CN1860243A - Improved hydrometallurgical processing of manganese containing materials - Google Patents
Improved hydrometallurgical processing of manganese containing materials Download PDFInfo
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- CN1860243A CN1860243A CNA2004800279936A CN200480027993A CN1860243A CN 1860243 A CN1860243 A CN 1860243A CN A2004800279936 A CNA2004800279936 A CN A2004800279936A CN 200480027993 A CN200480027993 A CN 200480027993A CN 1860243 A CN1860243 A CN 1860243A
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- 239000011572 manganese Substances 0.000 title claims abstract description 47
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 65
- 230000008569 process Effects 0.000 claims abstract description 61
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000243 solution Substances 0.000 claims abstract description 46
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229940075933 dithionate Drugs 0.000 claims abstract description 22
- 235000010269 sulphur dioxide Nutrition 0.000 claims abstract description 19
- 150000002500 ions Chemical class 0.000 claims abstract description 17
- 239000004291 sulphur dioxide Substances 0.000 claims abstract description 14
- 238000000638 solvent extraction Methods 0.000 claims abstract description 11
- 239000003929 acidic solution Substances 0.000 claims abstract 2
- 238000002386 leaching Methods 0.000 claims description 23
- 238000005363 electrowinning Methods 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 7
- 238000009854 hydrometallurgy Methods 0.000 claims description 6
- 239000011702 manganese sulphate Substances 0.000 claims description 6
- 235000007079 manganese sulphate Nutrition 0.000 claims description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 229910001447 ferric ion Inorganic materials 0.000 claims description 3
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 230000033116 oxidation-reduction process Effects 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000002002 slurry Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- -1 iron ion Chemical class 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 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 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 229910000616 Ferromanganese Inorganic materials 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012527 feed solution Substances 0.000 description 2
- 229910052598 goethite Inorganic materials 0.000 description 2
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 2
- 229910052935 jarosite Inorganic materials 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BPKGOZPBGXJDEP-UHFFFAOYSA-N [C].[Zn] Chemical compound [C].[Zn] BPKGOZPBGXJDEP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- RMGVZKRVHHSUIM-UHFFFAOYSA-N dithionic acid Chemical compound OS(=O)(=O)S(O)(=O)=O RMGVZKRVHHSUIM-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012633 leachable Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- OKVGBKABWITJQA-UHFFFAOYSA-L manganese dithionate Chemical compound [Mn+2].[O-]S(=O)(=O)S([O-])(=O)=O OKVGBKABWITJQA-UHFFFAOYSA-L 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011110 re-filtration Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
-
- 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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
- C22B3/402—Mixtures of acyclic or carbocyclic compounds of different types
- C22B3/404—Mixtures of acyclic or carbocyclic compounds of different types of organic acids and oximes
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Geochemistry & Mineralogy (AREA)
- Environmental & Geological Engineering (AREA)
- Geology (AREA)
- Oceanography (AREA)
- Ocean & Marine Engineering (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
A process for the improved hydrometallurgical processing of manganese containing materials, the process characterised by the formation of a leach solution or slurry of manganese dioxide containing feedstock and acidic solution, passing a volume of sulphur dioxide gas through the leach solution whereby the levels of dithionate ion generated in the pregnant leach solution are less than about 5g/l, and subsequently passing the pregnant leach solution to a solvent extraction step.
Description
Technical Field
The present invention relates to an improved hydrometallurgical process for manganese-containing materials, and more particularly to a solvent extraction process that efficiently utilizes low-grade manganese dioxide feedstock to produce manganese products, including electrolytic manganese dioxide.
Background
It is known to use sulphur dioxide to extract manganese from manganese dioxide containing ores, however, the extraction process produces by-product dithionate ions at concentrations greater than 5 g/l. This concentration increases significantly with increasing manganese extraction, and it is not uncommon to reach 20 g/l. Interestingly, it is described in Cotton and Wilkinson, advanced inorganic chemistry, 3 rd edition, page 452: "the process for the preparation of dithionate or dithionic acid is a reaction between sulphur dioxide or sulphite and manganese dioxide in the presence of acid".
Low grade manganese dioxide feedstocks (less than 40% manganese) are currently produced uneconomically by conventional roasting-reduction, sulfuric acid leaching processes to produce manganese sulfate. The economics of high grade manganese dioxide feedstock (manganese content greater than 40%) using this roasting-reduction process is also questionable. All current processes for extracting manganese from manganese dioxide containing feedstocks using sulphur dioxide result in a dithionate ion concentration in solution of greater than 5 g/l, thus requiring the addition of an expensive "oxidation" or "slaking" process for each process. The process of reducing the dithionate ion concentration from 5 g/l to less than 1 g/l by "oxidation" takes a long time and increases capital investment.
Poor control of dithionate levels in the manganese sulphate crystal product results in contamination of the product with manganese dithionate, which reacts slowly to release sulphur dioxide gas.
It is therefore necessary to provide a process for the extraction of manganese sulphate from a low grade manganese dioxide feed material in which the level of dithionate ion in the leach solution is less than 5 g/l, preferably less than 1 g/l.
The recovery of manganese dioxide from low grade raw materials will avoid or at least reduce the required manganese ore mining and land destruction, bringing great environmental benefits. The utilization of the manganese tailings can save limited resources.
In addition, Mn (IV) is reduced by adopting a hydrometallurgical process, a gas kiln and a fluidized bed reactor are not needed, and the raw material is not required to be roasted to about 1000 ℃ for cooling before leaching. The carbon requirement is greatly reduced, thereby reducing the emission of greenhouse gases.
The hydrometallurgical process is easily controlled and the degree of dissolution of mn (iv) can be indicated by monitoring the solution potential of the leach solution or slurry. The sulfur dioxide leaching method is adopted to realize the complete conversion of Mn (IV) to Mn (II), thereby avoiding the residual of leachable manganese elements in the solid waste residue.
In particular, when producing Electrolytic Manganese Dioxide (EMD), the increase in the dithionate ion concentration in the solution affects the quality and purity of the EMD produced in the electrowinning cell. Also, the discharge of hydrogen sulfide can present certain occupational health and environmental concerns.
The applicant has previously applied a hydrometallurgical process for manganese containing materials, in which 95% of the manganese dioxide is dissolved by sulphur dioxide leaching for 10 to 15 hours, theoretical amounts of sulphur dioxide are added to the leach solution, the reaction is terminated thereafter, the dithionate ion level is preferably maintained at less than 5 g/l, preferably at 1 g/l, and the resulting leach solution is passed through a jarosite process to reduce the potassium and sodium levels, and then through a goethite mineralization process to reduce the iron ion level to a level below ppm, thereby providing an electrolyte for the electrowinning process. In the electrowinning step, an electrolytic manganese dioxide precipitate is formed. In fact, the conditions of the leaching process need to be controlled such that dithionate ion formation is controlled to a minimum, which requires precise leaching process condition control. This process is described in International application PCT/AU03/01295(WO 04/033738).
US4423012 discloses a process for increasing the concentration of desired metals such as manganese, zinc and certain impurities in electrowinning feed solutions. The specific method is to mix aqueous effluent from the feed solution with extraction solvent (DEHPA), and then the effluent is counter-current extracted by the extraction solvent for multiple times, and the formed organic phase is back-extracted with spent electrolyte from the electrowinning process. The stripping liquid is returned to the electrowinning process to recover manganese and zinc metals. Importantly, the process is only applicable to the low flow effluent of conventional calcination concentrate/acid leach EMD and is not applicable to alkaline leach liquors and where phosphoric acid is used as the extract.
The foregoing background discussion is intended to facilitate an understanding of the present invention only. It should be appreciated that the discussion is not an acknowledgement or admission that any of the material referred to was common general knowledge in australia as at the priority date of the application.
In this document, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element but not the inclusion of … ….
Disclosure of Invention
The present invention provides an improved process for the hydrometallurgical processing of manganese containing materials, the improvement being characterised by providing a leach solution of a manganese dioxide containing feedstock and an acidic liquor, the leach solution having a dithionate ion concentration of less than 5 g/l after introduction of a volume of sulphur dioxide gas, and subsequently subjecting the leach solution to solvent extraction.
Preferably, the level of dithionate ion in the leach solution is less than 1 g/l.
Preferably, the pH of the leachate is maintained below 5. More preferably, the pH of the leachate is maintained below 3.
One mode of the present invention is: the leaching process is controlled below 60 ℃.
Preferably, sufficient sulphur dioxide gas is passed through the leach solution for a period of time not exceeding 2 hours to ensure that 95% of the manganese is leached.
Another mode of the present invention is: the manganese content of the manganese dioxide-containing raw material is less than 40%.
The ratio of ferric and ferrous ions was monitored throughout the leach to ensure that the Oxidation Reduction Potential (ORP) was greater than or equal to 550mV (vs an Ag/AgCl reference electrode).
The solvent extraction step is followed by a stripping step in which the organic phase is stripped in admixture with spent sulfuric acid electrolyte from the electrowinning step to produce a manganese sulfate solution which is returned to the electrowinning step. In the solvent extraction step, dithionate ions in the leach solution remain in the aqueous phase.
Drawings
The present invention is described by way of example only and comprises a specific embodiment and three figures, wherein:
FIG. 1 is a schematic flow diagram of the process of the present invention for producing electrolytic manganese dioxide from a low grade manganese-containing feedstock.
Detailed Description
Referring to figure 1 of the drawings, there is shown a process 10 for the production of electrolytic manganese dioxide according to the present invention, a manganese dioxide ore 12 having a manganese content of less than 40% is ground to a slurry and fed to a leach 14 having at least one intensive agitator to form a 10% w/w leach solution.
Sufficient sulphur dioxide 16 (in gaseous or liquid form) is passed into the leach solution at a temperature of less than 60 c, preferably less than 50 c, and at a pH of less than 5, preferably less than 3. The rate of sulphur dioxide addition to the leach solution is such that 95% of the manganese is extracted in 2 hours.
The ratio of ferric to ferrous ions in the leacher 14 is monitored by an Oxidation Reduction Potential (ORP) probe, the lowest value of which is 500mV (vs. Ag/AgCl reference). If the ORP is reduced, it can be increased by adding manganese dioxide ore 12. The ORP must be above this value during leaching to ensure that all the iron ions are in the ferric state.
The chemical reactions during leaching were as follows:
and (3) introducing sulfur dioxide into the leachate in a theoretical calculation amount so that 95% of manganese dioxide can be dissolved, stopping introducing sulfur dioxide gas into the leacher, and stopping the reaction. The pH of the solution is raised to between 5 and 7 by adding lime or limestone and subsequently subjected to a solid-liquid separation process using a thickener 18 and a filter (not shown).
It is noted that the sulphur dioxide 16 may also be provided by means of off-gases generated in a smelting or industrial process. Even sulphur dioxide can be added to the leach solution in the form of a sulphite solution.
The soluble manganese content at this stage is typically below 20 g/l, but its concentration depends on the capacity of the leacher 14. It should also be noted that any form of aqueous manganese solution may also be added to the leach solution, with the manganese being recovered for use in the manufacture of electrolytic manganese dioxide. Such aqueous manganese solutions may come from spills from neighboring ores, processing plants, or manganese processing facilities.
Although leaching of manganese dioxide with sulfur dioxide in an acid solution to produce manganese sulphate is the primary reaction of the present invention, a certain amount of dithionate is produced. High pH favors the formation of dithionate, which is produced by a combination reaction of free radicals:
after solid-liquid separation, the solution is passed to a solvent extraction step 20 in which an aqueous solution and a carboxylic acid extractant such as Versatic 10TMMixing, the carboxylic acid extractant has a concentration of about 0.5M, and the diluent is an aliphatic diluent such as Shellsol D70TMExtraction times of up to 5 times, of water with organic phaseThe ratio is approximately 2 to 1. The pH of the solution is adjusted by means of a suitable base, such as NaOH, NH4OH or Na2CO3The control is 4.5-7, preferably 5.5-6.5.
In this procedure, all dithionate ions, chloride ions and most of the magnesium, calcium and potassium ions are still present in the aqueous phase and do not enter the organic extract. The aqueous phase may be recycled to the leacher 14 for further manganese extraction or may be fed to a tailings pond 22 along with the solids separated in the thickener 18. An extraction synergist such as oxime LIX63 can be added into Versatic 10TMThe extraction agent promotes the separation of calcium.
The use of the above-mentioned extractants and diluents in the process of the invention proves to be effective and relatively inexpensive.
The manganese in the purified organic phase is back-extracted with sulfuric acid containing spent electrolyte 24, the spent electrolyte 24 being the recycled liquor of the electrowinning process 26. The stripped solution 24 contains about 40-70 g/l manganese and about 25-50 g/l sulfuric acid, as well as some minor impurities. The hydrogen ions generated in the electrowinning step 26 are replaced with manganese ions in the organic phase, and the pH rises to near neutral. The resulting solution, referred to as the manganese rich extract 28, is passed through a filtration process (not shown) to remove any residual organic components. The manganese rich extract 28 is then subjected to a sulfidation step 30 for further purification by adding a sulfidation reagent to remove heavy metals, and a re-filtration step 32. Finally, the solution 28 flows into an electrowinning cell in electrowinning process 26, where the manganese is electrolyzed to high quality Electrolytic Manganese Dioxide (EMD) suitable for use in alkaline cell production.
The electrowinning step 26 is carriedout in an immersed titanium anode, a tubular copper cathode and a completely wax-free environment, and after a two-week production cycle, the entire anode is filled with the product electrolytic manganese dioxide fines, and the initial product is refined and packaged.
A small bypass or bleed stream may also be included, with about 5% of the electrowinning liquor being returned to the leach 14 for manganese recovery and removal of undesirable materials such as sodium, and further to reduce calcium recycle, thereby reducing the chance of gypsum precipitation. The loss of volume of the manganese-rich extract can be compensated by adding demineralized water to the circulating electrolyte.
The process of the invention, particularly in the leaching step, wherein the leach solution of manganese containing material has dithionate ion concentrations of less than 5 g/l, preferably less than 1 g/l, can be used to treat various manganese dioxide containing ores (whether high or low grade), tailings, fines, dust and sludge from ferro-manganese alloy production plants, seafloor manganese nodules, ferromanganese nodules, sludge from zinc smelting plants and to recover manganese dioxide from alkaline or carbon-zinc batteries. The process of the invention allows the leachate produced from the said feedstock to be purified and used to produce EMD, EMM (electrolytic manganese metal) and other manganese compounds.
The cost of the hydrometallurgically improved process for manganese containing materials of the present invention is significantly reduced relative to previously similar processes, including the process described in the applicant's prior international application PCT/AU03/01295(WO 04/033738) and the processes described previously, for example, the relatively low temperature leaching process requires less steam and enables the use of standard glass Fibre Reinforced Polyester (FRP) as a leaching vessel. Moreover, the mild pH value adopted by the process of the invention causes less corrosion to equipment, and less acid liquor is needed compared with the prior art.
Since chlorine and magnesium are removed in the leaching step 14, the leaching step of the present invention can be carried out in plain water, such as water from the Kalgoorlie region of western australia, which reduces the amount of distilled water required in the process.
In comparison with the process described in international application PCT/AU03/01295(WO 04/033738), the process of the present invention does not require the jarosite process and goethite mineralization process, but uses a solvent extraction process, including the use of Versatic acid, potassium removal, and non-ferrous leaching, without the need for ferric ions. This provides a relative savings in investment and operating costs.
The pH value of the leaching solution is controlled to be 3 relatively suitably, the acid generated by electrowinning is used for regenerating the extracting agent, and the required amount of limestone and lime in the process is reduced compared with the prior art.
Because of the use of relatively fewer, smaller reactors, simpler processes, milder temperature and pH conditions, lower operating costs, and labor savings (1 to 2 people per shift).
Since manganese can be extracted from the brine and the water removed, all of the overflow can be directed to the leaching process, adding additional manganese recovery. This is concluded because the vessel volume is fully available, previously focused on the idea of increasing chloride concentration and expanding the total volume of solution.
The leaching tank used in the leaching process is a vessel suitable for the input of large quantities of manganese (solid and liquid), independent of the anions bound by manganese, as long as they prove to be less expensive.
In the prior art, there is a need for a control method and analytical capability to ensure that the dithionate content entering the cell is below 500 ppm. The process of the present invention uses a solvent extraction step to remove dithionate ions, avoiding its circulation throughout the process.
A portion of the effluent is returned to the leach tank and the frequency of the cathodic cleaning to remove gypsum can be greatly reduced, thus making the concentration of magnesium and sodium in the system far below expected. Since magnesium is not critical, the process of the invention does not have a step of reducing the magnesium content, but only by solution depletion and replenishment of clean deionized water. Reducing gypsum precipitation in pipes and vessels also has considerable economic benefits once the plant has reached stable production conditions.
Modifications and variations to the disclosed embodiments will be apparent to those skilled in the art and are intended to be within the scope of the invention.
Claims (11)
1. A process for the hydrometallurgical upgrading of manganese containing materials, the process characterised by forming a leach solution of a manganese dioxide containing feedstock and an acidic solution, passing a volume of sulphur dioxide gas through the leach solution, the leach solution having a dithionate ion concentration of less than 5 g/l, and subsequently subjecting the leach solution to solvent extraction.
2. The process of claim 1, wherein: the level of dithionate ion in the leach solution is less than 1 g/l.
3.The process of claim 2, wherein: the pH value of the leaching solution is maintained below 5.
4. The process of claim 1 or 2, wherein: the pH value of the leaching solution is maintained below 3.
5. The process according to any of the preceding claims, wherein: the temperature of the leaching process is controlled below 60 ℃.
6. The process according to any of the preceding claims, wherein: sufficient sulfur dioxide gas is introduced into the leachate for no more than 2 hours to ensure that 95% of the manganese is dissolved.
7. The process according to any of the preceding claims, wherein: the manganese content of the manganese dioxide-containing raw material is less than 40%.
8. The process according to any of the preceding claims, wherein: the ratio of ferric and ferrous ions was monitored throughout the leach to ensure that the Oxidation Reduction Potential (ORP) was greater than or equal to 550mV (vs an Ag/AgCl reference electrode).
9. The process according to any of the preceding claims, wherein: the solvent extraction step is followed by a back-extraction step in which the organic phase is back-extracted in admixture with spent sulfuric acid electrolyte from the electrowinning step to produce a manganese sulfate solution which is fed to the electrowinning step.
10. The process according to any of the preceding claims, wherein: in the solvent extraction step, dithionate ions of the leach solution remain in the aqueous phase.
11. An improved hydrometallurgical process for manganese-containing materials, which is characterized in that: the process is described in detail with reference to the accompanying drawings.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2003903992A AU2003903992A0 (en) | 2003-07-30 | 2003-07-30 | Improved hydrometallurgical processing of manganese containing materials |
| AU2003903992 | 2003-07-30 |
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| Publication Number | Publication Date |
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| CN1860243A true CN1860243A (en) | 2006-11-08 |
| CN100376698C CN100376698C (en) | 2008-03-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2004800279936A Expired - Lifetime CN100376698C (en) | 2003-07-30 | 2004-06-28 | Improved hydrometallurgical processing of manganese containing materials |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN100376698C (en) |
| AU (1) | AU2003903992A0 (en) |
| WO (1) | WO2005012582A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108928853A (en) * | 2018-08-15 | 2018-12-04 | 广西锰华新能源科技发展有限公司 | A kind of comprehensive reutilization method of manganese ore leaching slag |
| CN114207160A (en) * | 2019-08-09 | 2022-03-18 | 尤米科尔公司 | Method for recovering metals from oxidized ores |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HUE025388T2 (en) * | 2007-09-26 | 2016-02-29 | Hitec Energy Ltd | A micronutrient fertiliser and method for producing same |
| US20130316902A1 (en) * | 2010-12-08 | 2013-11-28 | Christopher Brett Ward | Micronutrient fertiliser and method for producing same |
| RU2607873C1 (en) * | 2015-09-28 | 2017-01-20 | федеральное государственное бюджетное образовательное учреждение высшего образования "Санкт-Петербургский горный университет" | Method of processing of ferromanganese concretions |
| CN108220595B (en) * | 2017-12-05 | 2019-11-05 | 中信大锰矿业有限责任公司大新锰矿分公司 | Utilize the method for cassava dry powder and formaldehyde reducing leaching manganese oxide ore |
| CN111111419B (en) * | 2020-01-02 | 2021-03-23 | 四川大学 | Method for removing high-concentration SO in flue gas by utilizing manganese carbonate ore2Method for producing manganese sulfate solution |
| WO2023148644A1 (en) * | 2022-02-04 | 2023-08-10 | Tata Steel Limited | A method for recovering manganese from manganese ore |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU606888A1 (en) * | 1975-05-15 | 1978-05-15 | Институт Металлургии Им А.А. Байкова Ан Ссср | Method of deforming carbonate manganese ores |
| SU1044651A1 (en) * | 1981-12-18 | 1983-09-30 | Научно-исследовательский и проектный институт по обогащению и агломерации руд черных металлов "Механобрчермет" | Method for processing manganese ores and sludges |
| SU1479540A1 (en) * | 1987-07-27 | 1989-05-15 | Научно-исследовательский и проектный институт по обогащению и агломерации руд черных металлов "Механобрчермет" | Method of processing manganese-containing initial material |
| CN1021809C (en) * | 1989-10-05 | 1993-08-18 | 广西大学 | Industrial manganese sulphate production method |
| CN1147027A (en) * | 1995-06-18 | 1997-04-09 | 陈德根 | Process for producing electrolytic metal manganese using SOx from waste flue gas |
| WO1998014623A1 (en) * | 1996-10-02 | 1998-04-09 | International Curator Resources Limited | Hydrometallurgical extraction of copper, zinc and cobalt from ores containing manganese dioxide |
| CN1055067C (en) * | 1997-02-18 | 2000-08-02 | 周保强 | Method for direct production of manganese sulfate by sulfur dioxide gas |
| AU2002952042A0 (en) * | 2002-10-10 | 2002-10-31 | Hitec Energy Limited | Hydrometallurgical processing of manganese containing materials |
-
2003
- 2003-07-30 AU AU2003903992A patent/AU2003903992A0/en not_active Abandoned
-
2004
- 2004-06-28 WO PCT/AU2004/000854 patent/WO2005012582A1/en active Application Filing
- 2004-06-28 CN CNB2004800279936A patent/CN100376698C/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108928853A (en) * | 2018-08-15 | 2018-12-04 | 广西锰华新能源科技发展有限公司 | A kind of comprehensive reutilization method of manganese ore leaching slag |
| CN114207160A (en) * | 2019-08-09 | 2022-03-18 | 尤米科尔公司 | Method for recovering metals from oxidized ores |
| CN114207160B (en) * | 2019-08-09 | 2023-10-31 | 尤米科尔公司 | Method for recovering metals from oxidized ores |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2005012582A1 (en) | 2005-02-10 |
| AU2003903992A0 (en) | 2003-08-14 |
| CN100376698C (en) | 2008-03-26 |
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