CN110431245B - Method for producing manganese metal - Google Patents
Method for producing manganese metal Download PDFInfo
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- CN110431245B CN110431245B CN201880017577.XA CN201880017577A CN110431245B CN 110431245 B CN110431245 B CN 110431245B CN 201880017577 A CN201880017577 A CN 201880017577A CN 110431245 B CN110431245 B CN 110431245B
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- 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 35
- 239000011572 manganese Substances 0.000 claims abstract description 157
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 139
- 238000010438 heat treatment Methods 0.000 claims abstract description 64
- 239000002699 waste material Substances 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 51
- 239000002184 metal Substances 0.000 claims abstract description 51
- 239000000126 substance Substances 0.000 claims abstract description 45
- 239000007788 liquid Substances 0.000 claims abstract description 44
- 238000005406 washing Methods 0.000 claims abstract description 44
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 37
- 239000007787 solid Substances 0.000 claims abstract description 35
- 238000000926 separation method Methods 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 230000004907 flux Effects 0.000 claims abstract description 20
- 239000002002 slurry Substances 0.000 claims abstract description 18
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 10
- 238000012216 screening Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 47
- 229910052799 carbon Inorganic materials 0.000 abstract description 40
- 239000011701 zinc Substances 0.000 abstract description 34
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 32
- 229910052725 zinc Inorganic materials 0.000 abstract description 32
- 239000002994 raw material Substances 0.000 abstract description 30
- 238000002844 melting Methods 0.000 abstract description 26
- 230000008018 melting Effects 0.000 abstract description 26
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 19
- 239000000460 chlorine Substances 0.000 abstract description 19
- 229910052801 chlorine Inorganic materials 0.000 abstract description 19
- 238000010298 pulverizing process Methods 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 9
- 238000007873 sieving Methods 0.000 abstract description 8
- 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 7
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000011946 reduction process Methods 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 43
- 238000000034 method Methods 0.000 description 40
- 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
- 239000008187 granular material Substances 0.000 description 22
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 18
- 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
- 239000002893 slag Substances 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000003832 thermite Substances 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
- 150000002739 metals Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 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
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 239000012535 impurity Substances 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
- 239000002245 particle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 238000013021 overheating Methods 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 239000000123 paper Substances 0.000 description 3
- 238000011084 recovery Methods 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
- 229910000616 Ferromanganese Inorganic materials 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
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 238000011109 contamination Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 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
- 230000014759 maintenance of location Effects 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
- 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
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000008247 solid mixture Substances 0.000 description 2
- 239000007858 starting material 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
- 239000004484 Briquette Substances 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal salts Chemical class 0.000 description 1
- 238000007133 aluminothermic reaction Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000015572 biosynthetic process 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
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000002801 charged material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000006028 limestone Substances 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
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 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
- 239000000155 melt Substances 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
- 239000003607 modifier 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
- 239000004033 plastic Substances 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
- 230000005855 radiation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 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
- 239000011343 solid material Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000003886 thermite process Methods 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
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
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- 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)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A method for producing high-quality metal manganese, comprising subjecting a manganese-containing substance, preferably a powder obtained by selecting a manganese dry cell and/or an alkali-manganese dry cell from waste dry cells, pulverizing the selected manganese dry cell and/or alkali-manganese dry cell, and sieving the resultant to a water washing treatment of preparing a slurry by adding water to the manganese-containing substance; then, carrying out solid-liquid separation treatment on the slurry subjected to the water washing treatment; the separated solid component is further subjected to a heating temperature: heating at 600 deg.C or higher; then, a reducing step of mixing the heated solid component with a reducing agent and a flux, charging the mixture into an arc melting furnace, and reducing the manganese-containing substance by energization heating and/or the heat of reaction of the reducing agent is performed to obtain metal manganese. As the reducing agent, metallic aluminum and/or metallic silicon are preferable. Chlorine contained in the raw material is dissolved and separated by washing treatment, carbon contained in the raw material is removed by heating treatment and burning, and further, manganese and zinc are reduced by an arc melting furnace reduction process, and the reduced zinc is volatilized and removed, thereby obtaining high-quality metal manganese.
Description
Technical Field
The present invention relates to a method for producing metallic manganese (hereinafter also referred to as "metallic Mn"), and more particularly to a method for producing high-quality metallic manganese from a manganese-containing substance recovered from a waste dry battery or the like as a raw material.
Background
In the field of steel and iron, manganese has been widely used as a useful element, and has become an important element in recent years, particularly in the production of high-tensile steel sheets for automobiles.
Manganese used in the steel field is sometimes used in a final stage of steel product production, that is, a component adjustment stage. In this case, high purity manganese is required. Therefore, in general, the manganese used at this stage is electrolytic manganese metal produced by an electrolytic method. The electrolytic method is a method in which a manganese raw material (manganese source) such as manganese ore is dissolved in an acid such as sulfuric acid, impurities are removed by solvent extraction or the like, and then electrolysis is performed to produce manganese metal, and high-purity manganese metal can be obtained. However, this method has various problems as follows: the cost of electrolysis is high, the electrode plate cannot be enlarged due to problems such as peeling, the automation is difficult, and the manual work is required, and the wastewater treatment of selenium added for improving the electrolysis efficiency is difficult, so that an alternative manufacturing method needs to be established.
As a conventional method for producing manganese metal other than the electrolytic method, there are a blast furnace method, an aluminothermic method, and the like. The blast furnace method is a method of charging manganese ore as a manganese raw material (manganese source) together with coke into a blast furnace and refining the same, and can be produced at a relatively low cost, but has the following problems: contains impurities such as silicon and carbon; it is difficult to use powdery raw materials; it is impossible to use a raw material containing a highly volatile substance such as zinc, sodium, or potassium. In addition, the thermite process is a process in which a metal such as magnesium or aluminum is mixed with a manganese raw material (manganese source) such as manganese ore and the mixture is subjected to a thermite reaction to obtain manganese metal, but since expensive metals such as magnesium or aluminum are used for reduction and temperature rise, the production cost rises, which is disadvantageous to the economy. Under such circumstances, the production of manganese metal is currently carried out industrially by an electrolytic method alone.
In the production of manganese metal, manganese ores such as manganese oxide ores and manganese carbonate ores are generally used as manganese raw materials (manganese sources), but these natural resources are limited and may be exhausted. In particular, in iron works, since a large amount of manganese is consumed as a steel-making raw material, securing a manganese source is a very important problem in the iron-making field. In recent years, the price of manganese ore as a raw material has also been increasing due to exhaustion thereof.
In recent years, attempts have been made to recover manganese from low-quality raw ores, concentrates, iron mill by-products, industrial wastes, and the like, in view of such depletion of metal resources, increase in trade price, and the like. For example, some dry batteries disposed of as industrial waste have a high manganese content. Manganese dioxide is used as a positive electrode material in a manganese dry cell and an alkaline manganese dry cell, which are typical primary batteries. Therefore, if a technique for recovering manganese from these waste dry batteries and reusing it as a steel-making raw material can be established, it is expected that a manganese source can be effectively secured. In addition, in countries around the world, a huge amount of dry cells are produced, consumed and discarded. In the dry battery, zinc is used as a negative electrode material.
However, in the present situation, only a part of zinc is recovered in a zinc refinery or a part of iron and carbon is recovered in an arc melting furnace manufacturer, and thus, it cannot be said that resource recycling is sufficiently performed for manganese dry batteries and alkali manganese dry batteries which are discarded after completion of discharge. Under the present circumstances, a lot of resources are not recycled but used as waste materials in a state of being unused for landfill disposal or the like.
Therefore, various techniques have recently been proposed for recovering not only zinc, iron and carbon but also manganese from waste dry batteries.
Patent document 1 describes a method for recovering a mixture containing manganese dioxide and carbon, which comprises the steps of: a step of selecting a manganese cell and an alkaline manganese cell from the waste dry cells; a step for obtaining a powder/granule by crushing and sieving; and dissolving the obtained powder with dilute hydrochloric acid or dilute sulfuric acid. According to the technique described in patent document 1, manganese dioxide and carbon components can be easily recovered simultaneously without causing a large loss, and the recovered mixture can be used as a starting material for ferromanganese production.
Patent document 2 describes a method for separating and recovering manganese dioxide and zinc chloride from waste dry batteries. The technique described in patent document 2 is a method of separating and recovering manganese dioxide and zinc chloride from waste dry batteries, in which a material containing a large amount of manganese and zinc is obtained from waste dry batteries, and if necessary, the material is washed with water and dissolved in hydrochloric acid, and the solution is purified to remove impurity components therefrom, and then concentrated by heating, and perchloric acid is added to the concentrate and then heated to obtain a solid mixture of manganese dioxide and zinc chloride, and the solid mixture is dissolved in water and filtered. In the technique described in patent document 2, zinc chloride is purified by dissolving the obtained zinc chloride in an organic solvent and removing insoluble alkali metal salts mixed therein. In addition, the recovered manganese dioxide and zinc chloride have a purity that can be reused in dry battery manufacture.
Patent document 3 describes a metal recovery method. The technique described in patent document 3 is a metal recovery method in which iron-reducing bacteria are allowed to act on a group consisting of metal oxides and metal hydroxides to reduce iron 3 into iron 2, the obtained iron 2 is used to leach metals such as cobalt, nickel, and manganese contained in the group consisting of metal oxides and metal hydroxides, and a leachate and a residue are produced, and the leachate and the residue are separated to recover the desired metals. Examples of the group consisting of metal oxides and metal hydroxides include deep-sea-bottom mineral resources, oxidized ores containing metals (terrestrial minerals), wastes such as metal-containing incineration residues, and the like. According to the technique described in patent document 3, low-quality metals contained in metal oxides and metal hydroxides can be recovered at high speed and high efficiency. Metals such as cobalt, nickel, and manganese contained in the leachate can be recovered by a conventional method.
Patent document 4 describes a method for producing manganese metal. The technique described in patent document 4 is a method for producing manganese metal, in which a substance containing manganese oxide is charged into a heating furnace together with a reducing agent, the heating furnace is heated to a furnace temperature of 1200 ℃ or higher to reduce the manganese oxide, and thereafter, the temperature is cooled to 700 ℃ or lower, and the manganese metal is discharged to the outside of the furnace. In the technique described in patent document 4, waste batteries, manganese ore, and the like can be used as the manganese oxide-containing substance, and a carbon-based reducing agent such as coal, coke, graphite, and the like is used as the reducing agent.
Patent document 5 describes a method for separating manganese and zinc from waste dry batteries. The technique described in patent document 5 is a method of separating manganese and zinc from waste dry batteries, in which a manganese dry battery and/or an alkaline manganese dry battery is selected from the waste dry batteries, the selected dry batteries are crushed and sieved to produce a powder, the powder is subjected to an acid leaching treatment using an acid solution to obtain a leachate containing manganese and zinc and a leaching residue containing manganese, after solid-liquid separation, ozone is allowed to act on the separated leachate to obtain a precipitate containing manganese and a solution containing zinc ions, solid-liquid separation is performed to convert manganese components contained in the waste dry batteries into the leachate residue and the precipitate containing manganese, and zinc components contained in the waste dry batteries are separated as the solution containing zinc ions.
Documents of the prior art
Patent document
Patent document 1 Japanese laid-open patent publication No. 2007-12527
Patent document 2 Japanese patent application laid-open No. 11-191439
Patent document 3, Japanese patent laid-open No. 2007-113116
Patent document 4, Japanese patent application laid-open No. 2011-
Patent document 5 Japanese laid-open patent publication No. 2015-206077
Disclosure of Invention
However, in the Mn-containing substances recovered by the respective techniques described in patent documents 1 to 3, the contained Mn becomes an oxide or a hydroxide, and for example, in order to be used as an iron-making raw material, it is necessary to further reduce Mn, which complicates the production process and consequently raises the cost. Manganese is never an expensive metal as a rare metal, but the increase in production cost has prevented the practical use of this technology. The technique described in patent document 3 has a problem that a reagent to be added as a culture medium for microorganisms and a complexing agent to be a nutrient source for microorganisms is expensive. In addition, the metal Mn produced by the technique described in patent document 4 has the following problems: carbon used as a reducing agent often remains and the carbon content (concentration) is high, and the quality of Mn as a metal is deteriorated. In addition, in the technique described in patent document 5, the conventional apparatus for generating ozone (ozone generating apparatus) is expensive and requires a large amount of electric power, which leads to an increase in manufacturing cost and has a problem in practical use.
An object of the present invention is to solve the above-described problems of the prior art and to provide a method for producing metallic manganese, which can produce metallic manganese that can be used as an iron-making raw material and metallic manganese that can be compared with electrolytic metallic manganese inexpensively and easily.
The present inventors have conducted intensive studies on a method for improving the quality of metallic manganese in order to achieve the above object. As a result, it has been thought that if a manganese-containing substance is charged into an electric furnace (typically, an arc melting furnace) together with a reducing agent and a flux and subjected to a reduction treatment in the electric furnace, high-purity manganese that can be used as a substitute for electrolytic manganese metal can be produced at a low cost. Further, according to this method, it has been found that "a material obtained by sorting, pulverizing and sieving a waste dry battery" (a powder or granule) can be used as a manganese source (a manganese-containing material) as it is. However, it has been found that the powder obtained by sorting, pulverizing and sieving the waste dry batteries may contain zinc, carbon and chlorine in addition to manganese as a main component.
Therefore, as a result of further studies, it was found that if the powder and granular material (manganese-containing substance) is subjected to a heat treatment as a pretreatment, carbon contained in the "manganese-containing substance" (powder and granular material) can be burned and removed, and the quality of metallic manganese obtained in a subsequent reduction treatment in an electric furnace can be easily improved. Further, it was found that zinc contained in the powder or granule was reduced to become a metal body (metallic zinc) during the reduction treatment. Since metallic zinc has a low boiling point, zinc contained in the powder can be volatilized and removed during reduction.
Further, the present inventors have considered that, when chlorine is contained in the manganese-containing substance (powder or granule), a treatment for removing chlorine needs to be performed in advance as a pretreatment because harmful substances are generated during the reduction treatment and the heat treatment. The present inventors have further studied and found that it is effective to perform a washing treatment of manganese-containing substances (powder and granular material) as a "treatment for removing chlorine".
As described above, the present inventors have found that by performing the above-described pretreatment in advance, it is possible to easily separate and remove components other than manganese contained in the manganese-containing substance (waste dry battery powder particles), and to produce (recover) high-quality (high-purity) metallic manganese at a low cost.
The present invention has been completed by further studies based on the above findings. That is, the gist of the present invention is as follows.
[1] A process for producing manganese metal, comprising reducing a manganese-containing substance to obtain manganese metal, wherein the manganese-containing substance is subjected to a water washing treatment, i.e., the manganese-containing substance is washed with water as a slurry,
then, the slurry subjected to the washing treatment is subjected to a solid-liquid separation treatment for separating the slurry into a solid component and a liquid,
further performing a heating treatment of heating the solid component separated by the solid-liquid separation treatment,
the solid component subjected to the heating treatment is charged into an electric furnace together with a reducing agent and a flux, and the solid component is subjected to a reduction treatment by energization heating of the electric furnace and/or reaction heat of the reducing agent to obtain metal manganese.
[2] The process for producing manganese metal according to [1], wherein the manganese-containing substance is obtained by sorting, pulverizing and sieving waste dry batteries.
[3] The method for producing metallic manganese according to [1] or [2], wherein a ratio of a solid component to a liquid of the slurry in the water washing treatment is 1: 10-5: 10.
[4] the method for producing metallic manganese according to any one of [1] to [3], wherein a water washing time of the water washing treatment is 15 minutes or more.
[5] The method for producing metallic manganese according to any one of [1] to [4], wherein the temperature of the heat treatment is 600 ℃ or higher.
[6] The method for producing metallic manganese according to any one of [1] to [5], wherein the reducing agent used in the reduction treatment is metallic aluminum and/or metallic silicon.
[7] The method for producing metal manganese according to any one of [1] to [6], wherein the flux used in the reduction treatment is a substance containing CaO as a main component.
According to the present invention, metal manganese comparable to electrolytic metal manganese can be produced at low cost and easily, and industrially significant effects can be achieved.
Drawings
Fig. 1 is an explanatory view showing a flow of a method for producing manganese metal of the present invention.
Detailed Description
The present invention relates to a method for producing manganese metal, which comprises using a manganese-containing substance as a raw material and subjecting the raw material to a reduction treatment to obtain manganese metal. In the present invention, the manganese-containing substance as a raw material is not particularly limited, and is preferably a substance containing 10 mass% or more of manganese, 0.03 mass% or more of zinc, and 0.1 mass% or more of carbon. More preferably, a powder obtained by sorting, pulverizing and sieving waste dry batteries (waste dry battery powder) is used.
The "sorting" referred to herein means a process of sorting out the alkaline unit cells and/or the alkaline manganese unit cells from the waste unit cells. In the "sorting" step, alkaline dry cells and/or alkaline manganese dry cells are selected from the discarded and recovered dry cells. The method of sorting is not particularly limited as long as it is a method capable of excluding mercury dry batteries, nickel cadmium batteries, and the like, and any commonly used method such as hand sorting, mechanical sorting using shapes, radiation, and the like can be used.
Further, the term "pulverization" as used herein refers to a treatment of pulverizing selected alkaline dry batteries and/or alkaline manganese dry batteries. The selected waste dry batteries are usually crushed by a crusher. The type of the pulverizer is not particularly limited, but is preferably a pulverizer of a type capable of favorably separating a packaging material or the like constituting a dry battery from the powder or granular material after pulverization, for example, a double-shaft rotary pulverizer.
When these dry batteries are crushed, the packaging material (iron, plastic, paper, etc.), the zinc can as the negative electrode material of the manganese dry battery, and the brass rod as the current collector of the alkaline manganese dry battery become a foil-like or sheet-like solid material. On the other hand, manganese dioxide as a positive electrode material for manganese dry batteries, a carbon rod as a current collector for manganese dry batteries, a zinc powder as a negative electrode material for alkali manganese dry batteries, MnO (OH) and Zn (OH) produced by discharge 2 、Mn(OH) 2 ZnO, and various electrolytic solutions are in the form of fine particles finer than the foil-like or sheet-like solid substance.
Therefore, when the sorted waste dry batteries are crushed and sieved using a sieve having a predetermined mesh, large solid matter such as a packaging material can be removed from the sorted waste dry batteries to obtain manganese dioxide, carbon, zinc chloride or ammonium chloride, iron, caustic potash, and MnO (OH) and Zn (OH) produced by discharge, which are main constituent materials of manganese dry batteries and/or alkali manganese dry batteries 2 、Mn(OH) 2 And powder particles (waste dry battery powder particles) obtained by mixing ZnO and the like. The mesh of the screen used for screening the pulverized material is preferably about 1mm to 20mm, and more preferably about 1mm to 10 mm.
The obtained waste dry battery powder contains manganese, zinc and carbon as main components (elements), and further contains a certain amount of chlorine. Therefore, in the production of manganese metal from waste dry battery powder particles as a raw material, the degree of separation and removal of zinc, carbon, and chlorine is important. Fig. 1 shows a flow of the method for producing manganese metal of the present invention.
In the present invention, before the reduction treatment, the manganese-containing material (waste dry battery powder) as a raw material is subjected to water washing treatment, solid-liquid separation treatment, and heating treatment in this order as pretreatment.
First, a manganese-containing material (waste dry battery powder) as a raw material is subjected to a water washing treatment as a pretreatment. The water washing treatment is a treatment of adding water to a manganese-containing substance (waste dry battery powder) to prepare a slurry, and washing the slurry with water. Specifically, the water washing treatment is preferably a treatment in which a manganese-containing substance (waste dry battery powder) is charged into a container, water is added to the container to prepare a slurry, and the slurry is stirred for a certain period of time. Thus, chlorine contained in the manganese-containing substance (waste dry battery powder) is dissolved in the added water, and chlorine can be removed from the manganese-containing substance (waste dry battery powder).
In the water washing treatment of the present invention, the ratio of the amount of manganese-containing substance (waste dry battery powder) to the amount of water added, i.e., the solid-to-liquid ratio, is preferably 5: 10 or less. If the solid-liquid ratio is exceeded, the amount of the solid manganese-containing substance (waste dry battery powder) increases, and handling as a slurry becomes difficult. On the other hand, if the solid-liquid ratio is decreased by decreasing the amount of solids, the vessel for water washing needs to be enlarged, which is economically disadvantageous. Therefore, the solid-to-liquid ratio is preferably 1: 10-5: 10, more preferably 1: 10 or more and 3: 10 or less.
In order to ensure the dissolution of chlorine into water, the time for the water washing treatment is preferably 15 minutes (hereinafter referred to as "min") or more. Since washing with water for a long time requires an increase in the size of the container, which is economically disadvantageous, the washing time is preferably about 1 hour (hereinafter referred to as "hr") or less.
Subsequently, the manganese-containing substance (waste dry battery powder) subjected to the washing treatment is subjected to solid-liquid separation treatment. The manganese-containing substance (waste dry battery powder) after the water washing treatment is separated into a solid component and a separation liquid (water) by a solid-liquid separation treatment. The separation liquid (water) contains dissolved chlorine, and thus the chlorine contained in the separation liquid can be separated and removed from the manganese-containing substance (waste dry battery powder). The solid-liquid separation treatment in the present invention can be carried out by a conventional method such as gravity settling separation, centrifugal filtration, filter press, membrane separation, or the like.
Subsequently, the solid component obtained by the water washing treatment-solid-liquid separation treatment is subjected to a heating treatment. This causes the carbon contained in the solid content (manganese-containing substance (waste dry battery powder) to be removed by combustion.
The heat treatment is a treatment of charging a solid component obtained by the solid-liquid separation treatment into a heating furnace or the like and heating the solid component. The heating temperature in the heating treatment is preferably 600 ℃ or higher. When the heating temperature is less than 600 ℃, the heating temperature is low, carbon combustion does not occur, carbon contained in the solid content cannot be removed, or the heating retention time for removing carbon contained in the solid content becomes long, and productivity is deteriorated. The heating temperature is more preferably 800 ℃ or higher. On the other hand, the upper limit of the heating temperature is preferably as high as possible, as long as the temperature at which manganese does not volatilize (boiling point: 2061 ℃ C.) is not higher. However, since the heat treatment at a high temperature causes an increase in the cost of the heat treatment, it is preferable to determine an appropriate temperature from the viewpoint of the treatment time and cost. The heat treatment time is preferably appropriately selected depending on the combustion state of carbon, and is preferably 15min to 3hr from the viewpoint of economy and productivity. More preferably, it is 30min to 1 hr.
Then, the solid component (manganese-containing substance) obtained by the water washing treatment, the solid-liquid separation treatment and the heating treatment is subjected to a reduction step. In the present invention, the reduction step is an electric furnace reduction step using an electric furnace. Here, a typical example of the electric furnace used is an arc melting furnace, and a resistance furnace, an induction melting furnace, or the like may be used. Hereinafter, a case where the electric furnace is an arc melting furnace will be described. In addition, a tiltable furnace is preferable for draining the molten metal (the molten metal is referred to as "molten metal" or "molten metal") produced and for removing slag from the molten slag.
In the reduction step in the arc melting furnace, the solid component (manganese-containing substance) obtained by the water washing treatment, the solid-liquid separation treatment, and the heating treatment is charged into the arc melting furnace together with the reducing agent and the flux (slag former). The charged manganese-containing substance is heated by passing electricity through a graphite electrode of an arc melting furnace, and the contained manganese and zinc are reduced by a reducing agent to obtain a molten metal (metal manganese and metal zinc). At this time, since the melt temperature is 1600 ℃ or higher and the boiling point of metallic zinc is 907 ℃, when it is reduced to metallic zinc, it turns into gas and volatilizes. Thus, only the metal manganese is contained in the molten metal, and high-quality metal manganese can be obtained. Here, the high-quality metal manganese means manganese that can be used as a final composition modifier for manganese steel, and specifically means a manganese having a Mn + Al concentration of 90 mass% or more, a carbon (C) concentration of 0.2 mass% or less, a phosphorus (P) concentration of 0.05 mass% or less, and a sulfur (S) concentration of 0.05 mass%.
The volatilized zinc reacts rapidly with oxygen in the air to form zinc oxide (melting point: 1975 ℃) dust, which is captured and recovered by a bag filter.
Examples of the reducing agent used in the reduction step in the arc melting furnace include metallic aluminum, metallic silicon, and carbon, but as the reducing agent in the production of high-quality metallic manganese, carbon is not suitable because it is easily mixed into metallic manganese (product), and metallic aluminum and/or metallic silicon are preferable. In place of silicon metal, inexpensive ferrosilicon may be used. In this case, the iron concentration in the product (manganese metal) becomes high, but iron is not an impurity when used as an iron-making raw material, and therefore, can be used as manganese metal.
Even when metallic aluminum or metallic silicon is used as a reducing agent, if the graphite electrode is brought into contact with the charged material, particularly molten metal (molten metal) generated by a reduction reaction, during heating and melting in the arc melting furnace, the carbon concentration in the molten metal inevitably increases to some extent. Therefore, in the arc melting furnace reduction step of the present invention, it is preferable to perform an operation (high voltage operation) for avoiding contact by increasing the distance (interval) between the graphite electrode and the charge or the molten metal. This prevents carbon from being picked up from the graphite electrode.
In the arc melting furnace reduction step of the present invention, the reduction may be performed in one step, but two-step reduction, i.e., primary reduction and final reduction, is preferable. When metallic aluminum and/or metallic silicon are used as the reducing agent, the reaction for reducing the degree of oxidation is maintained in the primary reduction, and the reaction for producing metallic Mn does not proceed. Therefore, the amount of the reducing agent to be added in the first reduction is a part of the total amount required. The manganese-containing material as the raw material is mixed in an amount required for the first reduction. The amount of the flux is preferably an amount suitable for the amount of the reducing agent. Then, at the time of final reduction, the entire required amount of the surplus reducing agent is charged together with the flux, and the reaction to generate metal Mn proceeds. This makes it possible to minimize the contact between the electrode and the molten metal (molten metal Mn) and to minimize the mixing of C (carbon) into the metal Mn.
In addition, aluminum metal undergoes a thermite reaction, generating a large amount of reaction heat. Therefore, when metallic aluminum is used as the reducing agent, if electric heating is performed when reaction heat of the reducing agent is generated, overheating may occur. Therefore, in the present invention, it is preferable to stop the energization heating by the electrode while the reaction heat of the reducing agent (thermite reaction heat) is generated. Thus, there are also the following advantages: the time for the electrical heating by the graphite electrode can be shortened, and the contamination of carbon into the product (manganese metal) can be suppressed.
In the arc melting furnace reduction step of the present invention, when metallic aluminum is used as the reducing agent, metallic aluminum as the reducing agent is preferably charged in portions in which the metallic aluminum is charged in plural times. This makes it possible to uniformize heat generation by the thermite reaction, prevent overheating, suppress evaporation (scattering loss) of the molten metal (metal Mn), and improve Mn retention. When the reducing agent is charged in portions, it is preferable to charge the manganese-containing substance and the flux or the flux as raw materials in portions in order to uniformize the reaction.
The flux used in the arc melting furnace reduction step of the present invention is preferably a flux containing CaO as a main component. Examples of the substance containing CaO as a main component include quicklime, limestone, and slaked lime.
The amount of the reducing agent to be added is, of course, not less than the amount of the reducing agent (theoretical reduction equivalent) required to completely carry out the reduction reaction of manganese or zinc, which is an oxide or hydroxide contained in the manganese-containing substance as the raw material, to metallic manganese or metallic zinc.
On the other hand, the amount of the flux is CaO/Al 2 O 3 And (4) adjusting the ratio. CaO/Al 2 O 3 The ratio is 0.55, but a good reaction progress can be obtained if the ratio is in the range of about 0.4 to 1.0. When the amount is less than 0.4, manganese oxide in the slag does not decrease, and when it exceeds 1.0, the amount of free quicklime increases, the melting point of the slag becomes too high, and the amount of slag increases excessively. Thus, the amount of the flux is preferably set to a ratio (mass ratio) of the amount of the flux in terms of CaO to the amount of the reducing agent in terms of oxide, that is, CaO/Al 2 O 3 The ratio is adjusted to be in the range of 0.4 to 1.0.
Examples
The present invention will be further described below with reference to examples.
Selecting manganese dry cells and/or alkaline manganese dry cells from waste dry cells, pulverizing the selected waste dry cells using a biaxial rotary pulverizer, sieving the crushed dry cells with a mesh: the resultant was sieved through a 3mm sieve to obtain a powder (waste dry battery powder). The composition of the resulting powder is shown in table 1. The obtained powder or granule contains oxygen and moisture derived from an oxide or hydroxide in addition to the elements shown in table 1.
First, water washing treatment is performed: 50g of the obtained powder/grain was put (charged) into a container (beaker), and 500mL of distilled water was added thereto so that the ratio of solid to liquid was 1: 10 washing with water. The water washing means the water washing time shown in table 2: 5. stirring in a container for 15min and 30 min.
Subsequently, the water-washed powder or granule was subjected to solid-liquid separation treatment by filtration using 5C filter paper, and separated into a solid component and a separation liquid. The obtained solid content was analyzed for chlorine. The results are shown in Table 2.
[ Table 1]
[ Table 2]
From table 2, it was confirmed that the chlorine content in the powder/granular material (waste dry battery powder/granular material) was determined by the treatment time: the washing treatment for about 15min can be sufficiently controlled to be less than 0.1 mass%. The chlorine content of less than 0.1 mass% is a target chlorine content of the raw material that can be charged into the arc melting furnace in the arc melting furnace reduction step.
Then, water washing treatment is performed: the solid-liquid ratio is 1: 10-5: the amount of the powder or granule obtained and the amount of distilled water added were changed to 10, and the powder or granule was put (charged) into a container (beaker) and washed with water. The water washing means that the treatment time is fixed as: stirring in a container for 15 min. Subsequently, the water-washed powder and granular material was subjected to solid-liquid separation treatment using 5C filter paper, and separated into a solid component and a separation liquid. The obtained solid content was analyzed for chlorine. The results are shown in Table 3.
[ Table 3]
From table 3, it was confirmed that even when the solid-liquid ratio reached 5: in the slurry having the increased solid content, the chlorine content in the powder (waste dry battery powder) can be sufficiently controlled to less than 0.1% by mass by the washing treatment, and the solid-liquid ratio has less influence on the chlorine content after the washing treatment. In this experiment, since the vessel was a small-sized vessel, sufficient stirring was possible by strong stirring, but when the vessel was large-sized, the solid-to-liquid ratio reached 3: about 10, uniform stirring is easy, but if the solid-liquid ratio is increased to 5: about 10, it is expected that uniform stirring is difficult. Therefore, when the apparatus is increased in size (the size of the powder or granule exceeds 20kg, which is a several-ton scale) as described below, the solid-to-liquid ratio is preferably 3: about 10. The present invention is implemented so that the solid-liquid ratio is 3: in the embodiment 10, after washing treatment in which 67kg of water was added to 20kg of the powder and granular material and agitated and washed, filtration was performed using a centrifugal filter, and as a result, powder and granular material having a recovery rate of 92 mass% and a water content of 20 mass% and having been washed with water was obtained. It was confirmed that if the solid-liquid ratio is such a degree, the treatment can be carried out without any problem in the water washing treatment and the solid-liquid separation treatment.
From this, it was judged that the solid-to-liquid ratio of the washing treatment of the manganese-containing substance (waste dry battery powder) was 5: about 10 min or less, and washing time of about 15min or more.
Next, the obtained powder/granular material (waste dry battery powder/granular material) was: about 100kg of the resultant was charged into a calciner, and heat treatment was carried out. The heat treatment was constant heating time: 180min, and changing the heating temperature within the range of 400-1000 ℃. Then, the residual carbon concentration in the heat-treated powder/granular material was measured. The obtained results are shown in table 4. Note that, at the heating temperature: the amounts of Mn and Zn were also measured at 800 ℃ and 1000 ℃.
[ Table 4]
From Table 4, it can be seen that the heating temperature: the residual carbon concentration after the heat treatment is reduced to 0.1 mass% or less at 600 ℃ or higher. Even at the heating temperature: the residual carbon concentration was also decreased by the heat treatment at 400 ℃ and 500 ℃, but the amount of decrease in the residual carbon concentration was small, and a long heat treatment exceeding 3hr was required to decrease the residual carbon concentration to 0.1 mass% or less. Therefore, it is understood that the heating temperature is not practical to be 400 ℃ or 500 ℃. It is understood from table 4 that the total weight is reduced by the removal of carbon by combustion as the heating temperature increases, and therefore the concentrations of manganese and zinc are relatively high.
Next, the heating temperature was set to 600 ℃ and 800 ℃, and the influence of the heating time on the residual carbon concentration in the powder/granular material was analyzed for a heating time within 60 min. The obtained results are shown in table 5.
[ Table 5]
At the heating temperature: at 600 ℃, it took about 60min for the residual carbon concentration to decrease to about 0.1 mass%. On the other hand, at the heating temperature: the residual carbon concentration decreased rapidly at 800 ℃ to about 0.1% by 30min of heat treatment. From this, it was determined that the heat treatment of the manganese-containing substance (waste dry battery powder) was about 60min at 600 ℃ or about 30min at 800 ℃.
Next, as described above, water washing treatment was performed: powder obtained by selecting, pulverizing and sieving waste dry batteries (waste dry battery powder): adding water into 90kg to prepare a solid-liquid ratio: 3: after 10 times of slurry, the slurry was stirred for 30min and washed with water; then, a solid-liquid separation treatment is further performed by a centrifugal filter apparatus to separate the solid component and the separated liquid. Next, the obtained solid content was charged into a calciner, and the heating temperature was set to: heating at 800 deg.C for 30 min.
Next, the solid component (waste dry battery powder) subjected to the above-described heating treatment is subjected to an arc melting furnace reduction step as a reduction step.
In the reduction step in the arc melting furnace, 5kg of a current-carrying metal Mn was charged into the furnace of the test arc melting furnace, and after lowering the graphite electrode, the initial mixed raw material was charged. The starting material mixture was a solid (waste dry battery powder) subjected to the above-described heat treatment: 50kg and metallic aluminum as a reducing agent: 12kg and CaO (quicklime) as a flux: 16.5 kg.
After the initial mixed raw materials are charged, the raw materials are melted by applying electric heating as initial heating. In the melting, the energization was stopped during the period from the start to the end of the thermite reaction.
After the completion of the thermite reaction after the initial heating, the reaction is stably accelerated to ensure a predetermined temperature, and then the current is applied again. This operation is repeated a plurality of times. The additional mixed raw materials are charged halfway. The additional raw materials to be mixed are aluminum metal: 4kg and CaO (quicklime) as a flux: 5.5 kg. The amount of the reducing agent added up to this point is less than the theoretical reduction equivalent required for the formation of metal Mn as a primary reduction treatment.
After the primary reduction treatment, a reducing agent and a flux are further additionally charged, and the final reduction treatment is performed. The additional reducing agent is metallic aluminum: 4kg, and the added flux is CaO: 3.5 kg. After the additional reducing agent is charged, the energization is stopped until the thermite reaction is completed in order to prevent overheating. In the final reduction treatment, after the completion of the aluminothermic reaction, slag is sufficiently generated, and then the electrode is immersed in the slag, and energization is performed for a predetermined time to promote the reaction and adjust the temperature. Note that, in the final reduction treatment, an operation of preventing carbon contamination by avoiding contact between the electrode and the molten metal is also performed.
After the reduction treatment is completed, molten slag is discharged, and molten metal (molten manganese metal) is poured into a mold and solidified. The amount of manganese metal obtained was 26 kg.
The composition of the obtained manganese metal is shown in table 6. Table 6 also shows the compositions of conventional electrolytic manganese and extremely low phosphorus and extremely low carbon ferromanganese for comparison.
[ Table 6]
Tuo) briquette
Blocks (instead of metal Mn)
From table 6, it was confirmed that in the examples of the present invention, zinc was almost volatilized by the reduction treatment using the arc melting furnace, and zinc was not remained in the metal, and carbon and other elements were less remained, and thus the examples were usable as an alternative to electrolytic manganese metal.
Claims (6)
1. A method for producing manganese metal, wherein manganese-containing material is obtained by selecting, crushing and screening waste dry batteries,
subjecting the manganese-containing substance to a water washing treatment in which the manganese-containing substance is subjected to water washing as a slurry,
then, the slurry subjected to the water washing treatment is subjected to a solid-liquid separation treatment for separating the slurry into a solid component and a liquid,
further, a heating treatment of heating the solid component separated by the solid-liquid separation treatment is performed,
the solid component subjected to the heating treatment is charged into an electric furnace together with a reducing agent and a flux, and the solid component is subjected to a reduction treatment by energization heating of the electric furnace and/or reaction heat of the reducing agent to obtain metal manganese.
2. The method for producing metallic manganese according to claim 1, wherein a ratio of a solid component to a liquid of the slurry in the water washing treatment is 1: 10-5: 10.
3. the method for producing metallic manganese according to claim 1 or 2, wherein a water washing time of the water washing treatment is 15 minutes or more.
4. The method for producing manganese metal according to claim 1 or 2, wherein the temperature of the heat treatment is 600 ℃ or higher.
5. The method for producing metallic manganese according to claim 1 or 2, wherein the reducing agent used in the reduction treatment is metallic aluminum and/or metallic silicon.
6. The method for producing metallic manganese according to claim 1 or 2, wherein the flux used in the reduction treatment is a substance mainly containing CaO.
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| JP6591675B2 (en) | 2019-10-16 |
| CN110431245A (en) | 2019-11-08 |
| JPWO2018168471A1 (en) | 2019-03-28 |
| WO2018168471A1 (en) | 2018-09-20 |
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