WO2011085438A1 - Procédé pour la production de dioxyde de manganèse électrolytique - Google Patents

Procédé pour la production de dioxyde de manganèse électrolytique Download PDF

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Publication number
WO2011085438A1
WO2011085438A1 PCT/AU2011/000023 AU2011000023W WO2011085438A1 WO 2011085438 A1 WO2011085438 A1 WO 2011085438A1 AU 2011000023 W AU2011000023 W AU 2011000023W WO 2011085438 A1 WO2011085438 A1 WO 2011085438A1
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WIPO (PCT)
Prior art keywords
liquor
soil conditioner
manganese
leach
sulphate
Prior art date
Application number
PCT/AU2011/000023
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English (en)
Inventor
Yatendra Sharma
Original Assignee
Galaxy Resources Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from AU2010900115A external-priority patent/AU2010900115A0/en
Application filed by Galaxy Resources Limited filed Critical Galaxy Resources Limited
Publication of WO2011085438A1 publication Critical patent/WO2011085438A1/fr

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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
    • 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
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00—Other inorganic fertilisers
    • C05D9/02—Other inorganic fertilisers containing trace elements
    • 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
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/21—Manganese oxides

Definitions

  • the present invention relates to a process for the production of electrolytic manganese dioxide. More particularly, the process for the production of 5 electrolytic manganese dioxide of the present invention may additionally produce a soil conditioner or improver.
  • EMD electrolytic manganese dioxide
  • the major factors include pH, organic matter content, nutrient interaction, soil water content, temperature and light.
  • the soil pH has increased to a level where availability of B, Cu, Fe, Mn and Zn has decreased dramatically.
  • IFIA International Fertiliser Industry Association
  • the process of the present invention has as one object thereof to overcome the abovementioned problems associated with the prior art, or to at least provide a useful alternative thereto.
  • step (iii) Passing the liquor from step (ii) to a jarositing step producing a precipitate
  • step (iv) Passing the liquor from step (iii) to a goethiting step producing a precipitate;
  • step (vi) Passing the remaining liquor from step (v) to an electrowinning step in which electrolytic manganese dioxide is deposited and a spent liquor produced;
  • step (vii) Recycling spent liquor from step (vi) directly or indirectly to the leach of step (ii) to leach manganese oxide thereby contributing favourably to the efficiency of the process.
  • the precipitates of steps (iii) and (iv) are used to produce a soil conditioner.
  • the precipitate from step (iii) is passed to a dense media separation step in which silica is removed before combination with the precipitate of step (iv) in the production of the soil conditioner.
  • the combination of the precipitates from steps (iii) and (iv) are preferably combined in a filter step that produces a generally solid- product that is in turn used in the production of the soil conditioner.
  • the remaining liquid from the filter step is preferably passed directly or indirectly to the leach of step (ii) to the manganese oxide slurry.
  • the solid product of the filtration of the precipitates of steps (iii) and (iv) has added thereto one or more trace elements.
  • the solid product is preferably also dried and granulated in the production of the soil conditioner.
  • the added trace elements may be provided in the form of one or more micronutrient compounds.
  • the micronutrient compounds preferably include one or more of zinc sulphate, copper sulphate, borax, and sodium molybdate.
  • the process of the present invention further preferably comprises the following additional method steps:
  • a soil conditioner characterised in that it comprises precipitated material from the jarositing and goethiting of a manganese sulphate liquor.
  • the manganese sulphate liquor is produced in the leaching of a manganese oxide material with sulphuric acid.
  • silica is removed from the precipitated material from jarositing.
  • One or more trace elements may be combined with the precipitated material from jarositing and goethiting.
  • the added trace elements may be provided in the form of one or more micronutrient compounds.
  • the micronutrient compounds preferably include one or more of zinc sulphate, copper sulphate t borax, and sodium molybdate.
  • the soil conditioner is provided in dried and granulated form.
  • FIG. 1 is a schematic flow sheet of a process for the production of electrolytic manganese dioxide in accordance with the present invention, the flow sheet also showing how precipitated material from jarositing and goethiting steps may be used to produce a soil conditioner.
  • FIG 1 there is shown a process 10 for the production of electrolytic manganese dioxide (“EMD").
  • EMD electrolytic manganese dioxide
  • Mn0 2 ore most commonly pyrolusite
  • MnO is an essential requirement for the hydrometallurgical processing of Mn0 2 ore in order for it to be leachable with sulphuric acid. That is, manganese is reduced from its 4+ valence state to its 2+ valence state to facilitate its dissolution in subsequent hydrometallurgical processing. Similarly, whatever iron oxides are also present will be reduced, whereby iron will be present in predominantly the 2+ valence state.
  • a Mn02 containing concentrate 12 is mixed with coke 14 (as a source of carbon) in a ratio ranging from 1 :0.1 to 1 :0.5 and heated at about 1000°C by compressed natural gas ("CNG") in a reduction furnace 16 to reduce the dioxide ore to mono-oxide of manganese.
  • CNG compressed natural gas
  • Calcination takes place at about 1000°C in the reduction furnace 16 with a residence time of between about 15 minutes to one hour (at temperature), during which the Mn0 2 is converted to MnO.
  • the converted product of the reduction furnace is passed to a calcine cooler 18.
  • Off-gases from the reduction furnace 16 are cleaned in an electrostatic precipitator (not shown) before discharging the off-gases to the atmosphere via a stack (not shown). Recovered solids from the off-gases are conveyed to the calcine cooler 18.
  • the cooled product from the calcine cooler 18 is then milled in a closed circuit wet grinding mill 20 to reduce the material to a Peo of 75 ⁇ and the mill product is then pneumatically conveyed to a storage silo (not shown). This fine size range is preferred to ensure high Mn recoveries in the subsequent process steps.
  • the reactions taking place are as follows:
  • Leaching takes place in continuous leach tanks 22 which receive solids from the wet grinding mill 20, spent sulphuric acid liquor from a spent sulphuric acid liquor tank 24, optionally sulphuric acid from sulphuric acid overhead tanks 26 and make up water from process water pumps (not shown).
  • the pH of the leach is about 1 to 1 .5, for example about 1.
  • a pulp density of 40% solids (w/w) is used for the leach to maximise the Mn concentration and to ensure that the solubility limit of Mn sulphate during leaching is not exceeded.
  • the leach tanks 22 operate at ambient pressure and a temperature of about 90°C with a nominal tank residence time of about 1 hour.
  • the leach provides manganese and iron recoveries of greater than 90%.
  • leach tanks 22 are pumped to a jarositing step, comprising jarositing tanks 28, for impurity removal.
  • the first precipitation stage removes potassium by increasing the pH of the manganese sulphate liquor to about 1.8 to 2 by adding limestone slurry.
  • the exact reaction taking place is not known but it is believed that potassium forms an insoluble complex with iron.
  • the aim of jarosite precipitation is the removal of potassium, preferably to a level less than 5 mg/L so as to prevent the formation of Cryptomelane which would be detrimental to the ultimate EMD product.
  • Jarosite precipitation is conducted with an Fe/K ratio of about 12:1 , although higher ratios of 12:1 may be utilised to ensure appropriate levels of potassium removal.
  • the product of the jarositing step is passed to a thickening step 30 from which the , thickener overflow is passed to a second precipitation or goethiting step 32.
  • a third precipitation stage or sulphiding step 34 receives overflow from a thickening step 36 that receives the product of the goethiting step 32.
  • the sulphiding step 34 removes heavy metal impurities by sulfiding the manganese sulphate liquor.
  • the manganese sulphate liquor is treated with barium sulfide to precipitate heavy metal impurities as sulphides.
  • the resulting liquor is passed to a filter, for example a belt filter 38, to obtain a manganese sulfate liquor to process electrochemically to deposit EMD on titanium anodes.
  • the precipitation circuit incorporating the jarositing step 28, the goethiting step 32 and the sulphiding step 34, is designed to remove potassium, iron, aluminium and calcium impurities, and heavy metal impurities, from the manganese sulphate solution and provide a clear, high purity filtrate for EMD electrowinning.
  • EMD deposition from the manganese sulphate liquor takes place in an electrowinning step 40 on titanium anodes (using copper cathodes) in cell houses.
  • the manganese sulphate liquor containing about 60 to 70 g/L manganese is pumped to an electrochemical cell house with a sufficient amount of sulphuric acid to maintain pH at about 1.
  • the electro-deposition of EMD takes place at about 90°C with current density of about 60 Amp/m 2 .
  • the EMD deposited on titanium anodes is scrapped off from the anodes in a scrapping step 42.
  • the EMD is neutralised using soda ash solution in a first neutralisation step 44, then wet ball milled 46, then passed to a second neutralisation step 48 and again wet ball milled 50, to the desired customer specifications, dried 52 and packaged 54.
  • the spent liquor from the electrowinning step 40 is passed to the spent liqubr tank 24 before being fed back to the leach step 22, either directly or via the wet grinding mill 20, to leach manganese oxide in the leach step 22.
  • the spent liquor contains significant amounts of sulphuric acid and some manganese sulphate. Generally, this recycled sulphuric acid is sufficient to achieve the necessary leaching of manganese oxide in the leach step 22, thereby contributing to the efficiency of the process 10 of the present invention.
  • the thickener underflow from the thickener 30 is passed to a dense media separation (“DMS") step 56 in which silica is separated from the other precipitated solids from the jarositing step 28.
  • the float from the DMS step 56 is filtered in a filter step 58, using for example a belt filter.
  • the thickener underflow from the goethiting step 32 and thickener 36 is also passed to this filter step 58.
  • the liquid product of the filter step 58 is passed to the leach step 22 either directly or via the wet grinding mill 20, again so as to leach manganese oxide.
  • the solids from the filter step 58 are passed to a drier 60 and in turn to a granulator 62.
  • Additives in the form of trace elements are added to the product from the drier 60 as it passes to the granulator 62.
  • These trace elements may be provided in the form of one or more micronutrient compounds.
  • the micronutrient compounds include, but are not limited to, zinc sulphate, copper sulphate, borax, and sodium molybdate.
  • the process of the present invention can also produce a soil conditioner that contains Mn, Fe, Ga, and S in sufficient quantities and in a form that is bioleachable, or available, for the plants. That is, the form in which the elements are present is such that they are available to plants to be taken up.
  • the basic product of the jarositing step 28 and the goethiting step 32 may be supplemented by blending with some other important trace elements, additives, not otherwise present, but that are considered necessary for plant growth. Whilst there is scope to vary the specific composition of the soil conditioner, Table 1 below contains one preferred example thereof:
  • Mn is present as mono-oxide of Mn (MnO), Fe as ferric oxide, Ca as calcium sulphate, Zn as zinc sulphate, Cu as copper sulphate, Mo as sodium molybdite, and B as borax.
  • MnO Mn
  • Fe ferric oxide
  • Ca calcium sulphate
  • Zn zinc sulphate
  • Cu copper sulphate
  • Mo sodium molybdite
  • B borax.
  • Mn is involved in regulation of enzymes and growth hormones. Mn also assists in photosynthesis and respiration.
  • Fe is involved in respiration and chlorophyll synthesis.
  • Ca is involved in formation of cell walls, and root and leaf development. Ca also participates in translocation of sugars.
  • S is involved in formation of nodules and. chlorophyll synthesis, structural components of amino acids and enzymes.
  • Zn is involved in production of growth hormones and chlorophyll. It also assists in respiration and carbohydrate synthesis. Mo is involved in enzymatic reduction of nitrates to ammonia. Mo also assists in conversion of inorganic phosphates to organic form. Cu is involved in photosynthesis and respiratory system. Cu also assists in chlorophyll synthesis and used as a reaction catalyst. Boron is involved in formation of cell walls, terminal buds and pollen tubes. B also participates in regulation of starch production and translocation of sugars and starches.
  • the growth is high because of soil and environmental factors affecting the availability of micronutrients to the plants in the developed countries.
  • the major factors include pH, organic matter content, nutrient interaction, soil water content, temperature and light.
  • the soil ]5H ⁇ has increased to a level where availability of B, Cu, Fe, Mn and Zn has decreased dramatically.
  • the soil conditioner of the present invention containing S as sulphates of Ca, Zn, and Gu, will act as a soil conditioner and remedy the soil pH. This will enable the plants to take up these micronutrients.
  • Concentrate feed composition being manganese ore from the Groote Eyiandt Mining Company Pty Ltd (GEMCO), a BHP Billiton subsidiary, project:
  • the solids concentration in the reactor was 8% (w/w) after adding the ore slurry, which contained 3.15 L of deionised water.
  • the ore slurry was generally added within the first 30 minutes of the leach.
  • the pH was first controlled at 3 by adding sulphuric acid solution.
  • the pH in the first leach test (L1 ) was adjusted by adding a 10 M (980 g/L) sulphuric acid solution, which was prepared by diluting concentrated sulphuric acid (98%) with the synthetic spent electrolyte. Dilution of concentrated acid with the synthetic electrolyte resulted in an increased manganese concentration in the PLS. As a result, the bulk synthetic electrolyte prepared was diluted with deionised water and used as a lixiviant for L2 and L3. The acid and manganese concentrations after dilution were 44 g/L and 24 g/L, respectively. A 9M sulphuric acid solution was used for pH adjustment in L2.
  • This solution was prepared by diluting concentrated sulphuric acid (98%) with deionised water decanted from the ore slurry and a small volume of the diluted synthetic solution.
  • the pH during L3 was adjusted by addition of a 9 M sulphuric acid solution, where concentrated sulphuric acid (98%) was diluted with deionised water decanted from the prepared ore slurry.
  • the filtrate from BLI was 46 L and it was reduced to 31 L after jarosite/goethite precipitation due to evaporation. This solution was less than the minimum of 50 L required to run electrowinning for 14 days. It was therefore, necessary to conduct another bulk !each test (BL2) to produce sufficient solution.
  • the filtrate from BL2 68 L and it was reduced to 53 L after jarosite/goethite precipitation.
  • the solution from BL1 and BL2 were combined after jarosite/goethite precipitation to conduct sulphide precipitation. After sulphide precipitation, some elements did not meet the specification required for the electrowinning solution.
  • a third bulk leach, BL3, was conducted to produce a fresh PLS that could be processed for potassium removal by jarosite precipitation, as previous results had shown that potassium removal was efficient when jarosite precipitation was conducted on a fresh PLS directly after leaching.
  • the ore used in BL3 was milled separately from the ore previously used.
  • the three bulk leach tests (BL1 , BL2 and BL3) were conducted in a 150 L reactor, fitted with baffles and steam coils for heating. The only variable in the bulk leach tests was the % solids (w/w), which were 6%, 4% and 3.5% for BL1 , BL2 and BL3, respectively. The same procedure was followed for all tests.
  • a fresh bulk synthetic electrolyte was prepared as a lixiviant with a composition resembling the spent electrolyte from the electrowinning circuit.
  • the manganese and sulphuric acid concentrations were 35 and 30 g/L, respectively.
  • the ore was fed as a 40% solids (w/w) slurry, and pH was controlled at 1.5 by adding concentrated sulphuric acid (98%). Concentrated sulphuric acid was used to avoid the slow pH adjustment observed when using diluted acid. The use of diluted acid would also result in larger volumes of acid solution required for pH adjustment at larger test scale which would lead to dilution especially at the lower % solids.
  • the Manganese and iron recoveries for the bulk leach tests, BL1 , BL2 and BL3 were > 90% and the highest recoveries for manganese and iron were 99% and 5 97%, respectively.
  • the average acid consumption calculated for L2, L3, BL1 and BL2 was approximately 1296 kg H2S04/ton ore.
  • the low acid consumption for L1 could be 10 attributed to the slurry spillage when feeding ore and acid into the reactor.
  • the reason for the unusually high acid consumption recorded for BL3 is unclear at this stage.
  • the ore used for this test was from a separate reduced batch of ore that was milled separately from the first batch of ore used in the first 5 leach tests.
  • Jarosite/geothite precipitation tests were carried out by heating up the PLS to 90°C and maintaining the pH at 1.5 for jarosite precipitation unless stated otherwise.
  • the aim of jarosite precipitation was to remove potassium in the PLS down to ⁇ 5mg/L to prevent formation of Cryptomelane, which is detrimental to the electrochemical activity of the EMD product.
  • Jarosite precipitation was conducted for two to three hours and thereafter, the pH was increased to 4.5 to 5 for goethite precipitation for iron removal.
  • Ferric sulphate was added to the PLS prior to jarosite precipitation to obtain an Fe/K ratio of 12/1.
  • J1 The only exception to ferric addition was the initial jarosite precipitation test (J1), where no ferric was added in an attempt to determine whether additional iron was required to remove potassium to ⁇ 5 mg/L by jarosite precipitation. Hydrated lime, and sometimes lime, was added as slurry to adjust the pH. An initial attempt was made during J1 to oxidise the ferrous using oxygen and to increase the redox potential to 550 mV. The maximum redox potential achieved using oxygen was 437 mV after 5 hours. EMD powder was added in an attempt to increase the redox potential, ⁇ 24 g of EMD was added, but the redox potential did not increase. Hydrogen peroxide was then added resulting in redox potential > 550 mV within minutes.
  • the initial jarosite precipitation test (J1) was conducted using the combined PLS from the first three leach tests (L1 , L2 and L3).
  • the filtrate from J1 was spiked with ferric (as anhydrous ferric sulphate salt) to remove the remaining potassium; however, the residual potassium did not meet the specification.
  • Potassium removal from this PLS was repeated " 5 times by spiking the filtrate from the previous jarosite/goethite precipitation test with ferric and conducting jarosite precipitation followed by goethite precipitation. The lowest potassium level attained was 15 mg/L.
  • the filtrate solutions from BL1 , BL2 and BL3 were used separately to conduct three bulk precipitation; BP1, BP2 and BP3, respectively.
  • BP1 and BP2 resulted in efficient potassium removal; however, BP3 was unsuccessful even after repeating jarosite precipitation on the filtrate twice.
  • the filtrate solution from BP3 was combined with the sulphide precipitation (SP1) filtrate, which had a potassium concentration of 5 mg/L. This was done to obtain sufficient solution for electrowinning.
  • the mixed solution was spiked with ferric sulphate and jarosite/goethite precipitation was conducted again in an attempt to lower the potassium to the required minimum; potassium removal to the required level was unsuccessful.
  • Jarosite precipitation was conducted first for a minimum of two hours at pH 1.8 (Tests J1, J2 and J3) and pH 1.5 (J4, J5, J6, BP1 , BP2 and BP3). Thereafter, the pH was increased by addition of lime slurry to pH 4.5 to 5 to conduct goethite precipitation for a minimum of 2 hours. Removal of potassium by jarosite precipitation proved to be inconsistent as indicated in the results in Tables 4 and 5 below. Potassium removal without ferric addition (J1) resulted in only 59% potassium removal at an Fe/K ratio of 7 and pH 1.8.
  • the filtrate from SP1 which was a sulphide precipitation test conducted using combined filtrate from BP1 and BP2, was mixed with the filtrate from BP3c to obtain sufficient solution to run the electrowinning test.
  • This mixed solution was spiked with ferric sulphate and jarosite precipitation (BPM) was conducted in an - - attempt to further reduce the potassium level, this was followed by goethite precipitation for iron removal. Results indicated that no additional potassium was removed from solution; the test only resulted in the dilution of the potassium in the filtrate from BP3c by the filtrate from SP1. The increase in potassium concentration in BPM filtrate will be confirmed by additional analysis.
  • the filtrate solution from BL1 and BL2 were mixed to make up approximately 83 L of solution for sulphide precipitation test (SP1).
  • the client specified stoichiometric addition of BaS (99.7%, w/w) with an excess of 5% with respect to base metal impurities.
  • stoichiometric amounts of BaS plus 12% excess was added twice in powder form to ensure complete removal of base metal impurities.
  • the test was conducted at 90°C for 2 hours with no pH control.
  • the filtrate was stored and the solids were processed; no moisture sample was taken in this case due to the low volume of solids produced.
  • the solids were washed with deionised water by displacing the entrained solution with 1 L of deionised water three times, the filter cake was dried and the moisture content of the solids was calculated.
  • ICP-OES Inductively Coupled Plasma Optical Spectroscopy
  • AAS Atomic Absorption Spectroscopy
  • Base metals below 2 mg/L were analysed using Inductively Coupled Plasma Mass Spectroscopy (ICP-MS) to determine the BaS stoichiometric requirement.
  • the detection limit for ICP-MS was 0,01 mg/L.
  • the soil conditioner of the present invention will find ready acceptance from farmers and others working with fertiliser products.
  • the expected advantages are:
  • the process of the present invention for the production of EMD is expected to allow for an increase in the efficiency of utilisation of manganese relative to traditional sulphuric acid leach processes for the production of EMD as a result of the novel recycle of process streams.

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Abstract

L'invention porte sur un procédé pour la production de dioxyde de manganèse électrolytique, le procédé comprenant les étapes de procédé consistant à : (i) réduire un minerai contenant du dioxyde de manganèse pour produire un produit à base d'oxyde de manganèse ; (ii) lixivier le produit à base d'oxyde de manganèse avec de l'acide sulfurique, ce qui produit une liqueur contenant du sulfate de manganèse ; (iii) faire passer la liqueur provenant de l'étape (ii) vers une étape de précipitation de jarosite produisant un précipité ; (iv) faire passer la liqueur provenant de l'étape (iii) vers une étape de précipitation de goethite produisant un précipité ; (v) faire passer la liqueur provenant de l'étape (iv) vers une étape de sulfuration et filtrer la liqueur ainsi obtenue pour enlever les impuretés métaux lourds sous forme de sulfures de métaux lourds ; (vi) faire passer la liqueur restante provenant de l'étape (v) vers une étape d'extraction électrolytique dans laquelle du dioxyde de manganèse électrolytique est déposé et une liqueur usée est produite ; et (vii) recycler la liqueur usée provenant de l'étape (vi) directement ou indirectement vers la lixiviation de l'étape (ii) pour lixivier l'oxyde de manganèse, ce qui contribue de cette manière favorablement au rendement du procédé.
PCT/AU2011/000023 2010-01-13 2011-01-10 Procédé pour la production de dioxyde de manganèse électrolytique WO2011085438A1 (fr)

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AU2010900115 2010-01-13
AU2010900115A AU2010900115A0 (en) 2010-01-13 Process for the Production of Electrolytic Manganese Dioxide

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102634819A (zh) * 2012-04-10 2012-08-15 四川大学 二氧化硫浸出氧化锰制取电解锰/电解二氧化锰的方法
CN102634656A (zh) * 2012-04-19 2012-08-15 四川大学 硫钙循环浸取氧化锰制备电解锰/电解二氧化锰的方法
CN104789755A (zh) * 2015-04-23 2015-07-22 中南大学 一种用高硫锰矿清洁高效生产金属锰的方法及装置
EP3134933B1 (fr) 2014-04-21 2020-10-21 Prince Specialty Products LLC Procédé de production de dioxyde de manganèse électrolytique ayant une densité compacte élevée et dioxyde de manganèse électrolytique produit à partir de celui-ci
WO2020232505A1 (fr) * 2019-05-21 2020-11-26 Mn Energy Limited Production de sulfate de manganèse
US10995413B2 (en) 2016-03-02 2021-05-04 Arash M. Kasaaian Sulfide recycling in manganese production
CN113088999A (zh) * 2021-03-31 2021-07-09 广西桂柳化工有限责任公司 一种无汞碱性锌锰电池用的电解二氧化锰的制备方法
WO2022205533A1 (fr) * 2021-03-31 2022-10-06 广西桂柳化工有限责任公司 Procédé de préparation de dioxyde de manganèse électrolytique à faible teneur en impuretés

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001048255A1 (fr) * 1999-12-23 2001-07-05 Noranda Inc. Procede de controle du manganese dans les circuits de lixiviation du zinc
WO2004033738A1 (fr) * 2002-10-10 2004-04-22 Hitec Energy Limited Traitement hydrometallurgique de materiaux contenant du manganese
WO2009039560A1 (fr) * 2007-09-26 2009-04-02 Hitec Energy Limited Engrais à micronutriments et son procédé de fabrication

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001048255A1 (fr) * 1999-12-23 2001-07-05 Noranda Inc. Procede de controle du manganese dans les circuits de lixiviation du zinc
WO2004033738A1 (fr) * 2002-10-10 2004-04-22 Hitec Energy Limited Traitement hydrometallurgique de materiaux contenant du manganese
WO2009039560A1 (fr) * 2007-09-26 2009-04-02 Hitec Energy Limited Engrais à micronutriments et son procédé de fabrication

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102634819A (zh) * 2012-04-10 2012-08-15 四川大学 二氧化硫浸出氧化锰制取电解锰/电解二氧化锰的方法
CN102634819B (zh) * 2012-04-10 2015-05-13 四川大学 二氧化硫浸出氧化锰制取电解锰/电解二氧化锰的方法
CN102634656A (zh) * 2012-04-19 2012-08-15 四川大学 硫钙循环浸取氧化锰制备电解锰/电解二氧化锰的方法
CN102634656B (zh) * 2012-04-19 2013-11-20 四川大学 硫钙循环浸取氧化锰制备电解锰或电解二氧化锰的方法
EP3134933B1 (fr) 2014-04-21 2020-10-21 Prince Specialty Products LLC Procédé de production de dioxyde de manganèse électrolytique ayant une densité compacte élevée et dioxyde de manganèse électrolytique produit à partir de celui-ci
CN104789755A (zh) * 2015-04-23 2015-07-22 中南大学 一种用高硫锰矿清洁高效生产金属锰的方法及装置
US10995413B2 (en) 2016-03-02 2021-05-04 Arash M. Kasaaian Sulfide recycling in manganese production
WO2020232505A1 (fr) * 2019-05-21 2020-11-26 Mn Energy Limited Production de sulfate de manganèse
CN113088999A (zh) * 2021-03-31 2021-07-09 广西桂柳化工有限责任公司 一种无汞碱性锌锰电池用的电解二氧化锰的制备方法
CN113088999B (zh) * 2021-03-31 2021-12-31 广西桂柳新材料股份有限公司 一种无汞碱性锌锰电池用的电解二氧化锰的制备方法
WO2022205534A1 (fr) * 2021-03-31 2022-10-06 广西桂柳化工有限责任公司 Procédé de préparation de dioxyde de manganèse électrolytique pour batterie alcaline de zinc-manganèse exempte de mercure
WO2022205533A1 (fr) * 2021-03-31 2022-10-06 广西桂柳化工有限责任公司 Procédé de préparation de dioxyde de manganèse électrolytique à faible teneur en impuretés

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