CN110431245A - The manufacturing method of manganese metal - Google Patents
The manufacturing method of manganese metal Download PDFInfo
- Publication number
- CN110431245A CN110431245A CN201880017577.XA CN201880017577A CN110431245A CN 110431245 A CN110431245 A CN 110431245A CN 201880017577 A CN201880017577 A CN 201880017577A CN 110431245 A CN110431245 A CN 110431245A
- Authority
- CN
- China
- Prior art keywords
- manganese
- metal
- manganese metal
- manufacturing
- reducing agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- 239000011572 manganese Substances 0.000 claims abstract description 125
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 108
- 238000010438 heat treatment Methods 0.000 claims abstract description 59
- 239000000126 substance Substances 0.000 claims abstract description 54
- 238000005406 washing Methods 0.000 claims abstract description 43
- 239000007788 liquid Substances 0.000 claims abstract description 41
- 239000007787 solid Substances 0.000 claims abstract description 37
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 35
- 238000000926 separation method Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 239000004411 aluminium Substances 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 230000009467 reduction Effects 0.000 claims description 35
- 230000033228 biological regulation Effects 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 4
- 239000013590 bulk material Substances 0.000 abstract description 58
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 45
- 229910052799 carbon Inorganic materials 0.000 abstract description 39
- 238000000034 method Methods 0.000 abstract description 33
- 239000011701 zinc Substances 0.000 abstract description 32
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 31
- 229910052725 zinc Inorganic materials 0.000 abstract description 31
- 239000002994 raw material Substances 0.000 abstract description 28
- 230000008569 process Effects 0.000 abstract description 14
- 238000011946 reduction process Methods 0.000 abstract description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000460 chlorine Substances 0.000 abstract description 12
- 229910052801 chlorine Inorganic materials 0.000 abstract description 12
- 239000003513 alkali Substances 0.000 abstract description 11
- 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 abstract description 9
- 229910052751 metal Inorganic materials 0.000 description 44
- 239000002184 metal Substances 0.000 description 44
- 238000006722 reduction reaction Methods 0.000 description 33
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 24
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 16
- 238000012545 processing Methods 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 15
- 239000000292 calcium oxide Substances 0.000 description 14
- 235000012255 calcium oxide Nutrition 0.000 description 14
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 14
- 229910052742 iron Inorganic materials 0.000 description 12
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 10
- 238000004064 recycling Methods 0.000 description 10
- 239000010439 graphite Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000011592 zinc chloride Substances 0.000 description 7
- 235000005074 zinc chloride Nutrition 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000006298 dechlorination reaction Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000009628 steelmaking Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000616 Ferromanganese Inorganic materials 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229910000617 Mangalloy Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000003196 chaotropic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 230000003694 hair properties Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- -1 refuse battery Chemical compound 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/04—Dry methods smelting of sulfides or formation of mattes by aluminium, other metals or silicon
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A kind of manufacturing method of high-quality manganese metal, addition water slurry is made and washes the slurry washing process implemented to substance containing manganese, above-mentioned substance containing manganese be preferably from pick out manganese dry cell in used dry batteries and/or alkali manganese dry cell crushed, sieved obtained from bulk material；Then, solid-liquid separation treatment is implemented to the slurry through the washing process；Heating temperature: 600 DEG C or more of heat treatment further is implemented to isolated solid component；Then implement to mix reducing agent and fluxing agent in heat-treated solid component, be packed into electrometal furnace, use the power on the reduction process that the reaction heat of heating and/or reducing agent restores substance containing manganese, thus obtain manganese metal.As reducing agent, preferably metallic aluminium and/or metallic silicon.The chlorine contained in raw material is removed by washing process separated and dissolved, the carbon contained in raw material is flared off by heat treatment, process is further restored by electrometal furnace and restores manganese, zinc, the zinc being reduced volatilization is removed, obtains the manganese metal of high-quality.
Description
Technical field
The present invention relates to the manufacturing method of manganese metal (hereinafter also referred to " metal Mn "), more particularly to will be from used dry batteries
The method that the substance containing manganese recycled in manufactures the manganese metal of high-quality as raw material.
Background technique
In iron and steel domain, all the time, manganese is that the element being widely used as useful element especially exists in recent years
Become important element in the manufacture of automobile high-tensile steel.
As manganese used in iron and steel domain, make sometimes in terminal stage, that is, ingredient adjusting stage of steel products manufacture
With.At this time, it is desirable that the manganese of high-purity.Therefore, in general, the manganese used at this stage is the electrolytic metal manufactured by electrolysis method
Manganese.Electrolysis method is after removing impurity by solvent extraction etc., to carry out the manganese such as manganese ore raw material (manganese source) acid dissolutions such as sulfuric acid
The method for being electrolysed and manganese metal being made can obtain the manganese metal of high-purity.But there are following various problems for this method: electricity
It solves at high cost, electrode plate can not be increased the problems such as additionally, due to removing, and difficulty is automated and need craft, furthermore in order to mention
High electrolytic efficiency and the wastewater treatment difficulty of selenium etc. added, it is therefore desirable to establish a kind of replacing autofrettage.
As the conventional manufacturing method of the manganese metal other than electrolysis method, there are blast furnace process, aluminothermic process etc..Blast furnace process is by conduct
The manganese ore of manganese raw material (manganese source) is packed into the method that blast furnace is refined together with coke, can be manufactured with less expensive price,
But there is problems in that containing the impurity such as silicon, carbon；It is difficult with the raw material of powdery；It is not available and is waved containing zinc, sodium, potassium etc.
The raw material etc. of the high substance of hair property.In addition, aluminothermic process is the metals such as mixed magnesium, aluminium in the manganese such as manganese ore raw material (manganese source), make
Thermit reaction occurs and the method that obtains manganese metal in it, but the metal due to using the high prices such as magnesium, aluminium in reduction and heating, institute
It is surging with there are manufacturing costs, to economic unfavorable problem.Based on such situation, status be the manufacture of industrial manganese metal only
It is carried out with electrolysis method.
In the manufacture of manganese metal, as the substance for being used as manganese raw material (manganese source), generally there are manganese oxide ore, manganese carbonate ore
The manganese ores such as stone, but these natural resources are limited, it is possible to it is exhausted.It is a large amount of due to consuming especially in iron-smelter
Manganese is as steelmaking feed, so manganese source ensures to become problem of crucial importance in ironmaking field.Also, in recent years, as
Also price is in rising trend due to its exhaustion for the manganese ore of raw material.
In recent years, it due to the exhaustion of such metal resource, rising of transaction value etc., begins trying to want from low-quality
Raw ore, concentrate, ironmaking plant by-products, energetically recycle manganese in industrial waste etc..For example, as industrial waste disposition
There are the substances that manganese containing ratio is high in a part of dry cell.The manganese dry cell and alkali manganese dry cell of representative as one-shot battery
Use manganese dioxide as positive electrode.If it is possible to establish from these used dry batteries recycle manganese and as
The technology that steelmaking feed recycles, it is expected that effectively ensuring that manganese source.Also, in countries in the world, production, is discarded at consumption
The dry cell of enormous amount.It should be noted that having used zinc as negative electrode material in dry cell.
However, status be for electric discharge after manganese dry cell, the alkali manganese dry cell discarded, only in zinc refiner
The recycling of a part of zinc, or the recycling of iron, a part of carbon in electrometal furnace manufacturer, it cannot be said that sufficiently carry out
Resource circulation utilization.Status is that still have many resources not to be recycled and directly sharp using unused state as waste material
For landfill disposal etc..
Therefore, zinc, iron, carbon will not only be recycled by being recently proposed from used dry batteries, also recycle the various technologies of manganese.
The recovery method for describing the mixture containing manganese dioxide and carbon in patent document 1, with following processes:
The process of manganese cell and alkaline Mn cell is picked out from used dry batteries；The process for obtaining bulk material by crushing, screening；Will
The process that the bulk material arrived dilute hydrochloric acid or dilute sulfuric acid carry out dissolution process.According to the technology recorded in patent document 1, Neng Gou
It does not generate in the case where big loss easily while recycling manganese dioxide and carbon component, it is iron that the mixture of recycling can be used as manganese
The initial feed made.
The method that manganese dioxide and zinc chloride are separated and recovered from used dry batteries is described in patent document 2.Patent text
Offering the technology recorded in 2 is the method that manganese dioxide and zinc chloride are separated and recovered from used dry batteries, that is, from used dry batteries
To the material for containing many manganese and zinc, it is dissolved in hydrochloric acid after washing as needed to it, is removed from the solution by purifying
Heating concentration is carried out after impurity component, is heated after perchloric acid is added in the concentrate, and consolidating for manganese dioxide and zinc chloride is obtained
Body mixture filters after the solid mixture is dissolved in water.In the technology described in patent document 2, the zinc chloride that will be obtained
It is dissolved in organic solvent, the insoluble alkaline metal salt being mixed in is eliminated and purifies zinc chloride.In addition, the titanium dioxide of recycling
Manganese and zinc chloride have the purity that can be re-used for dry cell manufacture.
Metal recovery processes are described in patent document 3.The technology recorded in patent document 3 is metal recovery processes, that is,
So that iron-reducing bacteria is acted on the group being made of metal oxide and metal hydroxides, trivalent iron is reduced into divalent iron, uses
Obtained divalent iron leaches the metals such as the cobalt contained in the group being made of metal oxide and metal hydroxides, nickel, manganese, raw
At leachate and residue, obtained leachate and residue are separated, required metal is recycled.As by metal oxide and metal
The group that hydroxide is constituted, can enumerate abyssal floor mineral resources, the oxide ore (land mineral) containing metal, containing metal
Wastes such as incineration residue etc..According to the technology recorded in patent document 3, metal oxidation can be recycled to high speed, high efficiency
The low-quality metal contained in object, metal hydroxides.In addition, the metals such as the cobalt contained in leachate, nickel, manganese can be used
Usual way recycling.
The manufacturing method of manganese metal is described in patent document 4.The technology recorded in patent document 4 is the manufacture of manganese metal
Method, that is, be packed into the substance containing manganese oxide together with reducing agent in heating furnace, the in-furnace temperature for being heated to heating furnace reaches
1200 DEG C or more restore manganese oxide, are cooled to 700 DEG C thereafter hereinafter, being discharged to outside furnace.The technology documented by patent document 4
In, as the substance containing manganese oxide, refuse battery, manganese ore etc. can be used, as reducing agent, used coal, coke, graphite
Equal carbon system reducing agent.
The method that manganese and zinc are separated from used dry batteries is described in patent document 5.The technology recorded in patent document 5 is
The method of manganese and zinc is separated from used dry batteries, that is, manganese dry cell and/or alkali manganese dry cell are picked out from used dry batteries, it is right
The dry cell picked out is crushed, is sieved and bulk material is made, and is implemented Ore Leaching processing to the bulk material using acid solution, is obtained
The leachate leached to manganese and zinc and the leaching residue containing manganese, after being separated by solid-liquid separation, make ozonization in separated
Leachate obtains the sediment containing manganese and the solution containing zinc ion, carries out being separated by solid-liquid separation the manganese for making to contain in used dry batteries
Ingredient becomes to leach residue and the sediment containing manganese, by the zinc ingredient contained in used dry batteries with the solution containing zinc ion
Form separation.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2007-12527 bulletin
Patent document 2: Japanese Unexamined Patent Publication 11-191439 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2007-113116 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2011-94207 bulletin
Patent document 5: Japanese Unexamined Patent Publication 2015-206077 bulletin
Summary of the invention
However, the Mn contained becomes in through the substance containing Mn of each technology recycling documented by Patent Documents 1 to 3
Oxide or hydroxide manufacture work for example, needing further to restore Mn in order to which the state that can be used as iron-smelting raw material is made
Sequence becomes complicated, and result has that cost is got higher.Manganese is definitely not the metal of high price as rare metal, but manufacturing cost
Increase interfere its technology functionization.It should be noted that in the technology described in patent document 3, existing as microorganism
The problem of reagent that the complexing agent of culture medium and the nutrient source as microorganism is added is high price.In addition, passing through patent
There are following problems by the metal Mn for the technology manufacture recorded in document 4: keeping carbon content (dense as the carbon residual that reducing agent uses
Degree) there are many case where getting higher, as metal Mn quality decline.In addition, in the technology described in patent document 5, currently used for
Producing ozoniferous equipment (ozone generating apparatus) is high price, and needs a large amount of electric power, therefore lead to the height of manufacturing cost
Rise, it is still problematic in practical.
It is an object of the invention to solve above-mentioned problem of the prior art, a kind of manufacturing method of manganese metal, energy are provided
Manganese metal enough cheap and that easily manufacture can be used as the manganese metal of iron-smelting raw material and can be equal to electrolytic manganese metal.
The inventors of the present invention in order to achieve the above purpose, have made intensive studies the quality improvement method of manganese metal.Its
If as a result contemplating to contain manganese substance and be packed into electric furnace together with reducing agent and fluxing agent and (as representative examples, having arc-melting
Furnace), reduction treatment is carried out in electric furnace, then can inexpensively manufacture and can be used as the high-purity that the substitute of electrolytic manganese metal uses
Manganese.In addition, according to this method, it was found that " substance obtained from being selected used dry batteries, crushed, being sieved " (bulk material)
It can be directly used as manganese source (substance containing manganese).It has however been found that the powder obtained from being selected used dry batteries, being crushed, sieved
In plastochondria in addition to the manganese as principal component, also contain zinc, carbon sometimes, and contain chlorine.
Therefore, it is further studied, bulk material (substance containing manganese) is implemented to heat if as a result contemplated
As pre-treatment, then it can be flared off the carbon contained in " substance containing manganese " (bulk material), can easily improved behind
The quality of manganese metal obtained in reduction treatment in electric furnace.Still further, it was discovered that in reduction treatment, the zinc that contains in bulk material
It is reduced and becomes metallic object (metallic zinc).Due to the low boiling point of metallic zinc, so the zinc contained in bulk material energy in reduction
Enough volatilizations remove.
In addition, the inventors of the present invention worry in the case where containing chlorine in substance containing manganese (bulk material), at reduction treatment, heating
When reason, harmful substance is generated, therefore, it is contemplated that before needing to implement the processing conduct except dechlorination to substance containing manganese (bulk material) in advance
Processing.The inventors of the present invention implement substance containing manganese (bulk material) as " except the processing of dechlorination " by further research, discovery
Washing process is effective.
In this way, the inventors of the present invention's discovery can be easily separated by implementing above-mentioned pre-treatment in advance and remove object containing manganese
Each ingredient other than the manganese contained in matter (used dry batteries bulk material) can inexpensively manufacture (recycling) high-quality (high-purity) gold
Belong to manganese.
The present invention is to conduct further research and complete on the basis of above-mentioned discovery.That is, purport of the invention is such as
Under.
[1] a kind of manufacturing method of manganese metal will contain the reduction of manganese substance and obtain manganese metal, wherein to above-mentioned object containing manganese
Matter implements washing process, that is, and water is added to above-mentioned substance containing manganese and is washed as slurry,
Then implement the solid-liquid separation treatment for being separated into solid component and liquid to the above-mentioned slurry through the washing process,
Further implement the heat treatment of above-mentioned solid component heating that will be separated by the solid-liquid separation treatment,
The above-mentioned solid component for implementing above-mentioned heat treatment is packed into electric furnace together with reducing agent and fluxing agent, utilizes this
Above-mentioned solid component is carried out reduction treatment and obtains manganese metal by the reaction heat of the electrified regulation of electric furnace and/or above-mentioned reducing agent.
[2] manufacturing method of the manganese metal according to [1], wherein above-mentioned substance containing manganese is chosen to used dry batteries
Choosing crushes, substance obtained from screening.
[3] manufacturing method of the manganese metal according to [1] or [2], wherein above-mentioned slurry in above-mentioned washing process
Solid component and liquid are 1:10~5:10 than by quality ratio.
[4] manufacturing method of the manganese metal according to any one of [1]~[3], wherein the washing of above-mentioned washing process
Time is 15 minutes or more.
[5] manufacturing method of the manganese metal according to any one of [1]~[4], wherein the temperature of above-mentioned heat treatment
It is 600 DEG C or more.
[6] manufacturing method of the manganese metal according to any one of [1]~[5], wherein used in above-mentioned reduction treatment
Above-mentioned reducing agent be metallic aluminium and/or metallic silicon.
[7] manufacturing method of the manganese metal according to any one of [1]~[6], wherein used in above-mentioned reduction treatment
Above-mentioned fluxing agent be substance using CaO as principal component.
In accordance with the invention it is possible to which manganese metal cheap and that easily manufacture can be equal to electrolytic manganese metal, industrially sends out
Wave significant effect.
Detailed description of the invention
Fig. 1 is the explanatory diagram for indicating the process of manufacturing method of manganese metal of the invention.
Specific embodiment
The present invention is to implement reduction treatment and the system of the manganese metal of obtained manganese metal to the raw material using substance containing manganese as raw material
Make method.In the present invention, the substance containing manganese as raw material is not particularly limited, manganese preferably containing 10 mass % or more,
The zinc of 0.03 mass % or more, 0.1 mass % or more carbon object.More preferable use is selected used dry batteries, is crushed, is sieved
Bulk material (used dry batteries bulk material) obtained from point.
" selecting " mentioned herein refers to from being picked out from alkaline dry battery and/or alkali manganese dry cell in used dry batteries
Reason.It " is selected " in process at this, alkaline dry battery and/or alkali manganese dry cell is picked out from the dry cell of discarded recycling.It chooses
As long as choosing method is that can exclude the method for mercury cell, nickel-cadmium cell etc. there is no need to be particularly limited to, shape is chosen or utilized to hand
The machinery of shape, radioactive ray etc. the common method such as is selected and be can be used.
In addition, " crushing " mentioned herein refers to that the alkaline dry battery that will be singled out and/or alkali manganese dry cell are crushed
Processing.The crushing for the used dry batteries picked out is usually using pulverizer.The type of pulverizer does not need to be particularly limited to, but preferably
Pulverizer for the type that after being pulverized can separate well packaging material for constituting dry cell etc. with bulk material, such as
The pulverizer of Double-shaft rotary.
If these dry cells are pulverized, packaging material (iron, plastics and paper etc.), as the negative electrode material of manganese dry cell
Zinc can, become as the brass bar of the collector of alkali manganese dry cell the solid matter of foil-like, sheet.On the other hand, as manganese
The manganese dioxide of the positive electrode of dry cell, as manganese dry cell collector carbon-point, as the cathode material of alkali manganese dry cell
The zinc powder of material, MnO (OH), the Zn (OH) generated by electric discharge2、Mn(OH)2, ZnO etc. and various electrolyte becomes than above-mentioned
The thinner bulk material of the solid matter of foil-like sheet.
Therefore, after the used dry batteries that will be singled out are crushed, if sieved using the sieve of regulation mesh,
The big solid matters such as packaging material can be removed from the used dry batteries picked out, and obtain belonging to manganese dry cell and/or alkali manganese
The main composition material of dry cell, manganese dioxide, carbon, zinc chloride or ammonium chloride, iron, caustic potash and pass through what electric discharge generated
MnO(OH)、Zn(OH)2、Mn(OH)2, the bulk material (used dry batteries bulk material) that mixes such as ZnO.It should be noted that crushing
The mesh of sieve used in the screening of object is preferably 1mm~20mm or so, further preferably 1mm~10mm or so.
The obtained used dry batteries bulk material contains manganese, zinc and carbon as main component (element), additionally containing certain
The chlorine of amount.Therefore, using used dry batteries bulk material as raw material manufacture manganese metal when, zinc, carbon, chlorine the degree being separated off be important
's.The process of the manufacturing method of manganese metal of the invention is shown in Fig. 1.
In the present invention, before implementing reduction treatment, to the substance containing manganese (used dry batteries bulk material) as raw material according to
Secondary implementation washing process, solid-liquid separation treatment, heat treatment are used as pre-treatment.
Firstly, implementing washing process as pre-treatment to the substance containing manganese (used dry batteries bulk material) as raw material.Washing
Processing refers to that water is added in substance containing manganese (used dry batteries bulk material) is made slurry, the processing washed to the slurry.Tool
For body, washing process is preferably packed into substance containing manganese (used dry batteries bulk material) in a reservoir, and addition water is made slurry and stirs afterwards
Mix the processing of certain time.The chlorine contained in substance containing manganese (used dry batteries bulk material) as a result, is dissolved in the water of addition, can
Dechlorination is removed from substance containing manganese (used dry batteries bulk material).
In washing process of the invention, the ratio of substance containing manganese (used dry batteries bulk material) amount and the water of addition is that is, solid
Liquor ratio is preferably 5:10 or less by quality ratio.If it exceeds above-mentioned solid-to-liquid ratio, belongs to (the used dry batteries of substance containing manganese of solid
Bulk material) amount increase, then become difficult as the operability of slurry.On the other hand, solid-to-liquid ratio is made to become smaller if reducing the amount of solid,
The container for needing to increase washing, to economic unfavorable.Therefore, solid-to-liquid ratio is preferably the range of 1:10~5:10, more preferably 1:
10 or more and 3:10 or less.
In addition, the time of washing process is preferably 15 minutes (being denoted as " min " below) in order to ensure the dissolution of chlorine Xiang Shuizhong
More than.It should be noted that prolonged washing needs to make container enlargement etc., it is unfavorable to economy, therefore washing time is preferably 1 small
When (be denoted as " hr " below) below left and right.
Then solid-liquid separation treatment is implemented to the substance containing manganese (used dry batteries bulk material) for implementing washing process.By solid
Substance containing manganese (used dry batteries bulk material) after washing process is separated into solid component and separating liquid (water) by liquid separating treatment.Point
Chlorine containing dissolution in chaotropic (water), thereby, it is possible to contained chlorine is separated off from substance containing manganese (used dry batteries bulk material).
It should be noted that gravity settling separation, centrifugal filtration, filter press, UF membrane etc. can be used in the solid-liquid separation treatment in the present invention
Common method carries out.
Then, implement heat treatment to by solid component obtained from washing process-solid-liquid separation treatment.It fires as a result,
Burn off removes the carbon contained in solid component (substance containing manganese (used dry batteries bulk material)).
Heat treatment, which will refer to, to be packed into heating furnace etc. by solid component obtained from solid-liquid separation treatment, by the solid at
Divide the processing of heating.Heating temperature in heat treatment is preferably 600 DEG C or more.When heating temperature is lower than 600 DEG C, heating temperature
It is low, the burning of carbon does not occur, the carbon contained in solid component can not be removed, or for removing the carbon contained in solid component
Heated hold time is elongated, productivity decline.It should be noted that preferred heating temperature is 800 DEG C or more.On the other hand, add
The upper limit of hot temperature as long as be the nonvolatile temperature of manganese (boiling point: 2061 DEG C) hereinafter, as long as the higher the better.But due under high temperature
Heat treatment cause to heat the surging of cost, it is appropriate it is advantageous to be determined from the viewpoint of processing time and cost
Temperature.It should be noted that heating treatment time is preferably properly selected according to the combustion position of carbon, from economy, productivity
Viewpoint consideration, preferably 15min or more and the left and right 3hr or less.More preferably 30min or more and the left and right 1hr or less.
Then to by solid component (substance containing manganese) obtained from washing process-solid-liquid separation treatment-heat treatment
Implement reduction process.In the present invention, reduction process is the electric furnace reduction process using electric furnace.Herein, the representative of the electric furnace used
Example is electrometal furnace, and resistance furnace, induction melting furnace etc. furthermore also can be used.Hereinafter, being the feelings of electrometal furnace to electric furnace
Condition is illustrated.In addition, in order to which the metal of molten condition (is known as " molten metal " or " molten by the molten metal generated
Liquid ") drain, molten slag deslagging, the furnace that can preferably fascinate.
It, will be by obtained from washing process-solid-liquid separation treatment-heat treatment in electrometal furnace reduction process
Solid component (substance containing manganese) and reducing agent and fluxing agent (slag former) are packed into electrometal furnace together.Via electrometal furnace
Graphite electrode is powered and heats the substance containing manganese being packed into, and contained manganese and zinc are reduced agent reduction, obtains molten metal (metal
Manganese and metallic zinc).At this point, the boiling point of metallic zinc is 907 DEG C, so being reduced and becoming since melt temperature is 1600 DEG C or more
When at metallic zinc, becomes gas and volatilize.As a result, in molten metal, only manganese metal can obtain the manganese metal of high-quality.
Herein, the manganese metal of high-quality refers to the manganese that the ultimate constituent regulator that can be used as manganese steel uses, and specifically refers to that Mn+Al is dense
Degree is 90 mass % or more, carbon (C) concentration is 0.2 mass % or less, phosphorus (P) concentration is 0.05 mass % or less and sulphur (S)
Concentration is the substance of 0.05 mass %.
It should be noted that the zinc of volatilization reacts rapidly and becomes the dust of zinc oxide (fusing point: 1975 DEG C) with the oxygen in air,
By pocket type filters trap, recycling.
As reducing agent used in electrometal furnace reduction process, metallic aluminium, metallic silicon, carbon can be illustrated, but as system
Reducing agent when high-quality manganese metal is made, carbon is easy to be mixed into manganese metal (product) and be not suitable for, preferably metallic aluminium and/or metal
Silicon.It should be noted that cheap ferrosilicon also can be used instead of metallic silicon.In this case, the concentration of iron in product (manganese metal)
Iron is not impurity when getting higher, but using as iron-smelting raw material, therefore can be used as manganese metal use.
Even if it should be noted that in the case where using metallic aluminium, metallic silicon as reducing agent, it is in electrometal furnace plus
When heat, melting, if graphite electrode and be packed into object especially with the molten metal (molten metal) that is generated by reduction reaction
Contact, the then concentration of carbon that not can avoid in the molten metal of generation increase to a certain extent.Therefore, molten in electric arc of the invention
Change in furnace reduction process, preferably increase graphite electrode is avoided contact at a distance from loading object or molten metal (interval)
Operation (high voltage operation).Thereby, it is possible to prevent from picking up carbon from graphite electrode.
In addition, can be the reduction of a step in electrometal furnace reduction process of the invention, but preferably once reduction
Such two steps reduction is restored with final.When using metallic aluminium and/or metallic silicon as reducing agent, in primary reduction, stop
In the reaction for reducing oxidizability, without the reaction to generation metal Mn.Therefore, in primary reduction, the use level of reducing agent
For all the desired amount of a part.Substance containing manganese as raw material cooperates whole aequums in primary reduction.It should be noted that excellent
The use level for selecting fluxing agent is also the amount for being suitble to the use level of reducing agent.It then, will be all the desired amount of surplus in final reduction
Remaining reducing agent is put into together with fluxing agent, proceeds to the reaction for generating metal Mn.Thereby, it is possible to electrode and molten metal is (molten
Melt metal Mn) contact control to necessary minimum limit, C (carbon) can be mixed into control to minimum limit to metal Mn.
In addition, thermit reaction occurs for metallic aluminium, a large amount of reaction heat is generated.Therefore, use metallic aluminium as reducing agent
In the case of, when generating the reaction heat of reducing agent, if carrying out electrified regulation, it is likely that excessively heating.Therefore, of the invention
In, during the reaction heat (thermit reaction heat) for generating reducing agent, preferably stop the electrified regulation carrying out using electrode.As a result,
Also with following advantage point: the electrified regulation time carried out using graphite electrode can be shortened, be able to suppress carbon to product
(manganese metal) is mixed into.
In addition, use in electrometal furnace reduction process of the invention metallic aluminium as reducing agent in the case where, preferably
Metallic aluminium as reducing agent is divided into the loading in batches being repeatedly packed into.Thereby, it is possible to the fever for generating thermit reaction is uniform
Change, can prevent from excessively heating, inhibit the evaporation (loss of dispersing) of molten metal (metal Mn), improves Mn retention.It should say
It is bright, when carrying out the loading in batches of reducing agent, in order to homogenize reaction, preferably by the substance containing manganese and fluxing agent as raw material
Or fluxing agent is packed into batches.
Fluxing agent used in electrometal furnace reduction process of the invention is preferably using CaO as the substance of principal component.Make
For quick lime, lime stone, calcium hydroxide can be illustrated using CaO as the substance of principal component.
The use level of reducing agent need certainly for carry out completely will as the oxide contained in the substance containing manganese of raw material or
Manganese, the zinc of hydroxide be reduced into manganese metal, metallic zinc reduction reaction needed for it is more than reduction dosage (theoretical reduction equivalent),
It is preferred that being determined by experiment suitable amount in advance.
On the other hand, the use level of fluxing agent utilizes CaO/Al2O3Than adjustment.CaO/Al2O3Than being 0.55, but as long as being
In the range of 0.4~1.0 or so, so that it may obtain the progress of sound response.When lower than 0.4, the manganese oxide in clinker will not decline,
In addition if it exceeds 1.0, then free quick lime becomes more, and the fusing point of clinker becomes excessively high, and slag amount is excessively increased.By
This, the use level of fluxing agent is preferably according to the ratio (quality of fluxing dosage and the reduction dosage to be converted with oxide by weight of CaO
Than), i.e. CaO/Al2O3It is adjusted than the mode in the range of becoming 0.4~1.0.
Embodiment
Hereinafter, being based on embodiment, further the present invention will be described.
Manganese dry cell and/or alkali manganese dry cell are picked out from used dry batteries, are chosen this using Double-shaft rotary pulverizer
The used dry batteries selected crush, and with mesh: the sieve of 3mm is sieved, and obtains bulk material (used dry batteries bulk material).It will obtain
Bulk material composition it is shown in table 1.It should be noted that obtained bulk material in addition to containing element shown in table 1, also contains and comes from
The oxygen and moisture of oxide or hydroxide.
Firstly, implementing washing process: by obtained bulk material 50g investment (loading) to container (beaker), adding thereto
Add distilled water 500mL, is washed with solid-to-liquid ratio 1:10.It should be noted that washing refers to according to washing time shown in table 2: 5,
15,30min, in the processing of container for stirring.
Then the bulk material for implementing washing process is implemented to use the filtering of 5C filter paper as solid-liquid separation treatment, separation
At solid component and separating liquid.Chlorine analysis is implemented to obtained solid component.It the results are shown in table 2.
[table 1]
[table 2]
According to table 2, can be confirmed that the chlorinity in bulk material (used dry batteries bulk material) passes through the processing time: 15min is left
Right washing process, which can be controlled into sufficiently, is lower than 0.1 mass %.It should be noted that the chlorinity lower than 0.1 mass % is in electricity
The target chlorinity of the raw material of electrometal furnace can be put into arc melting furnace reduction process.
Then, implement washing process: in such a way that solid-to-liquid ratio changes between mass ratio 1:10~5:10, changing
The input amount of bulk material and the additive amount of distilled water, investment (loading) are arrived in container (beaker), are washed.It should be noted that water
It washes and refers to and be fixed as the processing time: 15min and the processing in container for stirring.Then real to the bulk material for implementing washing process
It applies and uses the filtering of 5C filter paper as solid-liquid separation treatment, be separated into solid component and separating liquid.It is real to obtained solid component
Apply chlorine analysis.It the results are shown in table 3.
[table 3]
According to table 3, even if can be confirmed in the slurry that solid-to-liquid ratio reaches 5:10 and improves solid component, pass through washing
Processing also can sufficiently control the chlorine dose in bulk material (used dry batteries bulk material) at lower than 0.1 mass %, and solid-to-liquid ratio is to water
The influence for chlorinity of washing that treated is small.It should be noted that in this experiment, since container is small containers, so passing through strength
Stirring is just able to carry out sufficient stirring, but in the case where container enlargement, until solid-to-liquid ratio reaches 3:10 or so, uniformly
Stirring is easier to, but if solid-to-liquid ratio is increased to 5:10 or so, then it is envisioned that being difficult to uniformly be stirred.Therefore, when
When making device enlarged (bulk material is more than 20kg, several tons of scales) as described below, from the viewpoint of the easiness of stirring, Gu
Liquor ratio is preferably 3:10 or so.It should be noted that implementing to add 67kg in bulk material 20kg in a manner of becoming solid-to-liquid ratio 3:10
Water be stirred the washing process of cleaning after, be filtered using centrifugal filter, as a result available 92 matter of the rate of recovery
Measure the bulk material for completing washing process of %, 20 mass % of moisture content.It confirmed the solid-to-liquid ratio if it is this degree,
Can with there is no problem it implement in washing process, solid-liquid separation treatment.
Thus the washing process for judging substance containing manganese (used dry batteries bulk material) is that solid-to-liquid ratio is controlled as 5:10 or less, washed
Time is the processing of 15min or so or more.
Then, by obtained bulk material (used dry batteries bulk material): about 100kg is packed into calcining furnace, implements heat treatment.Add
Heat treatment is constant heating time: 180min, makes range of the heating temperature at 400 DEG C~1000 DEG C.Then, measurement heating
Residual concentration of carbon in treated bulk material.The obtained results are shown in tables 4.It should be noted that in heating temperature: 800 DEG C,
In the case where 1000 DEG C, Mn and Zn amount also measured were.
[table 4]
As shown in Table 4 by making heating temperature: 600 DEG C or more, the residual concentration of carbon after heat treatment drops to 0.1 matter
Measure % or less.Even if in heating temperature: in the case where 400 DEG C, 500 DEG C, it can make to remain concentration of carbon decline by heating also,
But the slippage for remaining concentration of carbon is few, in order to make remain concentration of carbon drop to 0.1 mass % hereinafter, need be more than 3hr compared with
Prolonged heat treatment.Therefore, it is known that make 400 DEG C of heating temperature, 500 DEG C be unpractical.It should be noted that can by table 4
The rising with heating temperature is known, because being flared off for carbon causes whole weight to reduce, so manganese and the opposite change of zinc concentration
It is high.
Then, make 600 DEG C of heating temperature, 800 DEG C, for the heating time within 60min, analyze heating time to powder
The influence of residual concentration of carbon in plastochondria.The obtained results are shown in tables 5.
[table 5]
In heating temperature: at 600 DEG C, residual concentration of carbon drops to quality % and needs 60min or so for 0.1% or so.Separately
On the one hand, in heating temperature: in the case where 800 DEG C, the decrease speed for remaining concentration of carbon is fast, is heated by 30min and is declined
To 0.1% or so.Thus when the heat treatment for judging substance containing manganese (used dry batteries bulk material) is 600 DEG C 60min or so or
30min or so at 800 DEG C.
Then, as described above, implementing washing process: obtained from being selected in used dry batteries and being crushed, sieved
Bulk material (used dry batteries bulk material): water is added in 90kg, solid-to-liquid ratio is made: after the slurry of 3:10, to the slurry agitation
30min is washed；Then further implement solid-liquid separation treatment with centrifugal filter device, be separated into solid component and separation
Liquid.Then, obtained solid component is packed into calcining furnace, implemented in heating temperature: the heat treatment of 800 DEG C of heating 30min.
Then, the solid component (used dry batteries bulk material) for implementing above-mentioned heat treatment is implemented as reduction process
Electrometal furnace restores process.
In electrometal furnace reduction process, the logical electric metal Mn of 5kg, drop are put into the furnace of test electrometal furnace
After lower graphite electrode, it is packed into initial mixing raw material.Initial mixing raw material is the solid component for implementing above-mentioned heat treatment
(used dry batteries bulk material): 50kg and the metallic aluminium as reducing agent: the 12kg and CaO (quick lime) as fluxing agent:
16.5kg。
After being packed into initial mixing raw material, implementing electrified regulation as initial heating makes melting sources.It should be noted that fusing
In, stop being powered during thermit reaction start and ending.
After thermit reaction after initial heating, in order to ensure defined temperature, steadily promotes reaction, lead to again
Electricity.The operation is repeated as many times.It should be noted that being packed into additional mixed raw material in midway.The cooperation of additional mixed raw material is conduct
The metallic aluminium of reducing agent: 4kg and as CaO (quick lime): 5.5kg of fluxing agent.It should be noted that reducing agent so far
Additive amount is as a reduction treatment, lower than theoretical reduction equivalent needed for generating metal Mn.
It is further additional to be packed into reducing agent and fluxing agent after a reduction treatment, carry out final reduction treatment.Additional
Reducing agent is metallic aluminium: 4kg, and additional fluxing agent is CaO:3.5kg.After being packed into additional reducing agent, overheats, stop in order to prevent
It is only powered until thermit reaction terminates.It,, will be electric after sufficiently generating clinker after thermit reaction in final reduction treatment
Pole is immersed in clinker, is powered the stipulated time, carries out reaction promotion, temperature is adjusted.It should be noted that in final reduction treatment
The contact avoided electrode with molten metal is carried out and the mixed operation of anti-blocking.
After reduction treatment, molten slag is discharged, molten metal (molten metal manganese) is then injected into mold, makes it
Solidification.Obtained manganese metal is 26kg.
The composition of obtained manganese metal is shown in table 6.It should be noted that also shown together in table 6 existing electrolytic manganese,
The composition of the extremely low extremely low carbon ferromanganese of phosphorus, which is used as, to be compared.
[table 6]
*) agglomerate
*) block (instead of metal Mn)
It according to table 6, can be confirmed in example of the present invention, by the reduction treatment carried out using electrometal furnace, zinc is almost
Volatilization, is not remain in metal, in addition, the residual of carbon or other elements is also few, can make as electrolytic manganese metal substitute
With.
Claims (7)
1. a kind of manufacturing method of manganese metal will contain the reduction of manganese substance and obtain manganese metal, wherein
To the substance containing manganese implement water is added and as the washing process that slurry is washed,
Then implement the solid-liquid separation treatment for being separated into solid component and liquid to the slurry through the washing process,
In turn, implement the heat treatment of solid component heating that will be separated by the solid-liquid separation treatment,
The solid component for implementing the heat treatment is packed into electric furnace together with reducing agent and fluxing agent, utilizes the electric furnace
Electrified regulation and/or the reducing agent reaction heat, by the solid component carry out reduction treatment and obtain manganese metal.
2. the manufacturing method of manganese metal according to claim 1, wherein the substance containing manganese is chosen to used dry batteries
Choosing crushes, substance obtained from screening.
3. the manufacturing method of manganese metal according to claim 1 or 2, wherein the slurry in the washing process
Solid component and liquid are 1:10~5:10 than by quality ratio.
4. the manufacturing method of manganese metal described in any one of claim 1 to 3, wherein the washing of the washing process
Time is 15 minutes or more.
5. the manufacturing method of manganese metal according to any one of claims 1 to 4, wherein the temperature of the heat treatment
It is 600 DEG C or more.
6. the manufacturing method of manganese metal according to any one of claims 1 to 5, wherein used in the reduction treatment
The reducing agent be metallic aluminium and/or metallic silicon.
7. the manufacturing method of manganese metal described according to claim 1~any one of 6, wherein used in the reduction treatment
The fluxing agent be substance using CaO as principal component.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017049454 | 2017-03-15 | ||
| JP2017-049454 | 2017-03-15 | ||
| PCT/JP2018/007554 WO2018168471A1 (en) | 2017-03-15 | 2018-02-28 | Production method for metallic manganese |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110431245A true CN110431245A (en) | 2019-11-08 |
| CN110431245B CN110431245B (en) | 2022-08-12 |
Family
ID=63522971
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201880017577.XA Active CN110431245B (en) | 2017-03-15 | 2018-02-28 | Method for producing manganese metal |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6591675B2 (en) |
| CN (1) | CN110431245B (en) |
| WO (1) | WO2018168471A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114107678A (en) * | 2021-12-03 | 2022-03-01 | 万循材料科技有限公司 | Method for recovering zinc and manganese metals from waste mercury-free zinc-manganese dry batteries |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111041247B (en) * | 2019-12-11 | 2022-04-05 | 遵义天磁锰业集团有限公司 | Preparation method of normal-temperature ferric oxide desulfurizer based on manganese metal liquid preparation |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1584089A (en) * | 2004-06-16 | 2005-02-23 | 吴光亮 | Mangan-alloy production |
| CN101054187A (en) * | 2007-04-03 | 2007-10-17 | 深圳市格林美高新技术股份有限公司 | Selective volatilization recovery process and recovery system for waste zinc-manganese battery |
| CN102154566A (en) * | 2011-03-25 | 2011-08-17 | 重庆大学 | Method for preparing high-manganese-content manganese-aluminum masteralloy by taking pyrolusite as raw material |
| JP5446735B2 (en) * | 2009-10-30 | 2014-03-19 | Ｊｆｅスチール株式会社 | Method for producing metal manganese |
| CN104060100A (en) * | 2014-05-08 | 2014-09-24 | 无锡市阳泰冶金炉料有限公司 | Process method of extracting metal manganese from manganese-enriched slag |
| CN104789778A (en) * | 2015-03-11 | 2015-07-22 | 长沙矿冶研究院有限责任公司 | Recovery treatment method for Mn containing waste batteries |
| WO2015162902A1 (en) * | 2014-04-21 | 2015-10-29 | Ｊｆｅスチール株式会社 | Method and equipment for recovering valuable components from waste dry batteries |
| JP5948637B2 (en) * | 2013-04-03 | 2016-07-06 | 東邦亜鉛株式会社 | Metal recovery method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61261443A (en) * | 1985-05-16 | 1986-11-19 | Nippon Mining Co Ltd | Method for separating and recovering valuables from waste dry battery |
| JP4418129B2 (en) * | 2001-03-02 | 2010-02-17 | 三井金属鉱業株式会社 | Collection method of valuable metals |
| JP5745348B2 (en) * | 2011-06-21 | 2015-07-08 | Ｎｐｏ法人サーモレックス・ラボ | Waste battery recycling method |
| JP6219325B2 (en) * | 2015-02-26 | 2017-10-25 | Ｊｆｅスチール株式会社 | Method for producing metal manganese |
-
2018
- 2018-02-28 WO PCT/JP2018/007554 patent/WO2018168471A1/en active Application Filing
- 2018-02-28 JP JP2018529076A patent/JP6591675B2/en active Active
- 2018-02-28 CN CN201880017577.XA patent/CN110431245B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1584089A (en) * | 2004-06-16 | 2005-02-23 | 吴光亮 | Mangan-alloy production |
| CN101054187A (en) * | 2007-04-03 | 2007-10-17 | 深圳市格林美高新技术股份有限公司 | Selective volatilization recovery process and recovery system for waste zinc-manganese battery |
| JP5446735B2 (en) * | 2009-10-30 | 2014-03-19 | Ｊｆｅスチール株式会社 | Method for producing metal manganese |
| CN102154566A (en) * | 2011-03-25 | 2011-08-17 | 重庆大学 | Method for preparing high-manganese-content manganese-aluminum masteralloy by taking pyrolusite as raw material |
| JP5948637B2 (en) * | 2013-04-03 | 2016-07-06 | 東邦亜鉛株式会社 | Metal recovery method |
| WO2015162902A1 (en) * | 2014-04-21 | 2015-10-29 | Ｊｆｅスチール株式会社 | Method and equipment for recovering valuable components from waste dry batteries |
| CN104060100A (en) * | 2014-05-08 | 2014-09-24 | 无锡市阳泰冶金炉料有限公司 | Process method of extracting metal manganese from manganese-enriched slag |
| CN104789778A (en) * | 2015-03-11 | 2015-07-22 | 长沙矿冶研究院有限责任公司 | Recovery treatment method for Mn containing waste batteries |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114107678A (en) * | 2021-12-03 | 2022-03-01 | 万循材料科技有限公司 | Method for recovering zinc and manganese metals from waste mercury-free zinc-manganese dry batteries |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2018168471A1 (en) | 2019-03-28 |
| CN110431245B (en) | 2022-08-12 |
| WO2018168471A1 (en) | 2018-09-20 |
| JP6591675B2 (en) | 2019-10-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108559846B (en) | Method for comprehensively recovering anode material of waste lithium ion battery | |
| CN113517484B (en) | Method for treating waste lithium cobalt oxide battery and product thereof | |
| JP6648674B2 (en) | Method for producing metallic manganese | |
| JP6125458B2 (en) | Resource recovery method and separation / recovery equipment from waste dry batteries | |
| JP6070898B2 (en) | Method and facility for recovering valuable components from waste dry batteries | |
| CN101824543B (en) | Method for sulfidizing heavy metal waste and recovering valuable metals in heavy metal waste | |
| JP6219325B2 (en) | Method for producing metal manganese | |
| CN109047285A (en) | Containing sodium, the method for transformation of fluorochemical and system in a kind of waste cathode of aluminum electrolytic cell carbon block | |
| CN101186969B (en) | Method for separating rare earth, iron, copper, cobalt and tungsten from alloy | |
| CN109371252B (en) | Device and method for treating antimony-arsenic alkali slag by combining fire method and wet method | |
| CN111684634B (en) | Method for producing micronutrients from waste alkaline batteries | |
| CN108941167A (en) | Mechanochemistry conversion and recovery method in a kind of waste cathode of aluminum electrolytic cell carbon block containing sodium, fluorochemical | |
| CN106077036A (en) | A kind of method of ultrasonic assistant acidleach process aluminum electrolytic waste and old cathode carbon block | |
| CN100586617C (en) | Method for recycling and preparing ultra-fine zinc dust from zinc dust containing material | |
| CN106676275B (en) | Extraction vanadium method based on discarded slag and acidic and alkaline wastewater | |
| CN110431245A (en) | The manufacturing method of manganese metal | |
| KR101966065B1 (en) | Manufacturing method of multi-mineral from industrial waste | |
| CN110402294A (en) | The manufacturing method of manganese metal | |
| CN109127656A (en) | Mechanochemistry conversion and recovery method in a kind of aluminium electroloysis dangerous waste slag containing sodium, fluorochemical | |
| GB1568362A (en) | Heavy metal recovery in ferrous metal production processes | |
| JP6820689B2 (en) | Manufacturing method of metallic manganese | |
| CN109055739A (en) | Alkali soaks electrolysis method from low-grade containing the method for producing zinc powder in zinc ore | |
| CN111748694A (en) | Method for enriching and recovering vanadium resource in vanadium-rich slag | |
| CN101876004B (en) | Method for recycling rare metal molybdenum from mineral dressing tailings of molybdenum | |
| JP2017150029A (en) | Manufacturing method of metal manganese |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |