CN101845562A - Improved device and method for producing electrolytic manganese metal by two-ore method - Google Patents
Improved device and method for producing electrolytic manganese metal by two-ore method Download PDFInfo
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- CN101845562A CN101845562A CN201010205757A CN201010205757A CN101845562A CN 101845562 A CN101845562 A CN 101845562A CN 201010205757 A CN201010205757 A CN 201010205757A CN 201010205757 A CN201010205757 A CN 201010205757A CN 101845562 A CN101845562 A CN 101845562A
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 238000000034 method Methods 0.000 title claims abstract description 84
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 67
- 239000011572 manganese Substances 0.000 claims abstract description 128
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 111
- 239000012535 impurity Substances 0.000 claims abstract description 51
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 41
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 40
- 238000002386 leaching Methods 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 34
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 34
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 34
- 230000008569 process Effects 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 230000002829 reductive effect Effects 0.000 claims abstract description 9
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052683 pyrite Inorganic materials 0.000 claims abstract description 7
- 239000011028 pyrite Substances 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 93
- 239000000243 solution Substances 0.000 claims description 61
- 239000000843 powder Substances 0.000 claims description 48
- 238000005868 electrolysis reaction Methods 0.000 claims description 47
- 239000007788 liquid Substances 0.000 claims description 44
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 35
- 238000001914 filtration Methods 0.000 claims description 29
- 229910052742 iron Inorganic materials 0.000 claims description 28
- 238000005987 sulfurization reaction Methods 0.000 claims description 28
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 230000003647 oxidation Effects 0.000 claims description 19
- 238000007254 oxidation reaction Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 13
- 239000011669 selenium Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 239000003153 chemical reaction reagent Substances 0.000 claims description 11
- 238000003825 pressing Methods 0.000 claims description 11
- 238000000746 purification Methods 0.000 claims description 11
- 238000002161 passivation Methods 0.000 claims description 10
- 229910001385 heavy metal Inorganic materials 0.000 claims description 9
- 150000002739 metals Chemical class 0.000 claims description 9
- 235000011149 sulphuric acid Nutrition 0.000 claims description 9
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 206010053615 Thermal burn Diseases 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 6
- 238000012856 packing Methods 0.000 claims description 6
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical group [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000001117 sulphuric acid Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000011010 flushing procedure Methods 0.000 claims description 5
- 239000004160 Ammonium persulphate Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000002516 radical scavenger Substances 0.000 claims description 4
- 229910052711 selenium Inorganic materials 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 238000009991 scouring Methods 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- 229910018162 SeO2 Inorganic materials 0.000 claims description 2
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 238000011161 development Methods 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract 2
- 239000011707 mineral Substances 0.000 abstract 2
- 235000010755 mineral Nutrition 0.000 abstract 2
- 239000000047 product Substances 0.000 description 27
- 238000005516 engineering process Methods 0.000 description 25
- 229910052759 nickel Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000011084 recovery Methods 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 229910000616 Ferromanganese Inorganic materials 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000012629 purifying agent Substances 0.000 description 3
- 238000012797 qualification Methods 0.000 description 3
- 238000004451 qualitative analysis Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229940116901 diethyldithiocarbamate Drugs 0.000 description 2
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ISWQCIVKKSOKNN-UHFFFAOYSA-L Tiron Chemical compound [Na+].[Na+].OC1=CC(S([O-])(=O)=O)=CC(S([O-])(=O)=O)=C1O ISWQCIVKKSOKNN-UHFFFAOYSA-L 0.000 description 1
- ZGSDJMADBJCNPN-UHFFFAOYSA-N [S-][NH3+] Chemical class [S-][NH3+] ZGSDJMADBJCNPN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 235000003599 food sweetener Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
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- 210000000582 semen Anatomy 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- -1 soapmaking etc.) Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000003765 sweetening agent Substances 0.000 description 1
- 238000003886 thermite process Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
Classifications
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- 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
- C22B47/0018—Treating ocean floor nodules
- C22B47/0045—Treating ocean floor nodules by wet processes
- C22B47/0054—Treating ocean floor nodules by wet processes leaching processes
- C22B47/0063—Treating ocean floor nodules by wet processes leaching processes with acids or salt solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
-
- 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
- C22B47/0018—Treating ocean floor nodules
- C22B47/0045—Treating ocean floor nodules by wet processes
- C22B47/0081—Treatment or purification of solutions, e.g. obtained by leaching
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses an improved device and method for producing electrolytic manganese metal by a two-ore method. The method comprises the following steps of leaching, purifying, deeply purifying and electrolyzing; and two ore raw materials for electrolyzing the manganese metal by the two-ore method are low-grade manganese oxide ores and pyrite ores respectively, wherein the low-grade manganese oxide ores are with the manganese content of 15-25%, and the pyrite ores are tailings (the pyrite ores) of the mineral dressing of non-ferrous metal ores or primary ores. The method has the advantages that a product contains C and S, has low impurity and short production flow, is used for deeply purifying a manganese sulfate solution to eliminate the influence of reductive impurities in the solution on the electrolytic process, thereby realizing the normal electrolytic production and improving the quality of products. The method especially creates ways for the development and the utilization of low-grade lean manganese oxide ores and tailings (the pyrite ores) of the mineral dressing of non-ferrous metal ore.
Description
Technical field
The present invention relates to the apparatus and method technical field of electrolytic metal Mn, particularly a kind of device and method of modified version method for producing electrolytic manganese metal by two-ore.
Background technology
In modern industry, manganese and compound thereof are applied to the every field of national economy.Wherein Iron And Steel Industry is most important field, accounts for 90%～95% with the manganese amount, mainly as reductor and the sweetening agent in ironmaking and the steelmaking process, and is used for alloying.All the other manganese of 10%～5% are used for other industrial circles; as chemical industry (making the various manganese salts that contain), light industry (being used for battery, match, seal lacquer, soapmaking etc.), building materials industry (tinting material and the decolourant of glass and pottery), national defense industry, electronic industry; and environment protection and husbandry, or the like.In a word, manganese has crucial strategic position in national economy.
The application of manganese on Iron And Steel Industry is the result of various countries metallurgist unremitting effort decades.After 1875, European various countries begin to contain the spiegel of manganese 15%～30% and contain manganese and reach 80% ferromanganese with blast furnace production.Produce ferromanganese with electric furnace in 1890, produced manganese metal with thermite process in 1898, and developed electric furnace desiliconization purifying method production low carbon ferromanganese.Nineteen thirty-nine begins to produce manganese metal with electrolytic process.
The refinement mode of manganese metal mainly contains two kinds of hot method (pyrogenic process) and electrolytic process (wet method), and hot method production (manganese metal) purity is no more than 95～98%, and pure manganese metal then is that its purity can reach more than 99.7～99.9% by electrolytic process preparation (electrolytic metal Mn).Now, electrolytic process is produced has become the main mode that manganese metal is produced.Electrolytic metal Mn is to go out to obtain manganese salt with manganese ore through acidleach, the elemental metals that send electrolytic tank electrolysis to separate out again.The outward appearance chalybeate is irregular sheet, and matter is hard and crisp, the one side light, another side is coarse, for silvery white to brown, be silver gray after being processed as powder; Easily oxidation in air, dissolving and displace hydrogen when meeting diluted acid, a little more than room temperature the time, but water of decomposition and releasing hydrogen gas.
In the process of electrolytic manganese, make manganous sulfate earlier.The production method of existing manganese sulfate solution is: with crusher manganese ore is crushed to particle below the 30mm, with dry grinding mill manganese ore is worn into one 100 purpose breezes again, again the troilite powder that contains S＞=32%, granularity 80 1 100 orders, prepare according to a certain percentage with the manganese ore powder, again Jia Shui, add sulfuric acid.Through reacting by heating, deironing, removing heavy metals, neutralization, press filtration. make manganese sulfate solution.
There is following weak point in this traditional technology method:
1. producing the restriction be subjected to manganese ore content needs just can produce the manganese sulfate product that manganese content is recognized 98-99% with manganese content at the higher-grade manganese ore more than 34%, as the manganous sulfate content that can only produce at the low-grade manganese of 10-20% with manganese content at the product below 96%;
2, production cost height, energy consumption height: 1 ton of manganous sulfate of every production need consume coal 1.2-1.5 ton:
3, manganese recovery ratio is low: manganese recovery ratio is only up to 60-65%.
Chinese invention patent (following is the number of patent application or the patent No.) CN91102845, CN 92112673, CN 200510020913, CN 200710192608, CN 200710192613, CN 200810058946 patent documents such as grade and/or patent application document also disclose several two ore deposit methods respectively and have produced the method for electrolytic manganese and use low-grade manganese stone two ore deposit methods to produce the method for electrolytic manganese or the preparation technology of manganous sulfate, but aforesaid method has the following disadvantages:
1, there is not to solve the purification and impurity removal technology make after the manganese sulfate solution, the Technology instability of the manganous sulfate electrolysis production that obtains by two ore deposit methods, Production Flow Chart length, not environmental protection, energy consumption height, production cost height, the yield of manganese metal is low;
2, the manganese metal product of producing with above-mentioned technology contains C, S and measures highly, and purity is low;
3, in the production technology to the unexecuted deep purifying of manganese sulfate solution, do not remove that reducing impurity has reduced quality product to the influence of electrolytic process in the electrolytic solution;
4, in two ore deposit method electrolytic processes, to having relatively high expectations of sulfurous iron ore, adopt the high sulfurous iron ore of sulphur content, big to environmental influence, the production cost height;
5, the manganese metal recovery rate is low, and the rate of recovery of manganese metal only is 60%～63%.
Summary of the invention
Technical problem to be solved by this invention is, having overcome does not have to solve the manganese sulfate solution purification and impurity removal technology afterwards that makes in the prior art, the Technology instability of the manganous sulfate electrolysis production that obtains by two ore deposit methods, Production Flow Chart length, not environmental protection, energy consumption height, production cost height, problem such as the yield of manganese metal is low.A kind of device and method of modified version method for producing electrolytic manganese metal by two-ore is provided, successfully solved the purification and impurity removal technology of manganese sulfate solution, acquisition meets the qualified solution of electrolysis requirement, thereby the Technology that reaches electrolysis production is stable, Production Flow Chart weak point, environmental protection, energy-saving and cost-reducing, production cost is low, the metal recovery rate of manganese improves 10～15%.
For solving the problems of the technologies described above, the invention provides a kind of method of modified version method for producing electrolytic manganese metal by two-ore, said method comprising the steps of: leaching, purification, deep purifying and electrolysis;
Two kinds of ores of described two ore deposit method electrolytic metal Mns are respectively: low-grade manganese oxide ore and low grade pyrite;
Described low-grade manganese oxide ore is: manganese content is 15～25% manganese oxide ore;
Described low grade pyrite is: the mine tailing sulfurous iron ore of nonferrous metals ore ore dressing or primary sulfurous iron ore; Wherein, the content of sulphur is 25～30%.
The step of described leaching can comprise:
With manganese content is that 15～25% manganese oxide ore is a raw material, choose to contain S25～30%, contain Fe30～45% nonferrous metals ore mine tailing is the reductive agent raw material;
With two kinds of ore grindings is granularity 80-130 purpose breeze, and anolyte mixes, and directly is heated to 90-100 ℃ in the sulphuric acid soln of 85-120g/l; Wherein, according to ratio of weight and number manganese ore powder: troilite powder: the vitriolic ratio is 1: 0.30-0.5: 0.40-0.50;
Agitation leach 2-4 hour.
The step of described purification can comprise:
In the oxidation and deironing: the pulp PH value after leaching with the ammoniacal liquor adjustment is to 4.0-5.0, by containing Fe in the liquid
+ 2Amount add manganese ore powder Oxidation of Fe SO4 and generate Fe2 (SO) 3;
Adjust pulp PH value to 6-7 with ammoniacal liquor again, Fe2 (SO) 3 hydrolysis generate Fe (OH) 3 and are deposited in the leached mud, and ore pulp gets thick manganese sulfate solution through filter pressing;
Sulfuration removing heavy metals impurity: described thick manganese sulfate solution adds the vulcanizing agent sulfuration and removes beavy metal impurity, liquid after press filtration obtains vulcanizing.
The step of described deep purifying can comprise:
With the solution after the sulfuration purification, to adopt strong oxidizer discharge manganese powder and/or ammonium persulphate/hydrogen peroxide to make scavenging agent and carry out deep purifying, reducing impurity is removed in oxidation, makes reducing impurity be transformed into the simple substance element ion and exists in the solution;
Flocculated heavy clear 24-48 hour with Tai-Ace S 150 reagent again, behind the adding selenium, obtain the qualified new liquid of use in electrolysis after the press filtration.
Described electrolytic step can comprise:
Solution with the deep purifying step process is crossed adds Se, is configured to: Mn18-23g/l, (NH4) 2SO4100-120g/l, the fluting liquid of Se30-50mg/l; Regulate pH value to PH7.0-7.5 with ammonia soln;
Electrolysis is carried out in energising, and strength of current raises gradually, switches on after 4-8 hour, and strength of current is raised to the setting operation value;
Electrolysing period is 24 hours.
Described electrolysis procedure control condition is preferably as follows:
Advance tank liquor: Mn35-40g/L, (NH4) 2SO4 100-120g/L PH 6.5-7.0;
Catholyte: Mn15-18g/L, (NH4) 2SO4 110-120g/L PH 6.5-7.5;
Anolyte: Mn15-18g/L, (NH4) 2SO4 110-120g/L H2SO4 38-45g/L;
Cathode current density: 340-380A/m2; Bath voltage: 4.3-4.8V;
Tank liquor temperature: 38-45 ℃;
Electrolysis additive: SeO2 contains Se 20-40mg/L;
Electrolysing period: 24 hours.
The step of described leaching can comprise:
Earlier in leaching vat, inject anolyte, after anolyte has the first road agitating vane, do not start stirrer, begin then in leaching vat, to throw in manganese ore powder and troilite powder, and add sulfuric acid, open the steam heating ore pulp,, start the clock when slurry temperature reaches 90 ℃;
Detect the Mn amount that contains of leach liquor, after containing the Mn amount and reaching the concentration of setting, leach and finish;
Wherein,
Manganese ore powder: sulfurous iron ore: the sulfuric acid mass ratio is 1: 0.3～0.5: 0.38～0.5;
Leach 90～100 ℃ of slurry temperatures;
Extraction time: the end that feeds intake, ore pulp is warmed up to 90 ℃, picks up counting, and leaches 2～4 hours.
For solving the problems of the technologies described above, the present invention also provides a kind of device of producing electrolytic metal Mn, and described device comprises: powder manufacturing apparatus, leaching plant, filtering equipment, sulfuration pond, treating pond, dark treating pond, settling pool, air compressor, adjustment bucket and electrolyzer.
Described powder manufacturing apparatus can be the Raymond mill of 3R, 4R or 5R type;
Described leaching plant can be leaching vat that paddle formula mixing component is housed;
Described electrolyzer is preferably made with the lumps of wood, in the wooden false end, arranged, the snakelike water-cooled tube that stainless steel tube is made is equipped with in the inner both sides of described electrolyzer, each electrolyzer is provided with one or more groups anode frame, be provided with negative plate N piece in each electrolyzer, positive plate N+1 piece; Wherein, N is a positive integer.
Described negative plate can be stainless steel plate;
Described positive plate can be lead, antimony, tin, silver-colored quad alloy plate;
The ratio of the preferred useful area of described positive plate and negative plate useful area 0.6: 1.0;
After the described negative plate electrolysis, become negative electrode manganese plate; Described negative electrode manganese plate in use is used following method Passivation Treatment: passivator is potassium dichromate aqueous solution, concentration 3%, a negative electrode manganese of every taking-up plate when transferring groove, dip in passivating solution immediately, make the manganese metal table generate layer oxide film, reach the not oxidized blackening in air of manganese plate, do not influence quality product;
Manganese plate after the passivation is used flushing with clean water, the passivator on flush away surface, and then put into 80～100 ℃ of boiling hot water and scald, impurity such as crystalline ammonium sulfate on the flush away manganese plate;
Scald back manganese plate through air-dry, peel off, obtain the sheet metal manganese product, then the packing warehouse-in;
Negative plate after the demanganize is treated to: the pole plate of non-cohesive residual manganese, and stand-by after cleaning; Be attached with and peel off to get off residual manganese plate and be put into anolyte drill traverse bubble, after residual manganese dissolve, dip in nitric acid liquid, the clear water scouring is afterwards stand-by again;
It is stand-by that the negative plate of brightless (turn white, scared) is electroplated the polishing back.
The method of modified version method for producing electrolytic manganese metal by two-ore of the present invention and device thereof belong to pure hydrometallurgical processes, and industrial production test shows, mature production technology, and advanced technology is reliable, and quality product height, especially product contain C, S, and impurity is low.The traditional technology that present method and manganese oxide ore are produced electrolytic manganese compares, and has improved workman's labor condition, and Production Flow Chart is short, is the producing and manufacturing technique of environmental protection and energy saving in fact.Production practice are carried out deep purifying to manganese sulfate solution, have removed in the solution reducing impurity to the influence of electrolytic process, thereby have reached the electrolysis ordinary production, improve the quality of products.Present method especially is that approach has been created in the development and use of the mine tailing (sulfurous iron ore) of low-grade oxygen deprivation manganese ore and nonferrous metals ore ore dressing.Moreover low product manganese oxide ore and sulfurous iron ore source are wide, and price is low, so production cost is low, and the manganese metal recovery rate is than traditional technology raising 10～15%.
Description of drawings
Fig. 1 is the schema of modified version method for producing electrolytic manganese metal by two-ore method in the embodiment of the invention.
Embodiment
The method of method for producing electrolytic manganese metal by two-ore of the present invention, be by: ore fine grinding, batch mixes, leaching, purification, deep purifying, electrolytic processing step carry out.Above-mentioned leaching step comprises: be raw material with the manganese oxide ore, sulfurous iron ore is a reductive agent, and two kinds of breezes (granularity 100% is the 80-130 order) mix with anolyte by proportioning, and directly heated and stirred leaches in sulphuric acid soln, and manganese is MnSO
4, iron is Fe
2(SO
4)
3Enter solution.The present invention has improved workman's labor condition, for approach has been created in the development and use of low-grade manganese oxide ore and nonferrous metals ore milltailings (sulfurous iron ore).The present invention is through production test for many years, successfully solved the purification and impurity removal technology of manganese sulfate solution, acquisition meets the qualified solution of electrolysis requirement, thereby the Technology that reaches electrolysis production is stable, Production Flow Chart weak point, environmental protection, energy-saving and cost-reducing, production cost is low, the metal recovery rate of manganese improves 10～15%.
In one embodiment of this invention, method for producing electrolytic manganese metal by two-ore carries out according to the following steps:
Raw material is manganese oxide ore (low-grade manganese oxide ore contains Mn15～25%).
Reductive agent is sulfurous iron ore (mine tailing of nonferrous metals ore ore dressing or a primary sulfurous iron ore).
One, the preparation of manganese ore powder processing
1, the mechanical means of preparation manganese ore powder
Manganese ore prepares particulate manganese ore powder through ore grinding, and it is powder process machinery that this technology is selected the Raymond mill of 3R, 4R, 5R type for use.These facility have the size separation device, can regulate the granularity and the output of output powder;
2, the granularity requirements of manganese ore powder and reductive agent
By experiment and production practice, be to produce to obtain satisfied technico-economical comparison, it be ideal that manganese ore powder and sulfurous iron ore fineness requirement 100% are crossed 80～130 mesh sieve holes;
3, the main chemical compositions of manganese ore powder and reductive agent
The main chemical compositions of manganese ore powder: require to contain Mn15～25%
The sulfurous iron ore main chemical compositions: require to contain S25～30%, Fe35～40%, other impurity element (Co, Ni, Zn, Cu etc.) content is low more good more, can reduce impurity removal reagents consumption like this.
Two, the leaching system liquid operation of manganese ore powder
1, leaching plant general introduction
Leaching vat are major equipments of this operation, for satisfying the requirement of producing 20,000 tons of production technique, have selected 7 leaching vat that paddle formula whipping appts is housed for use, and its volume is useful volume 300m
3/ groove), 7 (useful volume 300m have been selected for use
3/ groove) leaching vat are equipped with paddle formula whipping appts.
2, leach the operation of operation
The technical qualification of 2-1, leaching: established following technical qualification promptly by test:
Manganese ore powder: sulfurous iron ore: sulfuric acid (mass ratio) is that 1: 0.3～0.5: 0.3～0.5. leaches 90～100 ℃ of slurry temperatures
Extraction time: the end that feeds intake, ore pulp is warmed up to 90 ℃, picks up counting, and leaches 2～4 hours.
2-2, leaching operation concrete operations: in leaching vat, inject anolyte on request earlier, after having the first road agitating vane, anolyte do not start stirrer, begin then in leaching vat, to throw in manganese ore powder and troilite powder by measuring requirement, and add an amount of sulfuric acid by the requirement of sulfuric acid consumption, open the steam heating ore pulp, when slurry temperature reaches 90 ℃, start the clock.Process repeatedly detects the Mn amount of containing of leach liquor, after containing the Mn amount and reaching given concentration, leaches at last and finishes.
The chemical reaction of 2-3, leaching process: two ore deposit method leaching process, manganese is MnSO
4, iron is Fe
2(SO
4)
3Enter solution, other impurity element (Co, Ni, Zn, Cu etc.) also generates corresponding vitriol and enters in the solution, and leaching process belongs to very complicated heterogeneous chemical reaction, and its net reaction is
15MnO
2+2FeS
2+14H
2SO
4＝15MnSO
4+Fe
2(SO
4)
3+14H
2O
MeO+H
2SO
4＝MeSO
4+H
2O
MeO is heavy metal (Co, Ni, Zn, Cu an etc.) oxide compound.
2-4, leach in the ore pulp oxidation and deironing: leach and finish, pulp PH value is 2.5～3.0, sampling qualitative analysis Fe
2+Ion is according to Fe
2+The content situation is adjusted pulp PH value to 4.5～5.0 with ammoniacal liquor, drops into an amount of manganese ore powder in the leaching vat then and carries out oxidation, stirs oxidation 20～30 minutes, and qualitative analysis Fe takes a sample
2+, until Fe
2+Reach qualified requirement, adjust pulp PH value to 6.0～6.5 with ammoniacal liquor again.Fe in the leach liquor under this condition
2(SO
4)
3But complete hydrolysis generates Fe (OH)
3Be deposited in and reach deironing purpose, Fe in the leached mud
2(SO
4)
3Hydrolysis is undertaken by the following formula reaction:
Fe
2(SO
4)
3+6H
2O＝2Fe(OH)
3+3H
2SO
4
In the iron removal, most of heavy metal ion is hydrolytic precipitation also, impurity SiO
2In company with Fe (OH)
3Be deposited in the leached mud Mn
2+A small amount of hydrolytic precipitation is arranged, therefore must fine grasp in and the pulp PH value of deironing, to reduce the loss of Mn.In the ore pulp oxidation and after the deironing end,, obtain the qualified leach liquor of iron content through press filtration (filter residue send the slag field to store up).
The specification of quality of 2-5, qualified leach liquor: it is 38～42g/l that leaching solution in oxidation and after the deironing requires to contain Mn, qualitative detection Fe
2+For not having.
Three, manganous sulfate leach liquor sulfuration removing heavy metals impurity
1, device overview: filtering equipment 400m
2Four, 200m
2Four, sulfuration pond 300m
3Four, treating pond 300m
3Ten, dark treating pond 300m
3Ten, settling pool 300m
3Eight, air compressor 8m
3Two, an adjustment bucket 2m
3Three.
2, vulcanizing agent:
The vulcanizing agent that manganese sulfate solution sulfuration removing heavy metals impurity uses has: saturated ammonium sulfide, barium sulphide (BaS), Sodium Dimethyldithiocarbamate (S.D.D), diethyldithiocarbamate etc., represent vulcanizing agent with RS.
3, the remaining beavy metal impurity (Co, Ni, Zn, Cu etc.) of manganese sulfate solution that obtains through press filtration, must add vulcanizing agent vulcanizes, and makes it generate sulfide precipitation and removes, and the main chemical reactions formula is:
MeSO
4+ RS=RSO
4+ MeS ↓ Me → expression impurity element
Sulfuration removal of impurities major technique condition, 50～65 ℃ of solution temperatures, the vulcanizing agent consumption determines that by test our actually operating (contains NH with ammonium sulfide
38%) consumption is an example: every cube is come leach liquor consumption ammonium sulfide 2Kg.
Sulfuration removal of impurities concrete operations: manganese sulfate solution sulfuration removal of impurities can be carried out in special stirring truck for vulcanlzing pan, and we are added dropwise to ammonium sulfide liquid in the chute of pressing filtering liquid, the sulfuration liquid that adds ammonium sulfide liquid flows to Chu Chizai and stirred 20～30 minutes with the air compressor wind, get liquid analysis heavy metal content, after Ni, CO, Zn qualitative analysis are qualified, carry out press filtration, stack the special slag of filter residue field, and filtrate is carried out the deep purifying operation.
4, the specification of quality of sulfuration back liquid: sulfuration back pressing filtering liquid requires:
Contain Mn38～40g/l, Co＜1mg/l, Ni＜1mg/l,
Zn≤0.5mg/l，Fe＜1mg/l，Cu＜0.5mg/l.PH6.0～6.5.
Four, sulfuration back liquid deeply purifying and removing reducing impurity
Contain the reducing impurity ion in the pressing filtering liquid of manganese sulfate solution sulfuration removing heavy metals impurity, the electrolysis operation there is detrimentally affect even makes the electrolysis can't ordinary production, seriously influence simultaneously quality product, therefore must carry out deep purifying to pressing filtering liquid after vulcanizing and remove the reducing impurity ion, making it generate the simple substance ion is suspended in the solution, in solution, add flocculation agent then, flocculate, enter press filtration again behind the settling pool heavy clear more than 24 hours (time long more help more electrolysis) once more.In pressure-filtering process, in liquid, add an amount of selenium, thereby obtain to meet the seminal fluid of electrolysis requirement.
1, the selection of deep purifying agent: remove that the scavenging agent of reducing impurity has a lot of strong oxidizers available in the manganese sulfate solution: as manganese dioxide powder, ammonium persulphate, hydrogen peroxide etc., through a large amount of experimental studies, this process choice hydrogen peroxide obtains satisfied techno-economic effect for the deep purifying agent.
The add-on of 2, deep purifying agent (hydrogen peroxide), long-pending according to sulfuration back liquid, add by every cubic metre of amount that adds 0.25～0.35 kilogram of hydrogen peroxide, earlier hydrogen peroxide is mixed with the aqueous solution of 20～40% concentration, in the pressing filtering liquid chute, filtrate flow is to storing up the pond after sulfuration in dropping, after leaving standstill 4 hours, make its abundant oxidation, make the reducing impurity ion-oxygen change into the simple substance ion, and then it is heavy clear to flocculate.
3, flocculation is heavy clear: flocculation agent is selected Tai-Ace S 150 for use, and consumption is 0.1～0.15Kg/m
3Solution is dissolved into the aqueous solution with the Tai-Ace S 150 water earlier, adds and leaves standstill in the pond, starts the pressure fan pneumatic blending 4～5 minutes, carries out the pressure-sizing filter when leaving standstill after 24～48 hours.Add an amount of electrolysis additive by new liquid requirement in the pressure-sizing process, concrete add-on 10～15mg/l Se meter.
4, qualified new liquid composition requires behind the deep purifying:
Mn36～40g/l, Co＜1mg/l, Ni＜1mg/l, Zn≤0.5～1mg/l, S
2-＜2mg/l.Fe
2+Qualitative qualified.
Five, manganese sulfate solution electrolytic deposition manganese industrial practice
The electrolysis production manganese metal all is at neutral MnSO
4～(NH
4)
2SO
4～H
2Carry out diaphragm electrolysis in the manganese sulfate solution of O system, anode is placed in the diaphragm frame, and electrolytic process manganese is separated out on negative electrode, precipitated oxygen and a spot of MnO on the anode
2. production practice are pressed step and are carried out.
1, fluting liquid becomes assignment system to require: Mn18～23g/l, (NH
4)
2SO
4100～120g/l, Se30～50mg/l, after PH6.5～7.5. electrolyzer is filled with fluting liquid, in each electrolyzer, adorn 3～5 negative plates, begin energising and carry out electrolysis, pile the negative plate of all electrolyzers then as early as possible, supply current intensity raises by wash rice, and the 4 hours after-current intensity of switching on can rise to values for normal operation.
2, the technology condition of electrolysis procedure control:
Advance tank liquor: Mn35～40g/l, (NH
4)
2SO
4100～120g/l, Se10～15mg/l, PH6.5～7.5.
Catholyte: Mn15～18g/l, (NH
4)
2SO
4100～120g/l, Se25～30mg/l, PH6.5～7.5.
Anolyte: Mn15～18g/l, (NH
4)
2SO
4100～120g/l, H
2SO
438～45g/l.
Cathode current density 340～380A/m
2, bath voltage 4.3～4.8V, 38～45 ℃ of tank liquor temperatures, similar poles are apart from 70mm, electrolysing period 24 hours.
3, electrolytic cell assembly
3-1, electrolyzer: electrolyzer is made with the thick lumps of wood of 40mm, in the wooden false end, arranged, outage 170mm at the false end, sky is of a size of length * wide * height=3800 * 710 * 920 (mm) in the trough, the snakelike water-cooled tube that stainless steel tube is made is equipped with in trough two inboards, each electrolyzer is equipped with 5 groups of anode frames, and the dress negative plate is 50 in each electrolyzer, 51 of positive plates.
3-2, yin, yang plate plate: it is negative plate that electrolytic manganese adopts stainless steel plate: it is of a size of length * wide * thick=665 * 500 * 1.5 (mm).Selecting lead, antimony, tin, silver-colored quad alloy plate for use is positive plate, and anodic length * wide * thick=665 * 470 * 7.9 (mm) has 50 holes on the pole plate, and the chi in each hole is long 86 * wide by 28.3 (mm).The ratio 0.6 of positive plate useful area and negative plate useful area: 1.0.
4, the processing of negative electrode manganese plate
4-1, accent groove: when electrolysis reaches 24 hours, need to take out the negative plate that deposits manganese, load onto this process of stand-by negative plate (dipping in water glass liquid, water glass liquid concentration 1～3% before the dress) simultaneously and claim to transfer groove, half an hour before the accent groove, by given operational condition, adjust the pH value (7.5～8.0) of tank liquor with ammoniacal liquor, and add an amount of Se, make tank liquor Se content reach 35～45mg/l. treat whole negative plates get the dress finish, promptly transfer trough end.
The Passivation Treatment of 4-2, negative electrode manganese plate
In order to prevent manganese metal by deterioration by oxidation in the air, negative electrode manganese must carry out Passivation Treatment.Passivator is potassium dichromate aqueous solution, concentration 3%, and a negative electrode manganese of every taking-up plate dips in passivating solution immediately when transferring groove, and the manganese metal table generates layer oxide film, reaches the not oxidized blackening in air of manganese plate, influences quality product.
The manganese plate is used flushing with clean water after 4-3, the passivation, the passivator on flush away surface, and then put into 80～100 ℃ of boiling hot water and scald, impurity such as crystalline ammonium sulfate on the flush away manganese plate.Scald back manganese plate through air-dry, peel off, obtain the sheet metal manganese product, then packing warehouse-in (ton bag packing).Quality product reaches the requirement of electrolytic manganese industry standard (YB-T051-2003) general purpose grade DJMnD level quality standard through assay.
The processing of 4-4, negative plate: the negative plate after the demanganize is handled, and depends on the circumstances: the pole plate of non-cohesive residual manganese, and stand-by after cleaning; Be attached with and peel off to get off residual manganese plate and be put into anolyte drill traverse bubble, after residual manganese dissolve, dip in nitric acid liquid, the clear water scouring is afterwards stand-by again.It is stand-by that brightless negative plate is electroplated the polishing back.
In the another embodiment of the present invention, provide the method for another kind of method for producing electrolytic manganese metal by two-ore, pressed: leaching, purification, deep purifying, electrolysis process step are carried out, wherein:
(1) leaches: be raw material (15-25%Mn) 1. with low-grade manganese oxide ore, non-ferrous metal ore mine tailing (primary sulfurous iron ore) is a reductive agent (contain S20-30%, contain Fe30-35%), two kinds of breezes (granularity 100%-80-130 order) anolyte mixes, directly in sulfuric acid (85-120g/l) solution, heat (90-100 ℃) agitation leach 2-4 hour (manganese ore powder: troilite powder: sulfuric acid (weight ratio), in 1: 0.30-0.5: the ratio of 0.40-0.50, these several examples are adjusted with situation); Manganese is MnSO
4, iron is Fe
2(SO
4)
3Enter solution, leaching process belongs to complicated heterogeneous chemical reaction process, and generally acknowledged chemical reaction is pressed net reaction and carried out:
15MnO
2+2FeS
2+14H
2SO
4＝15MnSO
4+Fe
2(SO
4)
3+14H
2O
(2) purify:
1. in the oxidation and deironing: adjust pulp PH value to 4.0-5.0, by containing Fe in the liquid with ammoniacal liquor
+ 2Other adds suitable manganese ore powder Oxidation of Fe SO
4Generate Fe
2(SO)
3, adjust pulp PH value again to 6.5-7.0, Fe
2(SO)
3Hydrolysis generates Fe (OH)
3Be deposited in the leached mud, ore pulp gets thick manganese sulfate solution through filter pressing;
2. sulfuration removes and heavily belongs to impurity, and described thick manganese sulfate solution adds an amount of vulcanizing agent (ammonium sulfide, BaS, SDD, diethyldithiocarbamate) sulfuration and removes beavy metal impurity (Ni, Co.Zn.Cn etc.), liquid after press filtration obtains vulcanizing.
(3) deep purifying:
Sulfuration back liquid removes reducing impurity, adopt strong oxidizer discharge manganese powder, ammonium persulphate, hydrogen peroxide to make scavenging agent, oxidation removes the reducing impurity test, is finally carrying out deep purifying with hydrogen peroxide reagent, makes reducing impurity be transformed into the simple substance element ion and exists in the solution;
Flocculated heavy clear 24-48 hour with Tai-Ace S 150 reagent again, add the qualified new liquid that an amount of selenium (Se) obtains use in electrolysis after the press filtration.
(4) electrolysis:
1. liquid Composition Control: the Mn18-23g/l that slots, (NH
4)
2SO
4After 100-120g/l, Se30-50g/l, PH6.5-7.5, electrolyzer piled fluting liquid, every groove was put 3～5 negative plates earlier, and electrolysis is carried out in energising, and after negative plate was piled, strength of current raise gradually, switched on after 4 hours, and strength of current is raised to values for normal operation.
2.. the groove face management, after the energising electrolysis, strengthen electrolyzer facial canal reason: the contraposition of close inspection pole plate is correct, measures the composition of tank liquor on time, and as Mn concentration, pH value etc. are regulated the tank liquor composition with flow quantity at any time and are reached the technical qualification requirement.
3.. electrolysis procedure control condition is as follows:
Advance tank liquor: Mn35-40g/L, (NH
4)
2SO
4100-120g/L PH 6.5-7.0;
Catholyte: Mn15-18g/L, (NH
4)
2SO
4110-120g/L PH 6.5-7.5;
Anolyte: Mn15-18g/L, (NH
4)
2SO
4110-120g/L H2SO4 38-45g/L;
Cathode current density: 340-380A/m2; Bath voltage: 4.3-4.8V;
Tank liquor temperature: 38-45 ℃;
Electrolysis additive: SeO
2, contain Se 20-40mg/L;
Electrolysing period: 24 hours.
4. electrolysis was transferred groove after 24 hours, transferred groove promptly to take out the sedimentation manganese negative plate, and the stand-by negative plate of packing into carries out the next cycle electrolysis procedure.
5. amassing the manganese negative plate handles: the long-pending manganese negative plate of taking-up, carry out passivation immediately, and prevent that product is oxidized, reduce quality, pole plate after the passivation is used flushing with clean water earlier, scalds again, and the back is air-dry, peels off, and gets flaked product, the packing warehouse-in.
6. quality product reaches GB (GB3418-82) quality standard.
7. the negative plate of peeling off behind the product is handled, and has the negative plate of residual manganese to put into anolyte earlier and soaks a moment, takes out with putting into nitric acid liquid after the flushing with clean water and soaks a moment, uses the clear water cleaned standby seam again.The negative plate that does not have residual manganese, stand-by through the clear water scrub.
Among the embodiment more of the present invention, operation as follows:
Get percent of pass 100%, granularity is 80 purpose manganese ore powder and troilite powders, and in the manganese ore powder: troilite powder: the ratio of sulfuric acid=1: 0.35: 0.42 directly is heated to 90-100 ℃ in sulphuric acid soln, agitation leach 3 hours, adjusting ore pulp PH is 4.5-5.0 manganese powder Oxidation of Fe SO
4Generate Fe
2(SO)
3Adjust pulp PH value to 6-6.5 with ammoniacal liquor, Fe
2(SO)
3Hydrolysis generates Fe (OH)
3Be deposited in the leached mud, ore pulp gets thick manganese sulfate solution through filter pressing; The press filtration waste gets thick manganese sulfate solution.Described thick manganese sulfate solution is removed beavy metal impurity (Ni, Co.Zn.Cu etc.) through sulfuration, and described thick manganese sulfate solution adds the vulcanizing agent sulfuration and removes beavy metal impurity (Ni, Co.Zn.Cn etc.), liquid after press filtration obtains vulcanizing.Under 55-65 ℃ of condition, carry out deep purifying with hydrogen peroxide reagent again, make reducing impurity be transformed into the simple substance element ion and exist in the solution; Flocculated heavy clear 24 hours with Tai-Ace S 150 reagent, press filtration obtains the qualified new liquid of use in electrolysis again.Obtain to reach the electrolytic metal manganese product of GB (GB3418-82.99.7%Mn) through electrolysis.
In the fourth embodiment of the present invention, operation as follows:
Get percent of pass 100%, granularity is 90 purpose manganese ore powder and troilite powders, in the manganese ore powder: troilite powder: the ratio of sulfuric acid=1: 0.4: 0.4, directly in sulphuric acid soln, be heated to 90-100 ℃, agitation leach 3 hours, adjusting pulp PH value is 4.0～5.0, add an amount of manganese powder, with Fe
2+Ion-oxygen changes into Fe
3+Ion is adjusted pulp PH value to 6-6.5 with ammoniacal liquor, Fe
2(SO)
4Hydrolysis generates Fe (OH)
3Be deposited in the leached mud, ore pulp gets thick manganese sulfate solution through filter pressing; The press filtration waste gets thick manganese sulfate solution.Described thick manganese sulfate solution is removed beavy metal impurity (Ni, Co.Zn.Cu etc.), liquid after press filtration obtains vulcanizing through sulfuration.Under 55-65 ℃ of condition, carry out deep purifying with hydrogen peroxide reagent again, make reducing impurity be transformed into the simple substance element ion and exist in the solution; Flocculated heavy clear 32 hours with Tai-Ace S 150 reagent, press filtration obtains the qualified new liquid of use in electrolysis again.Obtain to reach the electrolytic metal manganese product of GB (GB3418-82.99.7%Mn) through electrolysis.
In the fifth embodiment of the present invention, operation as follows:
Get percent of pass 100%, granularity is 100 purpose manganese ore powder and troilite powders, in the manganese ore powder: troilite powder: the ratio of sulfuric acid=1: 0.45: 0.45, directly in sulphuric acid soln, be heated to 90-100 ℃, agitation leach 4 hours, ore pulp is in oxidation and after the deironing.Adjust pulp PH value to 6.5, Fe with ammoniacal liquor
2(SO)
4Hydrolysis generates Fe (OH)
3Be deposited in the leached mud, ore pulp gets thick manganese sulfate solution through filter pressing, and the press filtration waste gets thick manganese sulfate solution.Described thick manganese sulfate solution adds the vulcanizing agent sulfuration and removes beavy metal impurity (Ni, Co.Zn.Cn etc.), liquid after press filtration obtains vulcanizing.Under 55-65 ℃ of condition, carry out deep purifying with hydrogen peroxide reagent again, make reducing impurity be transformed into the simple substance element ion and exist in the solution; Flocculated heavy clear 48 hours with Tai-Ace S 150 reagent, press filtration obtains the new liquid of use in electrolysis again.Obtain to reach the electrolytic metal manganese product of GB (GB3418-82.99.7%Mn) through electrolysis.
Through overtesting, each above-mentioned processing parameter is all influential to improving manganese ore transformation efficiency and minimum raw material consumption etc., wherein, with example five processing condition best, output is the highest, energy consumption is low.The product of gained after the electrolytic solution electrolysis that makes according to above-mentioned embodiment through passivation, is washed, is scalded, air-dry, peel off flaked product, quality meets national standard (GB3418-82,99.7%).
Modified version method for producing electrolytic manganese metal by two-ore method of the present invention belongs to pure hydrometallurgical processes, and industrial production test showed in 2005～2009 years, mature production technology, and advanced technology is reliable, and quality product height, especially product contain C, S, and impurity is low.The traditional technology that present method and manganese oxide ore are produced electrolytic manganese compares, and has improved workman's labor condition, and Production Flow Chart is short, is the producing and manufacturing technique of environmental protection and energy saving in fact.Production practice are carried out deep purifying to manganese sulfate solution, have removed in the solution reducing impurity to the influence of electrolytic process, thereby have reached the electrolysis ordinary production, improve the quality of products.
Present method especially is that approach has been created in the development and use of the mine tailing (sulfurous iron ore) of low-grade oxygen deprivation manganese ore and nonferrous metals ore ore dressing.Moreover low product manganese oxide ore and sulfurous iron ore source are extensively, and price is low, so production cost is low, and the manganese metal recovery rate is 65%-67%.
All are above-mentioned to be the primary device for carrying out said and the method thereof of this intellecture property, does not set restriction and implements this improved method and device thereof with other form.Those skilled in the art will utilize this important information, foregoing be revised, to realize similar implementation status.But all are based on modification of the present invention or transform new device, belong to the right of reservation.
The above only is preferred embodiment of the present invention, is not to be the restriction of the present invention being made other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But every technical solution of the present invention content that do not break away from according to any simple modification, equivalent variations and the remodeling that technical spirit of the present invention is done above example, still belongs to the protection domain of technical solution of the present invention.
Claims (10)
1. the method for a modified version method for producing electrolytic manganese metal by two-ore is characterized in that:
Said method comprising the steps of: leaching, purification, deep purifying and electrolysis;
Two kinds of ores of described two ore deposit method electrolytic metal Mns are respectively: low-grade manganese oxide ore and low grade pyrite;
Described low-grade manganese oxide ore is: manganese content is the manganese oxide ore of 15-25%;
Described sulfurous iron ore is: the mine tailing of nonferrous metals ore ore dressing or primary sulfurous iron ore.
2. according to the method for the described modified version method for producing electrolytic manganese metal by two-ore of claim 1, it is characterized in that the step of described leaching comprises:
With manganese content is that 15～25% manganese oxide ore is a raw material, and nonferrous metals ore milltailings sulfurous iron ore is the reductive agent raw material;
With two kinds of ore grindings is granularity 80-130 purpose breeze, mixes with anolyte, directly is heated to 90-100 ℃ in the sulphuric acid soln of 85-120g/l; Wherein, according to ratio of weight and number manganese ore powder: troilite powder: the vitriolic ratio is 1: 0.30-0.5: 0.35-0.50;
Agitation leach 2-4 hour.
3. according to the method for the described modified version method for producing electrolytic manganese metal by two-ore of claim 1, it is characterized in that the step of described purification comprises:
In the oxidation and deironing: the pulp PH value after leaching with the ammoniacal liquor adjustment is to 4.0-5, by containing Fe in the liquid
+ 2Amount add manganese ore powder Oxidation of Fe SO
4Generate Fe
2(SO)
3
Adjust pulp PH value to 6-6.5 with ammoniacal liquor again, Fe
2(SO)
3Hydrolysis generates Fe (OH)
3Be deposited in the leached mud, ore pulp gets thick manganese sulfate solution through filter pressing;
Sulfuration removing heavy metals impurity: described thick manganese sulfate solution adds the vulcanizing agent sulfuration and removes beavy metal impurity, liquid after press filtration obtains vulcanizing.
4. according to the method for the described modified version method for producing electrolytic manganese metal by two-ore of claim 1, it is characterized in that the step of described deep purifying comprises:
With the solution after the sulfuration, adopt strong oxidizer discharge manganese powder and/or ammonium persulphate, hydrogen peroxide to make scavenging agent, reducing impurity is removed in oxidation;
Making reducing impurity be transformed into the simple substance element ion exists in the solution;
Flocculated heavy clear 24-48 hour with Tai-Ace S 150 reagent again, add selenium after the press filtration and (behind the 15-20mg/l, obtain the qualified new liquid of use in electrolysis.
5. according to the method for the described modified version method for producing electrolytic manganese metal by two-ore of claim 1, it is characterized in that described electrolytic step comprises:
Solution with the deep purifying step process is crossed is configured to: Mn18-23g/l, (NH4) 2SO4100-120g/l, Se30-50g/l, pH value are 7～7.5 fluting liquid.
Electrolysis is carried out in energising, and strength of current raises gradually, switches on after 4-8 hour, and strength of current is raised to the setting operation value;
Electrolysing period is 24 hours.
6. according to the method for each described modified version method for producing electrolytic manganese metal by two-ore among the claim 1-5, it is characterized in that described electrolysis procedure control condition is as follows:
Advance tank liquor: Mn35-40g/L, (NH4) 2SO4 100-120g/L PH 6.5-7.0;
Catholyte: Mn15-18g/L, (NH4) 2SO4 110-120g/L PH 6.5-7.5;
Anolyte: Mn15-18g/L, (NH4) 2SO4 110-120g/L H2SO4 38-45g/L;
Cathode current density: 340-380A/m2; Bath voltage: 4.3-4.8V;
Tank liquor temperature: 38-45 ℃;
Electrolysis additive: SeO2 contains Se 25-40mg/L;
Electrolysing period: 24 hours.
7. according to the method for each described modified version method for producing electrolytic manganese metal by two-ore among the claim 1-6, it is characterized in that the step of described leaching comprises:
Earlier in leaching vat, inject anolyte, after anolyte has the first road agitating vane, do not start stirrer, and continue to inject anolyte, begin then in leaching vat, to throw in manganese ore powder and troilite powder, and add sulfuric acid, open the steam heating ore pulp, when slurry temperature reaches 90 ℃, start the clock;
Detect the Mn amount that contains of leach liquor, after containing the Mn amount and reaching the concentration of setting, leach and finish;
Wherein,
Manganese ore powder: sulfurous iron ore: the sulfuric acid mass ratio is 1: 0.3-0.5: 0.4-0.5;
Leach 90-100 ℃ of slurry temperature;
Extraction time: the end that feeds intake, ore pulp is warmed up to 90 ℃, picks up counting, and leaches 2～4 hours.
8. device as the production electrolytic metal Mn that uses in the method for modified version method for producing electrolytic manganese metal by two-ore as described in each among the claim 1-7, it is characterized in that described device comprises: powder manufacturing apparatus, leaching plant, filtering equipment, sulfuration pond, treating pond, dark treating pond, settling pool, air compressor, adjustment bucket and electrolyzer.
9. the device of described according to Claim 8 production electrolytic metal Mn is characterized in that,
Described powder manufacturing apparatus is: the Raymond mill of 3R, 4R or 5R type;
Described leaching plant is: the leaching vat that paddle formula mixing component is housed;
Described electrolyzer is made with the lumps of wood, in the wooden false end, arranged, the snakelike water-cooled tube that stainless steel tube is made is equipped with in the inner both sides of described electrolyzer, each electrolyzer is provided with one or more groups anode frame, is provided with negative plate N piece in each electrolyzer, positive plate N+1 piece; Wherein, N is a positive integer.
10. according to the device of the described production electrolytic metal Mn of claim 9, it is characterized in that,
Described negative plate is a stainless steel plate;
Described positive plate is lead, antimony, tin, silver-colored quad alloy plate;
The ratio of described positive plate useful area and negative plate useful area 0.6: 1.0;
After the described negative plate electrolysis, become negative electrode manganese plate; Described negative electrode manganese plate in use is used following method Passivation Treatment: passivator is potassium dichromate aqueous solution, concentration 3%, a negative electrode manganese of every taking-up plate when transferring groove, dip in passivating solution immediately, make the manganese metal table generate layer oxide film, reach the not oxidized blackening in air of manganese plate, influence quality product;
Manganese plate after the passivation is used flushing with clean water, the passivator on flush away surface, and then put into 80～100 ℃ of boiling hot water and scald, impurity such as crystalline ammonium sulfate on the flush away manganese plate;
Scald back manganese plate through air-dry, peel off, obtain the sheet metal manganese product, then the packing warehouse-in;
Negative plate after the demanganize is treated to: the pole plate of non-cohesive residual manganese, and stand-by after cleaning; Be attached with and peel off to get off residual manganese plate and be put into anolyte drill traverse bubble, after residual manganese dissolve, dip in nitric acid liquid, the clear water scouring is afterwards stand-by again;
It is stand-by that brightless negative plate is electroplated the polishing back.
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| PCT/CN2011/076040 WO2011160578A1 (en) | 2010-06-22 | 2011-06-21 | Method for producing electrolytic manganese metal by using two ores and apparatus thereof |
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| CN101845562B (en) | 2013-03-20 |
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