WO2019161447A1 - Procédé de récupération de produits de manganèse à partir de différentes matières premières - Google Patents

Procédé de récupération de produits de manganèse à partir de différentes matières premières Download PDF

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Publication number
WO2019161447A1
WO2019161447A1 PCT/AU2019/050144 AU2019050144W WO2019161447A1 WO 2019161447 A1 WO2019161447 A1 WO 2019161447A1 AU 2019050144 W AU2019050144 W AU 2019050144W WO 2019161447 A1 WO2019161447 A1 WO 2019161447A1
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Prior art keywords
lean
leachate
precipitate
separating
alcohol
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PCT/AU2019/050144
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English (en)
Inventor
Bryn Harris
Carl White
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Nmr 360 Inc
Urban Mining Pty Ltd
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Publication of WO2019161447A1 publication Critical patent/WO2019161447A1/fr

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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
    • 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
    • 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
    • C22B3/065—Nitric 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
    • C22B3/04—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
    • C22B3/04—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
    • C22B3/10—Hydrochloric acid, other halogenated 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
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/16—Extraction of metal compounds from ores or concentrates by wet processes by leaching in organic solutions
    • C22B3/1608—Leaching with acyclic or carbocyclic agents
    • C22B3/1616—Leaching with acyclic or carbocyclic agents of a single type
    • C22B3/165—Leaching with acyclic or carbocyclic agents of a single type with organic acids
    • 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
    • C22B3/262—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds using alcohols or phenols
    • 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
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • 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
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • 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
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/20—Obtaining alkaline earth metals or magnesium
    • 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
    • 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

Definitions

  • the present invention relates generally to processes for the recovery of manganese and associated metal products in a pure form from various manganiferous feedstocks.
  • the process is applied to materials containing calcium and potassium.
  • Manganese is currently recovered from relatively high-grade concentrates by a variety of methods, both pyrometallurgical (ferro-manganese) and hydrometallurgical (electrolytic manganese metal and manganese dioxide, manganese carbonate and manganese sulphate).
  • pyrometallurgical ferro-manganese
  • hydrometallurgical electrolytic manganese metal and manganese dioxide, manganese carbonate and manganese sulphate
  • a process for separating Ca from a Ca- and Mn-containing solid feed including: leaching the solid feed stock with an aqueous leachant, the aqueous leachant including an acid to convert Ca in the solid feed to a soluble Ca salt and form a Ca-rich leachate and a Ca-lean Mn-containing solid residue; and separating the Ca-rich leachate and the Ca-lean Mn-containing solid residue.
  • the process further includes treating the Ca-rich leachate with a precipitant to form a Ca-containing precipitate and a Ca-lean leachate.
  • the process further includes separating the Ca-containing precipitate and the Ca-lean leachate.
  • the precipitant is selected from the group consisting of SO2 gas, or a soluble sulphite, and the precipitate is CaS0 3 .
  • the process preferably further includes calcining the Ca-containing precipitate to form CaO and SO2 gas; and recycling the SO2 gas as a feed (or component thereof) to the Ca-precipitation step.
  • the step of calcining the Ca-containing precipitate is carried out at a temperature of from about 500°C up to about l000°C. More preferably, the temperature is from about 600°C. Even more preferably the temperature is from about 700°C. Most preferably, the temperature is from about 750°C. Additionally or alternatively, it is preferred that the temperature is up to about 950°C. More preferably, the temperature is up to about 900°C. Most preferably, the temperature is up to about 850°C.
  • the acid is selected from the group consisting of: HC1, HNO3, and organic acids, such as formic acid, and acetic acid.
  • the step of leaching the solid feed stock is carried out at a temperature of from ambient up to l00°C.
  • the temperature is from about 40°C. More preferably the temperature is from about 45 °C. Most preferably, the temperature is from about 50°C. Additionally or alternatively, it is preferred that the temperature is up to about 90°C. More preferably, the temperature is up to about 80°C. Even more preferably, the temperature is up to about 70°C. Most preferably, the temperature is up to about 60°C.
  • a method of separating Mn from a Ca-lean Mn-containing solid residue from the process of the first aspect including: leaching the Ca-lean Mn-containing solid residue with sulphuric and a reductant to reduce Mn in the Ca-lean Mn-containing solid residue and form a MnSCU containing leachate and a Mn- lean solid residue; separating the nSCU containing leachate and the Mn-lean solid residue; contacting the MnSCU containing leachate with an alcohol to form a MnSCU precipitate and a Mn-lean liquor; and separating the nSCU precipitate and the Mn-lean liquor.
  • the reductant is a reducing sulphur species.
  • the reducing sulphur species is SO2.
  • a process for separating Mn from an Mn-containing solid feed including: leaching the Mn-containing feed with sulphuric acid and a reductant to reduce Mn in the solid feed and form a nSCU containing leachate and a Mn-lean solid residue; separating the MnSOr containing leachate and the Mn-lean solid residue; contacting the MnSCU containing leachate with an alcohol to form an nSCU precipitate and a Mn-lean liquor; and separating the nSCU precipitate and the Mn-lean liquor.
  • the reductant is a reducing sulphur species.
  • the reducing sulphur species is S0 2 .
  • the Mn-containing solid feed is produced according to the first aspect of the invention.
  • the process further includes: heating the Mn-lean liquor to separate the alcohol from the Mn-lean liquor and recycling the alcohol for use in the step of contacting the nSCU containing leachate with the alcohol.
  • the step of heating the Mn-lean liquor to separate the alcohol includes distilling the alcohol from the Mn-lean liquor at a temperature of from about 60°C to about l00°C.
  • the temperature is from about 65°C. More preferably the temperature is from about 70°C. Most preferably, the temperature is from about 75°C. Additionally or alternatively, it is preferred that the temperature is up to about 95°C. More preferably, the temperature is up to about 90°C. Most preferably, the temperature is up to about 85°C. A particularly preferred temperature is about 80°C.
  • the alcohol is selected from the group consisting of alcohol compounds having 1, 2, or 3 carbon atoms.
  • the alcohol is selected from the group consisting of methanol, ethanol, and 1 -propanol. Most preferably, the alcohol is methanol.
  • the reducing sulphate leaching step further results in the formation of K 2 SO 4 .
  • the Mn-lean liquor further includes K 2 SO 4 and residual Mn in a K:Mn molar ratio of from about 0.5: 1 to about 2: 1; and the process further includes: contacting the Mn-lean liquor with an oxidant to oxidise residual Mn in the Mn-lean liquor to heptavalent Mn while adding a neutralising agent to the Mn-lean liquor to adjust or maintain the pH of the Mn-lean liquor to a value of from pH 4 to pH 8; crystallising KMnOr in the Mn-lean liquor to form a slurry of KMnOr crystals; and separating the slurry into a KMn0 4 containing solids stream and a liquids stream.
  • the oxidant is selected from the group consisting of: hydrogen peroxide, ozone, sodium persulphate, potassium persulphate, and Caro’s acid.
  • the neutralising agent is selected from the group consisting of: sodium hydroxide and potassium hydroxide.
  • the pH of the Mn-lean liquor is adjusted to a value of from pH 4 up to pH 7. It is preferred that the value is from pH 4.5. More preferably, the value is from pH 5. Most preferably, the value is from pH 5.5. Alternatively or additionally, it is preferred that the value is up to pH 6.8. Most preferably, the value is up to pH 6.5.
  • the step of contacting the Mn-lean liquor with an oxidant is conducted at a temperature of from ambient to l00°C.
  • the temperature is from about 40°C. More preferably the temperature is from about 45°C. Most preferably, the temperature is from about 50°C. Additionally or alternatively, it is preferred that the temperature is up to about 90°C. More preferably, the temperature is up to about 80°C. Even more preferably, the temperature is up to about 70°C. Most preferably, the temperature is up to about 60°C.
  • the process further includes: converting the residual K2SO4 to KOH and H2SO4.
  • the step of converting the K2SO4 includes using bipolar cell to split the liquids stream into a KOH containing fraction and an H2SO4 containing fraction.
  • a process for separating Mn from a Mn-containing leachate including: contacting the Mn-containing leachate with an alcohol to form an Mn-precipitate and a Mn-lean liquor; and separating the Mn-precipitate and the Mn-lean liquor.
  • the Mn-containing leachate includes Mn in the form of MnSCU.
  • the Mn-containing leachate is a MnSCU leachate
  • the Mn-precipitate is a MnSCU precipitate.
  • the Mn-containing leachate is formed by: leaching the Mn-containing feed with sulphuric acid and a reductant to reduce Mn in the solid feed and form a nSCU containing leachate and an Mn-lean solid residue; and separating the nSCU containing leachate and the Mn-lean solid residue.
  • the reductant is a reducing sulphur species.
  • the reducing sulphur species is SCU.
  • Figure 1 A process flow diagram for the removal of calcium from a Ca- and Mn- containing solid according to embodiments of the first aspect of the invention.
  • Figure 2 A process flow diagram for the recovery of manganese according to embodiments of the first or second aspects of the invention.
  • Figure 3 A photograph of MnSCU crystals recovered in Example 3.
  • FIG. 1 there is shown a schematic representation of a leaching circuit.
  • Many manganese-bearing ores also contain significant amounts of calcium and of potassium, and for the purposes of this description, such an ore has been selected.
  • the feed 10 is leached 11 with recycled hydrochloric acid 12.
  • the purpose of this leach is to remove contained calcium without dissolving any manganese. Consequently, an acid with a corresponding soluble calcium salt is used; the leach conditions are mild with dilute acid, the strength and amount of acid being dependent on the amount of calcium present.
  • the leaching temperature may be from ambient to l00°C, but preferably in the range of 50-60°C.
  • the pH of the resultant solution is controlled to be in the range 4.0-6.5, preferably 5.0-5.5 in order to facilitate the subsequent precipitation of calcium.
  • Leaching may be carried out in any suitable vessel, such as, but not limited to, a column or a stirred tank and co-current, or more preferably, counter-current, the latter ensuring the relatively high pH of the final liquor.
  • the leach slurry 13 proceeds to solid-liquid separation, which may be effected by any convenient means, such as, but not limited to, flocculation and thickening, filter press or vacuum belt filter.
  • the filtrate 15 is sparged with recycled SO2 gas 17 in accordance with a process 16 described in a previous invention of one of the current applicants, Carl W. White, Jean Guimont, Denys Pinard and Serge Monette, Process and Apparatus for Treating Foundry Sludge to Recover Magnesium, US Patent 6,409,980, issued on June 25, 2002, and incorporated herein by reference.
  • the calcium sulphite slurry 20 so-produced proceeds to solid-liquid separation 21 which may be effected by any convenient means, such as, but not limited to, flocculation and thickening, filter press or vacuum belt filter.
  • the precipitation reaction is shown in Equation 1.
  • the calcium sulphite solids 20 are calcined at a temperature of 500-l000°C, preferably 700-800°C to generate a pure, reactive form of lime 22.
  • the SO2 17 generated is recycled to the precipitation reactor 16.
  • the decomposition reaction is shown in Equation 2.
  • the solids 23 from the first leach filter 14 undergo a reducing leach 24 with recycled sulphuric acid 26 and SO2 25, in accordance with minimising the amount of dithionates generated, familiar to those skilled in the art.
  • the leach may be carried out in any suitable vessel such as, but not limited to, a column or a stirred tank reactor.
  • the leach slurry 27 proceeds to solid-liquid separation 28 which may be effected by any convenient means, such as, but not limited to, flocculation and thickening, filter press or vacuum belt filter.
  • the solids 29 are sent to disposal, and the filtrate proceeds to manganese recovery as per Figure 2.
  • FIG 2 there is shown a schematic for the recovery of various manganese products.
  • the reducing leach solution 30 from Figure 1 is mixed 31 with recycled methanol (CH3OH) 32 in order to crystallise a very pure form of manganous sulphate 35.
  • CH3OH methanol
  • the amount of methanol added is dependent upon the concentration of the manganese present, but a typical ratio is 1 : 1 methanol to leach solution.
  • the crystal slurry proceeds to solid- liquid separation 34 which may be effected by any convenient means, such as, but not limited to, flocculation and thickening, filter press or vacuum belt filter.
  • the crystals 35 are pure manganese(II) sulphate of indeterminate waters of crystallisation, and denoted as MnSCU'xFFO. This is a product of its own accord, but may optionally be used as the precursor for producing other manganese chemicals 36 such EMM (electrolytic manganese metal), manganese oxide (MnO), manganese carbonate (MnC0 3 ), EMD or CMD (electrolytic or chemical manganese dioxide, Mn0 2 ).
  • EMM electrolytic manganese metal
  • MnO manganese oxide
  • MnC0 3 manganese carbonate
  • EMD or CMD electrolytic or chemical manganese dioxide
  • the filtrate 37 is heated 38 to 50-l00°C, preferably 80°C, in order to distill off the methanol 32 for recycle and re-use.
  • the remaining aqueous liquor 39 may be treated for recovery of potassium if present. If not, it simply recycled to the reducing leach. If potassium is present, then the amount of methanol added at 31 is limited such as to leave sufficient manganese in solution to react with the potassium, being a molar ratio of 1: 1 K:Mn.
  • the liquor is first oxidised 40 with a suitable oxidant 41, such as, but not limited to, hydrogen peroxide in order to convert the manganese to its heptavalent (VII) state.
  • a suitable oxidant 41 such as, but not limited to, hydrogen peroxide in order to convert the manganese to its heptavalent (VII) state.
  • the solution is neutralised with recycled potassium hydroxide 42 to a pH value of between 4 and 8, preferably between 5 and 7, and more preferably pH 6.0.
  • the oxidised and neutralised liquor 43 is then crystallised 44 in any suitable crystalliser, which may be, for example, a vacuum, cooling or evaporative crystalliser.
  • the crystal slurry proceeds to solid-liquid separation 45 which may be effected by any convenient means, such as, but not limited to, flocculation and thickening, filter press or vacuum belt filter.
  • the solids are potassium permanganate 46.
  • the liquid 47 is potassium sulphate, and may be treated for salt splitting 48 in a bipolar cell. This permits recycle of potassium hydroxide 42 to oxidation/neutralisation 40 and sulphuric acid 26 to the reducing leach of Figure 1.
  • Example 1 A series of leach tests similar to that of Example 1 were carried out, except that the slurry was then neutralised with lime to raise the pH to 4.0 in two tests, and 4.5 in the other 2, after which the slurry was filtered resulting in similar manganese and copper extractions.
  • the filtrate pH was raised 6.5 with caustic addition, with hydrogen peroxide, acting as an oxidant this time, being added simultaneously.
  • the temperature was then raised to 90°C, resulting in the formation of a brown precipitate. This was repeated four times, twice with the pH 4 filtrate (samples 1 and 2) and twice with the pH 4.5 filtrate (samples 3 and 4), with the final solids analysis as in the Table below.
  • Example 2 The leach test of Example 1 was repeated, and the slurry neutralised to pH 4.5 with 20% lime slurry as in Example 2. One litre of solution was taken, analysing 24 g/L Mn, to which 1.4 L of methanol was added at room temperature. Coarse, slightly pink, translucent crystals were obtained, characteristic of MnS0 4* H 2 0, which after washing in methanol and drying yielded 33 g. Based on these being the monohydrate as suggested by their colour, this represents a recovery of 27% of the manganese, but more importantly indicates that a residual solubility of manganese in solution of about 17 g/L is readily attainable. Thus, much higher recoveries would be attained form more concentrated solutions than that used in this example.
  • Figure 3 is a photograph showing the produced MnSCE crystals.

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
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Abstract

La présente invention concerne un procédé de récupération de sulfate de manganèse et d'oxydes de manganèse à partir de matières premières contenant du manganèse, comprenant la lixiviation de la charge dans de l'acide sulfurique, suivi d'une cristallisation sélective de sulfate de manganèse heptahydraté. La liqueur mère est traitée pour éliminer les impuretés et recyclée dans le procédé, de façon à conserver l'eau et réduire au minimum les effluents de procédé. Le sulfate de manganèse peut en outre être transformé en oxydes de manganèse purs.
PCT/AU2019/050144 2018-02-22 2019-02-22 Procédé de récupération de produits de manganèse à partir de différentes matières premières WO2019161447A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110642297A (zh) * 2019-09-04 2020-01-03 广西大学 低温结晶去除硫酸锰溶液中钙镁离子的方法
CN112657490A (zh) * 2020-12-08 2021-04-16 嘉应学院 一种三维片状β-MnO2的制备方法及其NH3-SCR中的应用
CN112827434A (zh) * 2020-12-24 2021-05-25 内蒙古华镒环境工程有限公司 铅银渣的高效回收装置及回收方法
CN115259231A (zh) * 2022-07-13 2022-11-01 绵阳师范学院 一种去除硫酸锰中钙和镁杂质的方法
CN115704062A (zh) * 2022-01-27 2023-02-17 江苏载驰科技股份有限公司 一种回收电解锰渣中有价金属并再生高纯度锰盐的方法

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US4208379A (en) * 1979-04-04 1980-06-17 The United States Of America As Represented By The Secretary Of The Interior Recovery of metals from Atlantic sea nodules
US5912402A (en) * 1995-10-30 1999-06-15 Drinkard Metalox, Inc. Metallurgical dust recycle process
US6409980B1 (en) * 2000-06-16 2002-06-25 Noranda, Inc. Process and apparatus for treating foundry sludge to recover magnesium
WO2009157620A1 (fr) * 2008-06-25 2009-12-30 Dongbu Fine Chemicals Co., Ltd. Procédé de récupération d'un composé comprenant du manganèse à partir de poussières d'un four électronique
WO2015193828A1 (fr) * 2014-06-17 2015-12-23 Samancor Manganese (Proprietary) Limited Procédé d'enrichissement du minerai de manganèse

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4208379A (en) * 1979-04-04 1980-06-17 The United States Of America As Represented By The Secretary Of The Interior Recovery of metals from Atlantic sea nodules
US5912402A (en) * 1995-10-30 1999-06-15 Drinkard Metalox, Inc. Metallurgical dust recycle process
US6409980B1 (en) * 2000-06-16 2002-06-25 Noranda, Inc. Process and apparatus for treating foundry sludge to recover magnesium
WO2009157620A1 (fr) * 2008-06-25 2009-12-30 Dongbu Fine Chemicals Co., Ltd. Procédé de récupération d'un composé comprenant du manganèse à partir de poussières d'un four électronique
WO2015193828A1 (fr) * 2014-06-17 2015-12-23 Samancor Manganese (Proprietary) Limited Procédé d'enrichissement du minerai de manganèse

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110642297A (zh) * 2019-09-04 2020-01-03 广西大学 低温结晶去除硫酸锰溶液中钙镁离子的方法
CN110642297B (zh) * 2019-09-04 2021-10-12 广西大学 低温结晶去除硫酸锰溶液中钙镁离子的方法
CN112657490A (zh) * 2020-12-08 2021-04-16 嘉应学院 一种三维片状β-MnO2的制备方法及其NH3-SCR中的应用
CN112827434A (zh) * 2020-12-24 2021-05-25 内蒙古华镒环境工程有限公司 铅银渣的高效回收装置及回收方法
CN112827434B (zh) * 2020-12-24 2022-09-09 内蒙古华镒环境工程有限公司 铅银渣的高效回收装置及回收方法
CN115704062A (zh) * 2022-01-27 2023-02-17 江苏载驰科技股份有限公司 一种回收电解锰渣中有价金属并再生高纯度锰盐的方法
CN115259231A (zh) * 2022-07-13 2022-11-01 绵阳师范学院 一种去除硫酸锰中钙和镁杂质的方法
CN115259231B (zh) * 2022-07-13 2023-04-18 绵阳师范学院 一种去除硫酸锰中钙和镁杂质的方法

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