration it is economical to set normal practical conditions (infusion amount: (0.1 times to 1 times the amount of exudate) / minute, aeration time: 15 to 60 minutes). It is preferable from the above viewpoint.
- a treatment of adding an oxidizing agent may be added.
- the oxidation treatment is preferably performed by adjusting the pH of the leachate with a pH adjuster. If the pH of the leachate is too low, less than 3, the iron component will not precipitate. On the other hand, if the pH of the leachate exceeds 7 and is too high, the manganese component will also precipitate at the same time. Therefore, the leachate is preferably adjusted to a pH range of 3 to 7. The leachate is more preferably pH 5 or higher, more preferably pH 6 or lower, and even more preferably around pH 5 to pH 6. As a result, the iron component can be precipitated / separated and removed from the leachate, and a high-purity manganese-containing solution having a low impure content can be obtained.
- the mixture obtained in the above-mentioned oxidation treatment step is mixed with a first solution containing manganese ions and zinc ions and an iron-containing precipitate that may mainly contain iron hydroxide. (Iron separation step).
- the iron component can be easily separated and removed from the mixture after the oxidation treatment step, and a first solution containing a manganese component and a zinc component can be obtained.
- the separation means is not particularly limited, and the solid-liquid separation step described above may be followed.
- Zinc removal step (procedure B)
- a zinc removing step is performed following the iron removing step described above.
- sulfide is allowed to act on the first solution obtained in the previous iron removal step, and zinc ions among the ions in the first solution are mainly precipitated as zinc sulfide and remain.
- the zinc component is also made removable from the first solution.
- a mixture of a second solution (manganese-containing solution) containing manganese ions with high purity and a zinc-containing precipitate can be obtained from the first solution.
- the first solution separated in the previous iron removal step contains manganese ions and zinc ions, and when sulfide is allowed to act on the first solution, it is the same as the sulfide precipitation treatment step in the above procedure (A).
- the zinc component selectively precipitates as a sulfide.
- the concentration of sulfide ions, and the pH of the first solution the zinc ion concentration in the first solution can be easily reduced below the analysis limit (0.1 mg / L). Can be done.
- the type of sulfide and the suitable pH of the first solution may be determined according to the sulfide precipitation treatment method in the above-mentioned procedure (A).
- the pH of the first solution is particularly preferably pH: 4.
- the amount of sulfide to act is preferably 1.1 equivalents or more, more preferably 2 equivalents or more, and preferably 5 equivalents or less as sulfur S with respect to dissolved zinc. If the amount of sulfide to act is less than 1.1 equivalents, zinc precipitation removal is progressing but incomplete and the final removal rate is not stable. If the amount of sulfide to act is 2 equivalents or more, the removal of zinc precipitates is also remarkable. On the other hand, if the amount of sulfide to be acted exceeds 5 equivalents, the amount of sulfide to be acted becomes excessive, and manganese may also be precipitated and removed.
- the mixture obtained in the above-mentioned sulfide precipitation treatment step is separated into a second solution and a zinc-containing precipitate in which zinc sulfide is mainly precipitated (zinc separation). Step), remove the zinc component. In this way, the remaining zinc component can also be removed, and the solution can be recovered as a high-purity solution containing only the manganese component.
- the separation means is not particularly limited, and the solid-liquid separation step described above may be followed.
- the carbon component, zinc component, and iron component other than the manganese component contained in the waste dry battery can be almost completely separated and removed, and the manganese contained in the waste dry battery can be removed from the zinc component and iron component. It can be recovered with a high yield as a high-purity manganese-containing solution reduced to less than the analysis limit.
- the obtained manganese-containing solution may be used for various purposes as, for example, alkali-precipitated as a high-purity manganese hydroxide. Further, the obtained manganese-containing solution may be mixed with other metals such as Ni and then subjected to an alkali precipitation treatment or the like to be used as a material for a secondary battery electrode material.
- the recovery equipment of the present invention is provided in order with a sorting device, a crushing device, a sieving device, a heating device, an acid leaching tank, a solid-liquid separation device, and a manganese extraction device group, and has the same features and effects as the manganese recovery method of the present invention.
- the manganese extraction device group includes a predetermined zinc removal device group and an iron removal device group in no particular order. Then, the manganese recovery equipment of the present invention can be suitably used, for example, when carrying out the manganese recovery method of the present invention.
- FIG. 9 shows a configuration (A) in which the above procedure (A) can be preferably performed.
- the recovery equipment includes a sorting device 10, a crushing device 20a, a sieving device 20b, a heating device 110, an acid leaching tank 30, a solution separating device 40, and sulfide.
- the precipitation treatment tank 52, the zinc separation device 62, the oxidation treatment tank 82, the iron separation device 92, and the manganese-containing solution recovery tank 100 can be provided in this order.
- the sulfide precipitation treatment tank 52 and the zinc separation device 62 form a zinc removal device group
- the oxidation treatment tank 82 and the iron separation device 92 form an iron removal device group.
- the zinc removing device group and the iron removing device group constitute a manganese extraction device group.
- the sorting device 10 sorts manganese dry batteries and / or alkaline manganese dry batteries from waste batteries.
- the type of the sorting device is not particularly limited, and an example of a device for sorting using a shape, radiation, or the like can be exemplified.
- the waste batteries may be sorted by hand.
- Any ordinary crusher can be applied to the crusher 20a, but it is preferable that the crusher 20a is a biaxial rotary type crusher.
- the sieving device 20b preferably includes a sieve having a mesh size of 1 mm or more and 20 mm or less.
- the opening of the sieving device 20b is preferably about 1 mm or more, preferably 20 mm or less, more preferably 10 mm or less, still more preferably 3 mm or less, for the same reason as described above for the manganese recovery method.
- the heating device 110 is a device capable of subjecting the powder or granular material obtained through the crushing device 20a and the sieving device 20b to a heat treatment for heating to a set temperature in a non-oxidizing atmosphere having an inert atmosphere or a reducing atmosphere.
- the structure is not particularly limited. If the heating device is a batch type, a heating furnace capable of adjusting the normal atmosphere is suitable. Further, if the heating device is a continuous type, a rotary kiln or the like capable of heating to a set temperature and adjusting the atmosphere is suitable.
- the atmosphere adjustment referred to here also includes a means for collecting exhaust gas containing zinc vapor.
- the acid leaching tank 30 is preferably a general stirring tank equipped with a stirrer in the tank because the powder or granular material is mixed with an acid solution or a reducing agent to promote the leaching reaction.
- the sulfide precipitation treatment tank 52 is subjected to the sulfide treatment in which the leachate is treated with sulfide to act on the leachate, it is preferable to use a general stirring tank equipped with a stirrer in the tank.
- the oxidation treatment tank 82 is subjected to the oxidation treatment on the first solution, it is preferable to use a general stirring tank equipped with a stirrer in the tank.
- each separation device is provided with recovery tanks 70a, 72b, 72c capable of recovering the solid-liquid separated precipitate and the like.
- the manganese-containing solution recovery tank 100 preferably collects the manganese-containing solution (second solution) solid-liquid separated by the iron separation device 92, can store the liquid, and is configured to be freely dispensed.
- FIG. 10 shows a configuration (B) in which the above procedure (B) can be preferably performed.
- the recovery equipment includes a sorting device 10, a crushing device 20a, a sieving device 20b, a heating device 110, an acid leaching tank 30, a solid-liquid separation device 40, and an oxidation treatment.
- a tank 53, an iron separation device 63, a sulfide precipitation treatment tank 83, a zinc separation device 93, and a manganese-containing solution recovery tank 100 can be provided in this order.
- the oxidation treatment tank 53 and the iron separation device 63 form an iron removal device group
- the sulfide precipitation treatment tank 83 and the zinc separation device 93 form a zinc removal device group.
- the iron removing device group and the zinc removing device group constitute a manganese extraction device group.
- the sorting device 10 the crushing device 20a, the sieving device 20b, the heating device 110, the acid leaching tank 30, the solid-liquid separating device 40, the iron separating device 63, the zinc separating device 93, the recovery tank 70a, 73b, 73c, manganese.
- the containing solution recovery tank 100 is as described above for the configuration A. Since the leaching solution is subjected to an oxidation treatment, the oxidation treatment tank 53 is preferably a general stirring tank equipped with a stirrer in the tank.
- the sulfide precipitation treatment tank 83 is subjected to the sulfide precipitation treatment in which the sulfide acts on the first solution, it is preferable to use a general stirring tank equipped with a stirrer in the tank.
- a general stirring tank equipped with a stirrer in the tank it is preferable to use a general stirring tank equipped with a stirrer in the tank.
- the structures, etc. of the various devices, reaction tanks, and recovery tanks constituting the recovery equipment are not limited as long as they have the above-mentioned functions.
- Example 1 Preparation of powders and granules The process of selecting manganese dry batteries and alkaline manganese dry batteries from waste batteries, and crushing the selected waste dry batteries and sieving them with a sieve with a mesh size of 2.8 mm to obtain powder and granules of the waste batteries. The separation step was performed to obtain powders and granules of waste batteries.
- the composition of the obtained powder or granular material is shown in Table 1.
- the obtained powder or granular material contains oxygen derived from an oxide or a hydroxide, some hydrogen, and water.
- a heat treatment step was performed in which the obtained powder or granular material was charged into the heating device 110 and heat-treated without adding graphite.
- the heat treatment was performed in an inert N 2 atmosphere with a heating temperature of 1000 ° C. and a heating time of 1 hour.
- the powder or granular material obtained through the heat treatment step was put into the acid leaching tank 30 and subjected to the acid leaching step.
- 100 mL of an acid solution was mixed with 10 g of the powder or granular material, and an acid leaching treatment was performed to leach manganese, zinc and iron from the powder or granular material.
- the acid concentration of the acid solution was sulfuric acid concentration: 3N (mass% concentration: about 13.2%).
- the acid leaching treatment time was 1 hour, and the acid leaching treatment was a stirring treatment.
- the solid-liquid ratio which is the ratio of the powder or granular material to the acid solution, is 100 g / L, and the amount of the reducing agent added to the acid solution is 100 g / L.
- the obtained leachate and the leachate residue were charged into the solid-liquid separation device 40, filtered through a filter paper having a pore size of 1 ⁇ m, and subjected to a solid-liquid separation step of solid-liquid separation.
- the manganese concentration, zinc concentration, and iron concentration in the obtained leachate were quantified by ICP emission spectrometry.
- Table 2 shows the concentrations (mg / L) of each component of manganese, zinc, and iron in the leachate after the solid-liquid separation step.
- the manganese mass in the leachate was calculated based on the manganese concentration in the obtained leachate, and the ratio of the manganese mass in the leachate to the manganese mass in the powder or granular material after the heat treatment, which was separately measured (manganese). (Element conversion) was calculated and used as the manganese leaching rate. The manganese leaching rate was 100%.
- the leachate obtained by the solid-liquid separation step was charged into the sulfide precipitation treatment tank 52, and a sulfide precipitation treatment step of allowing sulfide to act was performed.
- sodium hydrosulfide NaHS as a sulfide was added to the leachate so as to have 2 equivalents of sulfur S with respect to dissolved zinc.
- Sodium hydrosulfide was added in the form of a solution dissolved in distilled water.
- the pH of the leachate during the sulfide precipitation treatment was adjusted with a pH adjusting solution (3M sulfuric acid or 100 g / L sodium hydroxide) so as to be 4.
- the treatment time for the sulfide precipitation treatment was 30 minutes, and the treatment was agitation.
- the mixture after the above-mentioned sulfide precipitation treatment step is charged into the zinc separator 62, and a zinc separation step of suction filtration with a filter paper having a pore size of 1 ⁇ m for solid-liquid separation is performed to separate the first solution and the zinc-containing precipitate. did. Then, the components of the obtained first solution were quantitatively analyzed by ICP emission spectrometry. The amounts of the sodium hydrosulfide solution and the pH adjuster added were recorded, and the effect of dilution with these solutions was corrected from the analytical values. The obtained results are also shown in Table 2 as "the first solution after the zinc removal step".
- the first solution obtained through the zinc removing step was charged into the oxidation treatment tank 82, and the oxidation treatment step of carrying out the oxidation reaction was performed.
- the oxidation treatment step as an oxidation treatment, first, the obtained first solution was aerated with air.
- the conditions for air aeration were the amount of blown water: (the same volume as the amount of the first solution) / minute, and the aeration time: 30 minutes.
- the components contained in the first solution which was suction-filtered with a filter paper having a pore size of 1 ⁇ m, were quantitatively analyzed by the above method.
- the obtained results are also shown in Table 2 as "intermediate solution after oxidation treatment".
- an oxidizing agent was added to the first solution immediately after the above air aeration.
- a pH adjusting solution (3M sulfuric acid or 100g / L sodium hydroxide) so that the pH of the first solution becomes 5
- hydrogen peroxide solution is used as an oxidizing agent, and the redox potential is 550 mV or more.
- Approximately 8 to 16 mL was added so as to become. In this way, the iron component in the first solution was precipitated as iron hydroxide so that it could be removed.
- the treatment time with the oxidizing agent was 30 minutes.
- An iron separation step is performed in which the mixture after the oxidation treatment step by air aeration and addition of an oxidizing agent is charged into an iron separator 92, suction-filtered with a filter paper having a pore size of 1 ⁇ m, and solid-liquid separated into a second solution and an iron-containing precipitate. gave.
- the components contained in the obtained second solution were quantitatively analyzed by the above method.
- the amount of hydrogen peroxide solution and pH adjuster added was recorded, and the effect of dilution with these solutions was corrected from the analytical values.
- the obtained results are also shown in Table 2 as "the second solution after the iron removal step".
- Example 2 The powder or granular material was prepared in the same manner as in Example 1 to obtain a powder or granular material having the composition shown in Table 1. Further, when a leachate was prepared in the same manner as in Example 1, the contents (mg / L) of each component of manganese, zinc, and iron in the leachate after the solid-liquid separation step were as shown in Table 3. The manganese leaching rate obtained in the same manner as in Example 1 was 100%.
- the solution obtained through the second solid-liquid separation step was left at room temperature for one week, and then charged into the oxidation treatment tank 82 to carry out an oxidation treatment step of performing an oxidation reaction.
- the first solution obtained as the oxidation treatment was aerated with air.
- the conditions for air aeration were the amount of blown water: (the same volume as the amount of the first solution) / minute, and the aeration time: 30 minutes.
- the components contained in the first solution which was suction-filtered with a filter paper having a pore size of 1 ⁇ m, were quantitatively analyzed by the above method.
- the obtained results are also shown in Table 3 as "the second solution after the iron removal step".
- Example 3 The powder or granular material was prepared in the same manner as in Example 1 to obtain a powder or granular material having the composition shown in Table 1. Further, when the leachate was prepared in the same manner as in Example 1, the contents (mg / L) of each component of manganese, zinc, and iron in the leachate after the solid-liquid separation step were as shown in Table 4. The manganese leaching rate obtained in the same manner as in Example 1 was 100%.
- the leachate separated in the solid-liquid separation step was subjected to an oxidation treatment step.
- the obtained leachate was aerated with air to generate iron hydroxide from the iron component contained in the leachate, and the iron component could be separated and removed from the leachate as an iron-containing precipitate.
- the conditions for air aeration were the amount of blown water: (mL in the same volume as the amount of exudate) / minute, and the aeration time: 30 minutes.
- the leachate was adjusted to pH: 5 with a pH adjuster (3M sulfuric acid or 100 g / L sodium hydroxide).
- the first solution and the iron-containing precipitate were suction-filtered with a filter paper having a pore size of 1 ⁇ m, and separated into the first solution and the iron-containing precipitate (iron separation step). Then, the components (Mn, Zn, Fe) contained in the first solution obtained in the iron removal step were quantitatively analyzed by ICP emission spectrometry. The amount of the pH adjuster added was recorded, and the effect of dilution by the pH adjuster on the measured value was corrected. The concentrations (mg / L) of each component of manganese, zinc, and iron in the obtained first solution are also shown in Table 4 as "the first solution after the iron removal step".
- sulfide is allowed to act on the first solution separated in the iron separation step, and zinc ions mainly contained in the first solution are precipitated as zinc sulfide (zinc-containing precipitate), and separated and removed from the first solution.
- a sulfide precipitation treatment step was performed to make it possible.
- the sulfide used was sodium hydrosulfide NaHS, which was added to dissolved zinc in an amount of 2 equivalents of sulfur S.
- Sodium hydrosulfide was added in the form of a solution dissolved in distilled water.
- the pH of the first solution during the sulfide precipitation treatment was adjusted with a pH adjusting solution (3M sulfuric acid or 100 g / L sodium hydroxide) so as to be 4.
- the treatment time for the sulfide precipitation treatment was 30 minutes, and the treatment was agitation.
- the mixture after the sulfide precipitation treatment was suction-filtered with a filter paper having a pore size of 1 ⁇ m, and separated into a second solution and a zinc-containing precipitate (zinc separation step). Then, the components of the second solution obtained after separation were quantitatively analyzed by ICP emission spectrometry. The amounts of the sodium hydrosulfide solution and the pH adjuster added were recorded, and the effect of dilution with these solutions was corrected from the measured values. The obtained results are also shown in Table 4 as "the second solution after the zinc removal step".
- Sorting device 20a Crushing device 20b Sieving device 30 Acid leaching tank 40 Solid-liquid separation device 52 Sulfide precipitation treatment tank (Structure A) 53 Oxidation treatment tank (Structure B) 62 Zinc Separator (Configuration A) 63 Iron Separator (Configuration B) 70a, 72b, 72c, 73b, 73c Recovery tank 82 Oxidation treatment tank (Structure A) 83 Sulfide precipitation treatment tank (Structure B) 92 Iron Separator (Configuration A) 93 Zinc Separator (Structure B) 100 Manganese-containing solution recovery tank 110 Heating device
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Abstract
Description
さらに、特許文献2以外の上記した特許文献に記載された技術により廃乾電池から回収されたマンガンはいずれも、二次電池の電極材用原料としては純度が低いという問題がある。
なお、ここでいう「高純度のマンガン含有溶液」とは、溶液中に、不純物として、亜鉛(Zn)、鉄(Fe)、炭素(C)等が常用のJIS規格に規定される分析法を用いた分析でいずれも分析限界未満、例えば0.1mg/L未満であるマンガン含有溶液をいうものとする。
その結果、本発明者らは、上記のとおり得られた粉粒体に、まず所定の加熱処理を施すことに思い至った。本発明者らは、上記粉粒体に、不活性ガス雰囲気または還元性雰囲気中(つまり、非酸化性雰囲気中)で加熱処理を施すと、粉粒体に含まれる亜鉛を高効率で、高純度亜鉛として、容易に除去することができることを知見した。
そして、さらに、本発明者らは、加熱処理済みの粉粒体に酸と還元剤とを作用させて、マンガン、鉄、さらに残存する亜鉛を浸出させた浸出液を得たのち、この浸出液から、所定の手順に従って、残存する亜鉛成分と、鉄成分とを選択的に沈殿・分離させれば、その沈殿・分離工程の順序にかかわらず、高純度のマンガン溶液を簡便かつ安価に得ることができることを知見した。
そして、亜鉛を分析限界未満となるまでに分離した第1溶液に、さらに酸化処理工程を施し、鉄イオンを鉄含有沈殿物として更に分離(鉄分離工程)すれば、鉄成分の分離後に残された溶液(第2溶液)として、高純度のマンガン溶液を簡便かつ安価に得ることができることを知見した(手順Aにおける鉄除去工程)。
そして、鉄成分を分離した後の第1溶液に、続いて水硫化ナトリウムNaHS等の硫化物を作用させる硫化物沈殿処理を施して、残存する亜鉛イオンを亜鉛含有沈殿物として更に分離すれば、分離後に残された溶液(第2溶液)として、高純度のマンガン溶液を簡便かつ安価に得ることができることを知見した。
廃乾電池から、マンガン乾電池およびアルカリマンガン乾電池を選別し(選別工程)、更に破砕・篩い分け工程を施して粉粒体を得た。
得られた粉粒体に、さらに還元剤として黒鉛を、黒鉛配合比率(:黒鉛/粉粒体)として、質量比で0~1の範囲となるように配合した。ついで、各種比率で黒鉛を配合した粉粒体に、非酸化性雰囲気である窒素ガス雰囲気の加熱炉で、加熱温度:1000℃、加熱時間:30分の加熱処理工程を施した。加熱処理前後の粉粒体について、重量および亜鉛含有量を測定し、加熱処理前と加熱処理後との粉粒体に含まれる亜鉛含有量の差から、次式に従って加熱処理による亜鉛除去率を算出した。
亜鉛除去率[%]=(加熱処理前の粉粒体中のZn含有量[kg]-加熱処理後の粉粒体中のZn含有量[kg])×100/加熱処理前の粉粒体中のZn含有量[kg]
得られた結果を、加熱処理工程における還元剤(黒鉛)の配合比率と亜鉛除去率との関係を示すグラフとして図4に示す。
さらに図4からは、黒鉛の配合比率を高めるにつれて亜鉛除去率は上昇し、最大で96%の亜鉛除去率が得られることもわかる。しかし、図4から判断して、黒鉛配合比率が0.5を超えて高まっても、亜鉛除去率の著しい向上は望めないこともわかる。
廃乾電池から、マンガン乾電池やアルカリマンガン乾電池を選別し、更に破砕・篩い分け工程を施して得られた粉粒体に、黒鉛等の還元剤を添加することなく窒素雰囲気(不活性雰囲気)中で加熱温度:1000℃で30分間加熱処理を施した。得られた加熱処理済みの粉粒体に、酸溶液と還元剤とを混合する酸浸出工程を実施した。酸浸出処理条件はつぎのとおりとした。この酸浸出工程によって、少なくともマンガンイオンと、残存する亜鉛イオンと、鉄イオンとを含有する浸出液と、それ以外の浸出残渣との混合物が得られた。
酸溶液:硫酸50mL
硫酸濃度:1.5mol/L(質量%濃度約13.2%)
還元剤:35%過酸化水素水H2O2
還元剤添加量:0g(0g/L)、0.56g(11g/L)、1.1g(22g/L)、1.7g(33g/L)、2.2g(45g/L)
酸浸出処理時間:1時間(攪拌処理)
粉粒体と酸溶液との固液比:100g/L
なお、加熱処理前の粉粒体に含まれる/添加される黒鉛量や、加熱温度、加熱時間といった加熱条件によっては、加熱処理後であってもMnO2、Mn2O3、Mn3O4といったMn形態が残り、酸のみでマンガンが全量浸出しない場合もある。そのような場合は、還元剤(過酸化水素水)を添加すれば、MnO2、Mn2O3、Mn3O4として存在するマンガンもMn2+として浸出させることが可能である。
得られた浸出液中のマンガン濃度、亜鉛濃度、鉄濃度を、ICP発光分析法で定量分析したところ、マンガン濃度は66198mg/L、亜鉛濃度は5031mg/L、鉄濃度は1131mg/Lであった。
硫化物沈殿処理の条件はつぎのとおりとした。
浸出液:100mL
硫化物の種類:水硫化ナトリウム(NaHS)
硫化物の添加量:溶解亜鉛に対して硫黄として1~3当量
反応中の浸出液のpH:0.5~5
pH調整剤:3M硫酸または100g/L水酸化ナトリウム
処理時間:水硫化ナトリウム添加後0.5時間(撹拌処理)
そして、硫化物沈殿処理後、孔径1μmのろ紙で吸引ろ過して固液分離を行い(亜鉛分離工程)、分離された第1溶液の成分(亜鉛、鉄、マンガン)をICP発光分析法で定量分析した。なお、得られた分析値は、水硫化ナトリウム溶液とpH調整剤の添加で希釈された影響を補正した。得られた結果を図7に示す。図7にはマンガンの分析結果は図示していない。
一方、図7(b)に示すように、硫化物の添加量が2当量(NaHS:2当量)となると、亜鉛の沈殿除去が顕著になっている。とくに、浸出液のpHが3以上である条件では、亜鉛除去工程(硫化物沈殿処理工程および亜鉛分離工程)後の第1溶液中の亜鉛濃度が分析限界(0.1mg/L)未満となるまで除去されていることがわかる。また、図7(c)に示す硫化物の添加量が3当量(NaHS:3当量)の場合でも、2当量の場合と同様の傾向を示し、とくに、pHが3以上であるときの亜鉛濃度が分析限界(0.1mg/L)を下回り、亜鉛の沈殿除去が顕著となっている。
実験(A)と同様の手法に従い、固液分離工程によって分離された浸出液中のマンガン濃度、亜鉛濃度、鉄濃度をICP発光分析法により測定したところ、マンガン濃度は66198mg/L、亜鉛濃度は5031mg/L、鉄濃度は1131mg/Lであった。
吹込み量:(浸出液量と同体積)/分
曝気時間:30分
反応中の浸出液のpH:4~6
pH調整剤:3M硫酸または100g/L水酸化ナトリウム
ここで、吹込み量および曝気時間は、通常の実用的な条件(吹込み量:溶液量に対して0.1~1倍量/分、曝気時間:15~60分)の範囲内である。
そして、空気曝気後の浸出液全量を孔径:1μmのろ紙で吸引ろ過して固液分離し(鉄分離工程)、分離された第1溶液の成分濃度(亜鉛、鉄、マンガン)をICP発光分析法で測定した。なお、得られた測定値については、pH調整剤による希釈の影響を補正した。得られた結果を図8に示す。酸化処理工程によるマンガンおよび亜鉛の沈殿はほとんど確認されなかったため、図8には、鉄除去工程(酸化処理工程および鉄分離工程)後の第1溶液中の鉄濃度のみを示す。
硫化物沈殿処理の条件は次のとおりとした。
第1溶液:100mL
硫化物の種類:水硫化ナトリウム(NaHS)
硫化物の添加量:溶解亜鉛に対して硫黄として、1~3当量
反応中の第1溶液のpH:0.5~5
pH調整剤:3M硫酸または100g/L水酸化ナトリウム
処理時間:水硫化ナトリウム添加後0.5時間(撹拌処理)
上記した硫化物沈殿処理工程後、孔径1μmのろ紙で吸引ろ過して固液分離を行い(亜鉛分離工程)、分離された第2溶液について、その成分をICP発光分析法で分析した。
一方、硫化物の添加量が2当量(NaHS:2当量)となると、亜鉛の沈殿除去が顕著になり、とくに、第1溶液のpHが3以上である条件では、亜鉛除去工程後の第2溶液中の亜鉛濃度は分析限界(0.1mg/L)未満となるまでに、沈殿・除去されることを見出した。
また、硫化物の添加量が3当量(NaHS:3当量)の場合でも、2当量の場合と同様の傾向を示し、亜鉛の沈殿除去が顕著となることを知見した。なお、硫化物の添加量が3当量の場合(NaHS:3当量)には、pHが5程度になると、マンガンの沈殿除去も大きくなる傾向を示した。
(1)廃乾電池からマンガン乾電池および/またはアルカリマンガン乾電池を選別する選別工程と、
前記選別工程で選別された前記マンガン乾電池および/または前記アルカリマンガン乾電池を破砕、篩い分けして粉粒体を得る破砕・篩い分け工程と、
前記破砕・篩い分け工程で得られた前記粉粒体に、非酸化性雰囲気中で加熱処理を施す加熱処理工程と、
前記加熱処理工程を施された粉粒体に、酸溶液、あるいはさらに還元剤を混合して、該粉粒体が含有するマンガン、亜鉛および鉄を該粉粒体から浸出させて、マンガンイオン、亜鉛イオンおよび鉄イオンを含有する浸出液を得る酸浸出工程と、
前記酸浸出工程で得られた前記浸出液とそれ以外の浸出残渣とを分離する固液分離工程と、
前記固液分離工程で分離された前記浸出液から、前記亜鉛イオンおよび鉄イオンを除去して、前記マンガンイオンを含有する溶液を得るマンガン抽出工程と、
をこの順に施す、廃乾電池からのマンガン回収方法であって、
前記マンガン抽出工程が、
前記亜鉛イオンに硫化物を作用させて該亜鉛イオンを沈殿させる硫化物沈殿処理工程と、さらに、得られた亜鉛含有沈殿物を分離する亜鉛分離工程と、を含む亜鉛除去工程と;
前記鉄イオンを酸化させて該鉄イオンを沈殿させる酸化処理工程と、さらに、得られた鉄含有沈殿物を分離する鉄分離工程と、を含む鉄除去工程と;
を順不同に含むことにより、高純度のマンガン含有溶液を得ることを特徴とする廃乾電池からのマンガン回収方法。
前記亜鉛除去工程では、前記浸出液に硫化物を作用させて該浸出液中の亜鉛イオンを沈殿させる硫化物沈殿処理工程を施した後に、該硫化物沈殿処理工程で得られた亜鉛含有沈殿物とマンガンイオンおよび鉄イオンを含有する第1溶液とを固液分離し、
前記鉄除去工程では、前記亜鉛除去工程で得られた前記第1溶液を酸化させて該第1溶液中の鉄イオンを沈殿させる酸化処理工程を施した後に、該酸化処理工程で得られた鉄含有沈澱物とマンガンイオンを含有する第2溶液とを固液分離することを特徴とする、廃乾電池からのマンガン回収方法。
前記鉄除去工程では、前記浸出液を酸化させて該浸出液中の鉄イオンを沈殿させる酸化処理工程を施した後に、該酸化処理工程で得られた鉄含有沈澱物とマンガンイオンおよび亜鉛イオンを含有する第1溶液とを固液分離し、
前記亜鉛除去工程では、前記鉄除去工程で得られた前記第1溶液に硫化物を作用させて該第1溶液中の亜鉛イオンを沈殿させる硫化物沈殿処理工程を施した後に、該硫化物沈殿処理工程で得られた亜鉛含有沈澱物とマンガンイオンを含有する第2溶液とを固液分離することを特徴とする、廃乾電池からのマンガン回収方法。
前記選別装置で選別された前記マンガン乾電池および/またはアルカリマンガン乾電池を装入して破砕処理を施し、破砕処理物を得る破砕装置と、
前記破砕装置で得られた前記破砕処理物に篩い分け処理を施して粉粒体を得る篩い分け装置と、
前記篩い分け装置で得られた前記粉粒体に、非酸化性雰囲気中で加熱処理を施す加熱装置と、
前記加熱装置で加熱処理された前記粉粒体に、酸溶液、あるいはさらに還元剤を混合して、該粉粒体が含有するマンガン、亜鉛および鉄を該粉粒体から浸出させて、マンガンイオン、亜鉛イオンおよび鉄イオンを含有する浸出液を得る酸浸出槽と、
前記酸浸出槽で得られた前記浸出液と浸出残渣とを分離する固液分離装置と、
前記固液分離装置で分離された前記浸出液から、前記亜鉛イオンおよび鉄イオンを除去して、前記マンガンイオンを含有する溶液を得るマンガン抽出装置群と、
をこの順で備える、廃乾電池からのマンガン回収設備であって、
前記マンガン抽出装置群が、
前記亜鉛イオンに硫化物を作用させて該亜鉛イオンを沈殿させる硫化物沈殿処理槽と、さらに、得られた亜鉛含有沈殿物を固液分離する亜鉛分離装置と、を含む亜鉛除去装置群と、
前記鉄イオンを酸化させて該鉄イオンを沈殿させる酸化処理槽と、さらに、得られた鉄含有沈殿物を固液分離する鉄分離装置と、を含む鉄除去装置群と;
を順不同に含むことにより、廃乾電池から有価成分を回収することを特徴とする、廃乾電池からのマンガン回収設備。
以下、本発明の実施形態について、図を参照して具体的に説明する。以下の実施形態は、本発明の好適な一例を示すものであり、これらの例によって本発明が何ら限定されるものではない。
本発明のマンガンの回収方法は、図1に示すように、選別工程、破砕・篩い分け工程、加熱処理工程、酸浸出工程、固液分離工程、およびマンガン抽出工程を順に有する。また、マンガン抽出工程は、所定の亜鉛除去工程および鉄除去工程を順不同で含む。
本発明のマンガン回収方法が上記所定の工程に従うことにより、廃乾電池に含まれるマンガン以外の成分を、順に、確実に除去することができる。その結果、本発明のマンガン回収方法に従えば、廃乾電池を利用して、マンガン成分を、二次電池電極材用の原料として利用できる程度の高純度で、容易に回収可能である。
廃乾電池は、様々な種類のものが混在した形で回収されるのが一般的である。このため、本発明では、回収された廃乾電池の中から、マンガン乾電池および/またはアルカリマンガン乾電池を選別する。後の工程でマンガン成分を効率的に抽出するために、マンガン乾電池のみを選別してもよく、アルカリマンガン乾電池のみを選別してもよく、マンガン乾電池およびアルカリマンガン乾電池の両方を選別してもよい。選別方法としては、手選別、機器を利用する機械選別など、いずれの方法を用いてもよい。
次に、選別工程で選別したマンガン乾電池および/またはアルカリマンガン乾電池を破砕する。破砕の目的は、選別工程で選別したマンガン乾電池および/またはアルカリマンガン乾電池の構成材料から、マンガン、亜鉛、炭素以外の成分を含む材料を可能な限り排除することにある。
これらの廃乾電池を破砕すると、包装材(鉄、プラスチックおよび紙等)や、マンガン乾電池の負極材料である亜鉛缶、アルカリマンガン乾電池の集電体である真鍮棒は、箔状または片状の固形物となる。一方、正極材料である二酸化マンガン、マンガン乾電池の集電体である炭素棒、アルカリマンガン乾電池の負極材料である亜鉛粉、放電により生成したMnO(OH)、Zn(OH)2、Mn(OH)2、ZnOなどの化合物、および各種電解液は、箔状・片状の固形物よりも更に細かい粉粒体となる。
上記した破砕物の篩い分け(箔状または片状の固形物と、粉粒体との篩い分け)に使用する篩の目開きは、おおよそ、1mm以上が好ましく、20mm以下が好ましく、10mm以下がより好ましく、3mm以下が更に好ましい。篩の目開きは、1~20mm程度が好ましく、1~10mm程度がより好ましく、1~3mm程度が更に好ましい。篩の目開きが上記下限以上であれば、マンガン成分を含む粉粒体をより多く確保できる。また、篩の目開きが上記上限以下であれば、マンガン以外の目的外成分を含む固形物をより排除でき、後の工程をより効率的に行える。
このように、破砕・篩い分け工程を経て得られた粉粒体は、マンガン乾電池および/またはアルカリマンガン乾電池の主要構成材料である、二酸化マンガン、炭素、塩化亜鉛または塩化アンモン、苛性カリ、更には、放電によって生成したMnO(OH)、Zn(OH)2、Mn(OH)2、ZnOなどが混合した粉粒体である。なお、通常、この粉粒体には、鉄成分が不可避的に混入する。
破砕・篩い分け工程を経て得られた粉粒体に、加熱処理工程として、不活性雰囲気中または還元性雰囲気中などの非酸化性雰囲気中で加熱処理を施す。粉粒体中の亜鉛(Zn)は主としてZnOとして存在しており、加熱処理を施すことにより、粉粒体中の黒鉛とZnOとが反応し、ZnOから亜鉛(Zn)へと還元される。加熱処理を酸化性雰囲気中で行うと、粉粒体中の黒鉛、あるいは還元剤として混合した黒鉛の一部が、ZnOではなく、雰囲気中の酸素と反応して燃焼するため、ZnOから亜鉛への還元反応が阻害され、粉粒体からの亜鉛の除去率が低下する。このため、加熱処理は非酸化性雰囲気中で行うこととし、不活性雰囲気中で行ってもよく、還元性雰囲気中で行ってもよい。
なお、金属系の還元剤を使用すると、未反応の還元剤が後続の工程で使用する酸で溶解し、マンガン含有溶液の品位を低下させる恐れがあるため、使用する還元剤は非金属系の炭素材料とすることが好ましい。
酸浸出工程では、加熱処理工程を経て得られた加熱処理済み粉粒体に、酸溶液とあるいはさらに還元剤とを混合して、粉粒体に酸浸出処理を施す。この酸浸出処理により、粉粒体から、主にマンガン成分、鉄成分、さらに残存する亜鉛成分が酸溶液に浸出された浸出液が得られる。なお、炭素成分は固体状態の浸出残渣として残存する。
る。
硫酸を用いる場合には、硫酸濃度が質量%濃度で1.4%以上45%以下の希硫酸を用いることが好ましい。より具体的には、硫酸濃度は、1.4%以上が好ましく、2%以上がより好ましく、5%以上が更に好ましく、45%以下が好ましく、30%以下がより好ましく、25%以下が更に好ましい。硫酸は、濃度が2%以上30%以下の希硫酸であることがより好ましく、さらに好ましくは、濃度が5%以上25%以下の希硫酸である。
塩酸を用いる場合には、塩酸濃度が質量%濃度で1%以上14%以下の希塩酸を用いることが好ましい。より具体的には、塩酸濃度は、1%以上が好ましく、2%以上がより好ましく、14%以下が好ましく、8%以下がより好ましい。塩酸は、濃度が2%以上8%以下の希塩酸であることがより好ましい。
使用する硫酸または塩酸は、市販されているものであればいずれも使用できるが、工業用或いは有害金属成分の少ない廃酸を希釈して使用すれば、酸のコストを低減することができる。また、ここでの「質量%濃度」は、酸溶液中の酸の質量を溶液全体の質量で除したものに100を乗じた値である。
なお、粉粒体に含まれる亜鉛成分については、還元剤の有無に拘わらず酸の濃度を上昇していけば、ほぼ全量が溶解(浸出)する。
固液分離工程では、酸浸出工程で得られた浸出液と浸出残渣とを固液分離する。分離された浸出液は、マンガンイオン、鉄イオン、および残存する亜鉛イオンを含有する。一方、分離された固体の浸出残渣は、主として炭素が残留した結果である。これにより、粉粒体に含まれていたマンガン成分、亜鉛成分および鉄成分と、炭素とを分離することができる。
固液分離手段は特に限定されない。固液分離工程には、常用の手段である、例えば重力沈降分離、ろ過、遠心分離、フィルタプレス、膜分離などから選ばれる手段を用いることが好ましい。
本発明では、固液分離工程で分離された浸出液から、亜鉛イオンおよび鉄イオンを除去して、マンガンイオンを高純度で含有する溶液(マンガン含有溶液)を得る、所定のマンガン抽出工程を行う必要がある。具体的には、マンガン抽出工程は、所定の亜鉛除去工程および鉄除去工程を順不同で含む。より具体的には、マンガン抽出工程が含む亜鉛除去工程は、亜鉛イオンに硫化物を作用させて亜鉛イオンを沈殿させる硫化物沈殿処理工程と、得られた亜鉛含有沈殿物を分離する亜鉛分離工程とを含む。また、マンガン抽出工程が含む鉄除去工程は、鉄イオンを酸化させて鉄イオンを沈殿させる酸化処理工程と、得られた鉄含有沈殿物を分離する鉄分離工程とを含む。
このように、マンガン抽出工程において、亜鉛イオンおよび鉄イオンをそれぞれ選択的に沈殿させて、浸出液から亜鉛イオンおよび鉄イオンを確実に取り除くことにより、最終的に、目的成分であるマンガン成分を高純度で得ることができる。
手順(A)における亜鉛除去工程では、固液分離された浸出液に、まず硫化物沈殿処理工程を施す。この硫化物沈殿処理工程では、浸出液に硫化物を作用させ、浸出液中に含まれるイオンのうち主として残存する亜鉛イオンを亜鉛硫化物として沈殿させ、浸出液から除去可能にする。この処理により、浸出液から、マンガンイオンおよび鉄イオンを含有する第1溶液と亜鉛含有沈殿物との混合物が得られる。
MnS:KSP=2.5×10-10
ZnS:KSP=1.6×10-24
FeS:KSP=6.3×10-18
(Lange, N.A.:Lange's Handbook of Chemistry. Thirteenth edition 1985)
溶解度積KSPの値が小さいほど、硫化物を形成しやすいことから、マンガン、亜鉛、鉄のうちでは、亜鉛(Zn)が最も硫化物を形成しやすいことになる。したがって、マンガン、亜鉛、鉄のイオンを含む浸出液に硫化物を作用させた場合には、亜鉛(Zn)を選択的に硫化物として沈殿させることができる。そして、硫化物イオンの濃度、浸出液のpHを調整することにより、浸出液中の亜鉛イオン濃度を分析限界(0.1mg/L)未満に容易に低減することができる。
より具体的には、硫化物沈殿処理工程で得られた、マンガンイオンおよび鉄イオンを含有する第1溶液と、主として残存する亜鉛の硫化物が沈殿した亜鉛含有沈殿物とを分離する。これにより、硫化物沈殿処理工程後の混合物から亜鉛成分を容易に分離でき、マンガンイオンおよび鉄イオンを含む第1溶液とすることができる。分離手段は特に限定されることなく、上述した固液分離工程に従えばよい。
なお、上記した硫化物沈殿処理では、溶液中から鉄(Fe)分の一部が沈殿除去される場合がある。この場合、予め設定した鉄分濃度未満に鉄分が除去されていれば、この段階で処理を終えることも考えられる。しかし、手順(A)では、鉄分をさらに分離除去して高純度のマンガン成分を得るべく、後述する鉄除去工程を更に行う。
手順(A)では、上述した亜鉛除去工程に続き、鉄除去工程を施す。手順(A)における鉄除去工程では、まず、先の亜鉛除去工程で得られたマンガンイオンおよび鉄イオンを含有する第1溶液に酸化処理工程を施し、第1溶液中の鉄イオンを鉄含有沈殿物として、鉄成分も分離除去可能にする。この処理により、第1溶液からは、マンガンイオンを高純度に含有する第2溶液(マンガン含有溶液)と鉄含有沈殿物との混合物が得られる。
分離手段は特に限定されることなく、上述した固液分離工程に従えばよい。
手順(B)における鉄除去工程では、固液分離工程で得られた浸出液に、まず酸化処理を施す。この酸化処理では、浸出液を酸化させて浸出液中に含まれるイオンのうち鉄イオンを鉄含有沈殿物として沈殿させ、まず鉄成分を浸出液から除去可能にする。この処理により、浸出液から、マンガンイオンおよび亜鉛イオンを含有する第1溶液と鉄含有沈殿物との混合物が得られる。
分離手段は特に限定されることなく、上述した固液分離工程に従えばよい。
手順(B)では、上述した鉄除去工程に続き、亜鉛除去工程を施す。手順(B)における亜鉛除去工程では、先の鉄除去工程で得られた第1溶液に硫化物を作用させ、第1溶液中のイオンのうち主として亜鉛イオンを亜鉛硫化物として沈殿させ、残存する亜鉛成分も第1溶液から除去可能にする。この処理により、第1溶液からは、マンガンイオンを高純度に含有する第2溶液(マンガン含有溶液)と亜鉛含有沈殿物との混合物が得られる。
硫化物の種類および第1溶液の好適なpHは、上述した手順(A)での硫化物沈殿処理方法に従えばよい。第1溶液のpHは、特にpH:4が好ましい。
また、作用させる硫化物量は、溶解亜鉛に対する硫黄Sとして1.1当量以上が好ましく、2当量以上がより好ましく、5当量以下とすることが好ましい。作用させる硫化物量が1.1当量未満では、亜鉛の沈殿除去は進行しているものの不完全であり、しかも最終的な除去率も安定しない。作用させる硫化物量が2当量以上であれば、亜鉛の沈殿除去も顕著となる。また、作用させる硫化物量が5当量を超えると、作用させる硫化物量が過剰となり、マンガンも沈殿除去される場合がある。
分離手段は特に限定されることなく、上述した固液分離工程に従えばよい。
なお、得られたマンガン含有溶液は、例えば、アルカリ沈殿させて高純度のマンガン水酸化物として各種用途に用いてもよい。また、得られたマンガン含有溶液は、Ni等の他の金属を混合したのち、アルカリ沈殿処理等を施し、二次電池電極材用の材料として利用してもよい。
つぎに、本発明の回収設備について説明する。本発明の回収設備は、選別装置、破砕装置、篩い分け装置、加熱装置、酸浸出槽、固液分離装置、およびマンガン抽出装置群を順に備え、本発明のマンガン回収方法と同様の特徴及び効果を有する。また、マンガン抽出装置群は、所定の亜鉛除去装置群および鉄除去装置群を順不同で含む。
そして、本発明のマンガン回収設備は、例えば、本発明のマンガン回収方法を実施する際に好適に利用することができる。
本発明の回収設備の一態様として、上述の手順(A)を好適に実施可能な構成(A)について図9に示す。図9に模式的に示すように、回収設備は、選別装置10と、破砕装置20aと、篩い分け装置20bと、加熱装置110と、酸浸出槽30と、固液分離装置40と、硫化物沈殿処理槽52と、亜鉛分離装置62と、酸化処理槽82と、鉄分離装置92と、マンガン含有溶液回収槽100とを、この順で備えることができる。ここで、硫化物沈殿処理槽52および亜鉛分離装置62は亜鉛除去装置群を構成し、酸化処理槽82および鉄分離装置92は鉄除去装置群を構成する。また、亜鉛除去装置群および鉄除去装置群はマンガン抽出装置群を構成する。
破砕装置20aは、通常の破砕機がいずれも適用できるが、2軸回転式の破砕機とすることが好ましい。
篩い分け装置20bは、目開き1mm以上20mm以下の篩を備えたものとすることが好ましい。篩い分け装置20bの目開きは、マンガン回収方法について上述した理由と同様に、おおよそ、1mm以上が好ましく、20mm以下が好ましく、10mm以下がより好ましく、3mm以下が更に好ましい。
マンガン含有溶液回収槽100は、鉄分離装置92で固液分離されたマンガン含有溶液(第2溶液)を回収して、貯液でき、払い出し自在に構成されたタンクとすることが好ましい。
また、本発明の回収設備の他の態様として、上述の手順(B)を好適に実施可能な構成(B)について図10に示す。図10に模式的に示すように、回収設備は、選別装置10と、破砕装置20aと、篩い分け装置20bと、加熱装置110と、酸浸出槽30と、固液分離装置40と、酸化処理槽53と、鉄分離装置63と、硫化物沈殿処理槽83と、亜鉛分離装置93と、マンガン含有溶液回収槽100とを、この順で備えることができる。ここで、酸化処理槽53および鉄分離装置63は鉄除去装置群を構成し、硫化物沈殿処理槽83および亜鉛分離装置93は亜鉛除去装置群を構成する。また、鉄除去装置群および亜鉛除去装置群はマンガン抽出装置群を構成する。
酸化処理槽53は、浸出液に酸化処理を施すため、タンクに撹拌機を備えた一般的な撹拌槽とすることが好ましい。硫化物沈殿処理槽83は、第1溶液に硫化物を作用させる硫化物沈殿処理を施すため、タンクに撹拌機を備えた一般的な撹拌槽とすることが好ましい。
なお、本発明では、回収設備を構成する各種装置、反応槽、回収槽は、上記したそれぞれの機能を有する限り、その構造等は問わない。
粉粒体の作製
廃乾電池からマンガン乾電池およびアルカリマンガン乾電池を選別する工程と、選別した廃乾電池を破砕し、目開き2.8mmの篩で篩い分けし、廃乾電池の粉粒体を得る粉砕・篩い分け工程と、を施し、廃乾電池の粉粒体を得た。得られた粉粒体の組成を表1に示す。なお、得られた粉粒体は、表1に示す元素の他に、酸化物または水酸化物に由来する酸素、若干の水素および水分を含む。
得られた粉粒体に、黒鉛を配合することなく、加熱装置110に装入して加熱処理を施す加熱処理工程を行った。加熱処理は、不活性雰囲気であるN2雰囲気中で加熱温度:1000℃、加熱時間:1時間とする処理とした。
加熱処理工程を経て得られた粉粒体を、酸浸出槽30に投入し、酸浸出工程を施した。酸浸出工程では、粉粒体10gに、酸溶液100mLを混合し、粉粒体からマンガン、亜鉛および鉄を浸出させる酸浸出処理を施した。酸溶液の酸濃度は、硫酸濃度:3N(質量%濃度約13.2%)とした。なお、酸浸出処理時間は1時間とし、酸浸出処理は撹拌処理とした。この場合、粉粒体と酸溶液との比である固液比は100g/Lであり、酸溶液に対する還元剤の添加量は100g/Lとなる。
なお、得られた浸出液のマンガン濃度をもとに、浸出液中のマンガン質量を算出し、別途測定しておいた加熱処理後の粉粒体中のマンガン質量に対する浸出液中のマンガン質量の割合(マンガン元素換算)を算出し、マンガン浸出率とした。マンガン浸出率は100%であった。
つぎに、固液分離工程により得られた浸出液を、硫化物沈殿処理槽52に装入し、硫化物を作用させる硫化物沈殿処理工程を行った。硫化物沈殿処理工程では、浸出液に、硫化物として水硫化ナトリウムNaHSを、溶解亜鉛に対し硫黄Sとして2当量となるように添加した。なお、水硫化ナトリウムは、蒸留水に溶解させた溶液の状態で添加した。また、硫化物沈殿処理中の浸出液のpHが4となるようにpH調整液(3M硫酸または100g/L水酸化ナトリウム)で調整した。また、硫化物沈殿処理の処理時間は30分とし、撹拌処理とした。
ついで、亜鉛除去工程を経て得られた第1溶液を、酸化処理槽82に装入し、酸化反応を行う酸化処理工程を行った。酸化処理工程では、酸化処理として、まず、得られた第1溶液に空気曝気を施した。空気曝気の条件は、吹込み量:(第1溶液量と同体積)/分、曝気時間:30分とした。空気曝気を施した後、孔径1μmのろ紙で吸引ろ過した第1溶液について、含まれる成分を上記手法で定量分析した。得られた結果を「酸化処理後の中間溶液」として表2に併記した。
得られた第2溶液について、含まれる成分を上記手法で定量分析した。なお、過酸化水素水とpH調整剤の添加量を記録し、これら溶液で希釈された影響を分析値から補正した。得られた結果を「鉄除去工程後の第2溶液」として表2に併記した。
実施例1と同様に粉粒体の作製を行い、表1に示す組成の粉粒体を得た。また、実施例1と同様に浸出液の作製を行ったところ、固液分離工程後の浸出液中のマンガン、亜鉛、鉄の各成分の含有量(mg/L)は表3のとおりであった。なお、実施例1と同様に求めたマンガン浸出率は100%であった。
実施例1と同様に粉粒体の作製を行い、表1に示す組成の粉粒体を得た。また、実施例1と同様に浸出液の作製を行ったところ、固液分離工程後の浸出液中のマンガン、亜鉛、鉄の各成分の含有量(mg/L)は表4のとおりであった。なお、実施例1と同様に求めたマンガン浸出率は100%であった。
つぎに、固液分離工程で分離された浸出液に酸化処理工程を施した。酸化処理工程では、得られた浸出液に空気曝気を施し、浸出液中に含まれる鉄成分から水酸化鉄を生成し、鉄含有沈殿物として、浸出液から鉄成分を分離除去可能な状態とした。空気曝気の条件は、吹込み量:(浸出液量と同体積 mL)/分、曝気時間:30分とした。なお、酸化処理を施すに当たり、浸出液を、pH調整剤(3M硫酸または100g/L水酸化ナトリウム)を用いて、pH:5に調整した。
ついで、鉄分離工程で分離された第1溶液に硫化物を作用させ、主として、第1溶液中に含まれる亜鉛イオンを亜鉛硫化物(亜鉛含有沈殿物)として沈殿させ、第1溶液から分離除去可能な状態とする硫化物沈殿処理工程を施した。使用した硫化物は水硫化ナトリウムNaHSであり、溶解亜鉛に対し硫黄Sとして2当量となるように添加した。なお、水硫化ナトリウムは、蒸留水に溶解させた溶液の状態で添加した。また、硫化物沈殿処理中の第1溶液のpHが4となるようにpH調整液(3M硫酸または100g/L水酸化ナトリウム)で調整した。また、硫化物沈殿処理の処理時間は30分とし、撹拌処理とした。
このように、本発明によれば、廃乾電池に含まれるマンガン成分を、高純度のマンガンイオン含有溶液として、容易に、しかも高い歩留りで回収できることがわかる。
20a 破砕装置
20b 篩い分け装置
30 酸浸出槽
40 固液分離装置
52 硫化物沈殿処理槽(構成A)
53 酸化処理槽(構成B)
62 亜鉛分離装置(構成A)
63 鉄分離装置(構成B)
70a、72b、72c、73b、73c 回収槽
82 酸化処理槽(構成A)
83 硫化物沈殿処理槽(構成B)
92 鉄分離装置(構成A)
93 亜鉛分離装置(構成B)
100 マンガン含有溶液回収槽
110 加熱装置
Claims (14)
- 廃乾電池からマンガン乾電池および/またはアルカリマンガン乾電池を選別する選別工程と、
前記選別工程で選別された前記マンガン乾電池および/または前記アルカリマンガン乾電池を破砕、篩い分けして粉粒体を得る破砕・篩い分け工程と、
前記破砕・篩い分け工程で得られた前記粉粒体に、非酸化性雰囲気中で加熱処理を施す加熱処理工程と、
前記加熱処理工程を施された粉粒体に、酸溶液、あるいはさらに還元剤を混合して、該粉粒体が含有するマンガン、亜鉛および鉄を該粉粒体から浸出させて、マンガンイオン、亜鉛イオンおよび鉄イオンを含有する浸出液を得る酸浸出工程と、
前記酸浸出工程で得られた前記浸出液とそれ以外の浸出残渣とを分離する固液分離工程と、
前記固液分離工程で分離された前記浸出液から、前記亜鉛イオンおよび鉄イオンを除去して、前記マンガンイオンを含有する溶液を得るマンガン抽出工程と、
をこの順に施す、廃乾電池からのマンガン回収方法であって、
前記マンガン抽出工程が、
前記亜鉛イオンに硫化物を作用させて該亜鉛イオンを沈殿させる硫化物沈殿処理工程と、さらに、得られた亜鉛含有沈殿物を分離する亜鉛分離工程と、を含む亜鉛除去工程と;
前記鉄イオンを酸化させて該鉄イオンを沈殿させる酸化処理工程と、さらに、得られた鉄含有沈殿物を分離する鉄分離工程と、を含む鉄除去工程と;
を順不同に含むことにより、高純度のマンガン含有溶液を得ることを特徴とする廃乾電池からのマンガン回収方法。 - 前記マンガン抽出工程が、前記亜鉛除去工程、続いて前記鉄除去工程の順に行われ、
前記亜鉛除去工程では、前記浸出液に硫化物を作用させて該浸出液中の亜鉛イオンを沈殿させる硫化物沈殿処理工程を施した後に、該硫化物沈殿処理工程で得られた亜鉛含有沈殿物とマンガンイオンおよび鉄イオンを含有する第1溶液とを固液分離し、
前記鉄除去工程では、前記亜鉛除去工程で得られた前記第1溶液を酸化させて該第1溶液中の鉄イオンを沈殿させる酸化処理工程を施した後に、該酸化処理工程で得られた鉄含有沈澱物とマンガンイオンを含有する第2溶液とを固液分離することを特徴とする、請求項1に記載の廃乾電池からのマンガン回収方法。 - 前記硫化物沈殿処理工程において、前記浸出液をpH:2以上6以下に調整することを特徴とする、請求項2に記載の廃乾電池からのマンガン回収方法。
- 前記酸化処理工程において、前記マンガンイオンおよび鉄イオンを含有する第1溶液に対して空気曝気を行う、またはさらに該第1溶液に対して酸化剤を添加し、かつ該第1溶液をpH:3以上7以下に調整することを特徴とする、請求項2または3に記載の廃乾電池からのマンガン回収方法。
- 前記マンガン抽出工程が、前記鉄除去工程、続いて前記亜鉛除去工程の順に行われ、
前記鉄除去工程では、前記浸出液を酸化させて該浸出液中の鉄イオンを沈殿させる酸化処理工程を施した後に、該酸化処理工程で得られた鉄含有沈澱物とマンガンイオンおよび亜鉛イオンを含有する第1溶液とを固液分離し、
前記亜鉛除去工程では、前記鉄除去工程で得られた前記第1溶液に硫化物を作用させて該第1溶液中の亜鉛イオンを沈殿させる硫化物沈殿処理工程を施した後に、該硫化物沈殿処理工程で得られた亜鉛含有沈澱物とマンガンイオンを含有する第2溶液とを固液分離することを特徴とする、請求項1に記載の廃乾電池からのマンガン回収方法。 - 前記硫化物沈殿処理工程において、前記マンガンイオンおよび亜鉛イオンを含有する第1溶液をpH:2以上6以下に調整することを特徴とする、請求項5に記載の廃乾電池からのマンガン回収方法。
- 前記酸化処理工程において、前記浸出液に対して空気曝気を行い、かつ該浸出液をpH:3以上7以下に調整することを特徴とする、請求項5または6に記載の廃乾電池からのマンガン回収方法。
- 前記加熱処理工程における前記加熱処理が、800℃以上1200℃以下の範囲の温度に加熱する処理であることを特徴する、請求項1~7のいずれか一項に記載の廃乾電池からのマンガン回収方法。
- 前記加熱処理工程において、前記粉粒体に、さらに炭素材料を前記粉粒体全量に対する質量比で、0.5以下の範囲で配合することを特徴とする、請求項1~8のいずれか一項に記載の廃乾電池からのマンガン回収方法。
- 前記酸浸出工程における前記酸溶液が、質量%濃度1.4%以上45%以下の希硫酸または質量%濃度1%以上14%以下の希塩酸であることを特徴とする、請求項1~9のいずれか一項に記載の廃乾電池からのマンガン回収方法。
- 前記酸浸出工程における前記粉粒体と前記酸溶液との固液比が50g/L以上であることを特徴とする、請求項1~10のいずれか一項に記載の廃乾電池からのマンガン回収方法。
- 前記酸浸出工程における前記還元剤が、過酸化水素、硫化ナトリウム、亜硫酸水素ナトリウム、チオ硫酸ナトリウム、および硫酸鉄のいずれかであることを特徴とする、請求項1~11のいずれか一項に記載の廃乾電池からのマンガン回収方法。
- 前記硫化物沈殿処理工程において使用する硫化物が、水硫化ナトリウム、硫化ナトリウム、硫化水素のうちのいずれかであることを特徴とする、請求項1~12のいずれか一項に記載の廃乾電池からのマンガン回収方法。
- 廃乾電池からマンガン乾電池および/またはアルカリマンガン乾電池を選別する選別装置と、
前記選別装置で選別された前記マンガン乾電池および/またはアルカリマンガン乾電池を装入して破砕処理を施し、破砕処理物を得る破砕装置と、
前記破砕装置で得られた前記破砕処理物に篩い分け処理を施して粉粒体を得る篩い分け装置と、
前記篩い分け装置で得られた前記粉粒体に、非酸化性雰囲気中で加熱処理を施す加熱装置と、
前記加熱装置で加熱処理された前記粉粒体に、酸溶液、あるいはさらに還元剤を混合して、該粉粒体が含有するマンガン、亜鉛および鉄を該粉粒体から浸出させて、マンガンイオン、亜鉛イオンおよび鉄イオンを含有する浸出液を得る酸浸出槽と、
前記酸浸出槽で得られた前記浸出液と浸出残渣とを分離する固液分離装置と、
前記固液分離装置で分離された前記浸出液から、前記亜鉛イオンおよび鉄イオンを除去して、前記マンガンイオンを含有する溶液を得るマンガン抽出装置群と、
をこの順で備える、廃乾電池からのマンガン回収設備であって、
前記マンガン抽出装置群が、
前記亜鉛イオンに硫化物を作用させて該亜鉛イオンを沈殿させる硫化物沈殿処理槽と、さらに、得られた亜鉛含有沈殿物を固液分離する亜鉛分離装置と、を含む亜鉛除去装置群と、
前記鉄イオンを酸化させて該鉄イオンを沈殿させる酸化処理槽と、さらに、得られた鉄含有沈殿物を固液分離する鉄分離装置と、を含む鉄除去装置群と;
を順不同に含むことにより、廃乾電池から有価成分を回収することを特徴とする、廃乾電池からのマンガン回収設備。
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JP7196974B1 (ja) | 2021-09-15 | 2022-12-27 | Jfeスチール株式会社 | 廃乾電池に含有されるマンガンの回収方法および回収設備 |
WO2023042606A1 (ja) * | 2021-09-15 | 2023-03-23 | Jfeスチール株式会社 | 廃乾電池に含有されるマンガンの回収方法および回収設備 |
JP2023043099A (ja) * | 2021-09-15 | 2023-03-28 | Jfeスチール株式会社 | 廃乾電池に含有されるマンガンの回収方法および回収設備 |
CN113860385A (zh) * | 2021-10-09 | 2021-12-31 | 四川天人能源科技有限公司 | 一种铁锰脱硫剂固体废弃物的资源化方法 |
CN113860385B (zh) * | 2021-10-09 | 2023-11-17 | 四川天人能源科技有限公司 | 一种铁锰脱硫剂固体废弃物的资源化方法 |
JP7298754B1 (ja) | 2022-06-06 | 2023-06-27 | Jfeスチール株式会社 | 廃乾電池に含有されるマンガンの回収方法及び回収設備 |
WO2023238446A1 (ja) * | 2022-06-06 | 2023-12-14 | Jfeスチール株式会社 | 廃乾電池に含有されるマンガンの回収方法及び回収設備 |
JP2023178917A (ja) * | 2022-06-06 | 2023-12-18 | Jfeスチール株式会社 | 廃乾電池に含有されるマンガンの回収方法及び回収設備 |
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