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WO2024052760A1 - Procédé de production de monohydrate de sulfate de manganèse - Google Patents

Procédé de production de monohydrate de sulfate de manganèse Download PDF

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Publication number
WO2024052760A1
WO2024052760A1 PCT/IB2023/058530 IB2023058530W WO2024052760A1 WO 2024052760 A1 WO2024052760 A1 WO 2024052760A1 IB 2023058530 W IB2023058530 W IB 2023058530W WO 2024052760 A1 WO2024052760 A1 WO 2024052760A1
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WIPO (PCT)
Prior art keywords
manganese
solution
carbonate
produce
calcium
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Ceased
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PCT/IB2023/058530
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English (en)
Inventor
Walter FOURIE
Paul Savage
Anca NACU
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Manganese Metal Co Pty Ltd
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Manganese Metal Co Pty Ltd
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Publication of WO2024052760A1 publication Critical patent/WO2024052760A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B47/00—Obtaining manganese
    • C22B47/0018—Treating ocean floor nodules
    • C22B47/0045—Treating ocean floor nodules by wet processes
    • C22B47/0054—Treating ocean floor nodules by wet processes leaching processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/10—Sulfates
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Definitions

  • This invention relates to a process for producing manganese sulphate monohydrate.
  • the invention relates to a process for producing a high purity manganese sulphate monohydrate from an ore.
  • the ore is previously calcined.
  • step (b) the first manganese solution may be boiled and aerated, and the pH of the first manganese solution may be raised to above 5.
  • the amount of heavy metals in the first manganese solution is less than about 5ppm.
  • the source of bicarbonate may be ammonium bicarbonate, alternatively the source of carbonate may be sodium carbonate, and the source of hydroxide may be ammonium hydroxide.
  • step (c) the pH may be controlled at about 6 - 7 and the amount of magnesium in the manganese carbonate may be less than about 50ppm.
  • step (d) manganese carbonate is heated in air at about 650°C to 950 °C for about 0.5-2 hours, and then cooled to ambient temperature.
  • the manganese oxide mixture of step (e) is washed with deionised water, and preferably the deionised water is at a pH of about 7.
  • the second manganese solution of step (f) may be an ultra-pure manganese sulphate solution, having a calcium and magnesium content less than 20 ppm.
  • the content of the other metals in the second manganese solution is less than 5 ppm.
  • the second manganese solution may have a concentration of about 160 g/kg as manganese sulphate.
  • the crystallisation step (g) may further include the following steps:
  • step (i) Adjusting the pH of the second manganese solution of step (f) to about 2 by adding sulphuric acid;
  • step (ii) Evaporating the solution of step (i) to produce crystals
  • step (iii) filtering the solution of step (ii) to remove moisture from a crystal slurry
  • Evaporation may take place at a temperature of about 80°C to 85°C, optionally under a vacuum until the specific gravity is about 1 .67.
  • the crystals are dried at a temperature of about 105°C to 150 °C, even more preferably at a temperature of about 105°C to 120°C.
  • the two-step crystallization process may include an intermediate calcium seeded precipitation process, which may or may not include aeration.
  • the second manganese solution of step (f) undergoes a two-step crystallization process and intermediate calcium seeded precipitation process, before the manganese sulphate monohydrate dissolution of step (h).
  • step (h) further includes dissolving the manganese sulphate monohydrate of step (g) in water and adding sulphuric acid to produce a third manganese solution.
  • the third manganese solution is manganese sulphate.
  • the manganese sulphate may be filtered and evaporated in order to produce crystals and a crystal slurry.
  • the solution is evaporated at about 80°C to 85°C under a vacuum to produce crystals.
  • the removal or precipitation of calcium in step (i) may further include:
  • the crystals are a high purity manganese sulphate monohydrate having a calcium and magnesium content of less than about 50 g/t.
  • the crystals which are a high purity manganese sulphate monohydrate conform to the following maximum impurity limits (ppm):
  • the manganese content in the crystals is greater than 32%.
  • the manganese carbonate of step (c) is not roasted or heated, but the manganese carbonate is redissolved in sulphuric acid and water, and the solution may undergo a two-step crystallization process.
  • a process for producing manganese sulphate monohydrate comprising the steps of: a) Providing an ore containing Mn 2+ ; b) Leaching the ore in sulphuric acid to produce a first manganese solution; c) Filtering the first manganese solution to produce a filtrate; d) Contacting the filtrate with a source of bicarbonate to precipitate manganese carbonate; e) Dissolving the manganese carbonate in sulphuric acid to provide a second manganese solution; f) Removing calcium from the second manganese solution; and g) Crystallising manganese sulphate monohydrate from the second manganese solution.
  • steps (h), (I) and (J) are the same as the steps of the first embodiment described above.
  • Figure 1 shows a block diagram for a process of producing manganese sulphate monohydrate in accordance with the invention
  • FIG. 2 shows a process flowsheet for a leaching step B and precipitation step C in accordance with the invention of Figure 1 ;
  • FIG 3 shows a process flowsheet for a heating step C, washing step D and reductive leach step F in accordance with the invention of Figure 1 ;
  • Figure 4 shows a process flowsheet for a crystallization step G in accordance with the invention of Figure 1 ;
  • Figure 5 shows a process flowsheet for manganese carbonate dissolution, polishing leach filtration, residual iron oxidation and iron filtration in accordance with another embodiment of the invention.
  • Figure 6 shows a process flowsheet for calcium sulphate removal, 1 st stage crystallisation, and 2 nd stage crystallisation in accordance with another embodiment of the invention.
  • a nonlimiting example of a process for producing manganese sulphate monohydrate in accordance with the invention is generally indicated by reference numeral 10.
  • the process 10 consists of the steps of (A) providing an ore 12 containing Mn 2+ , (B) leaching the ore 12 in sulphuric acid 14 to produce a first manganese solution 16; (C) contacting the first manganese solution 16 with a source of bicarbonate, carbonate or carbon dioxide 18 and a source of hydroxide 20 to precipitate manganese carbonate 22; (D) heating the manganese carbonate 22 to produce a manganese oxide mixture 24; (E) washing the manganese oxide mixture 24 with water 26 to remove calcium 28; (F) contacting the washed manganese oxide mixture 30 with hydrogen peroxide 32 and sulphuric acid 34 or with gaseous SO2 in acid to convert the manganese oxide to a second manganese solution 36; (G) crystallising manganese
  • the ore 12 is a reduced ore which was previously calcined.
  • the leaching process of step (b) includes addition of pre-wetted (ratio of about 1 :1), milled, calcined ore 12 to a dilute sulphuric acid solution 14 to produce a first manganese solution 16.
  • the leach or first manganese solution 16 is held at a gentle boil during leaching for about 1 to 2 hours while being aerated and boiled (air is added to the mixture).
  • the volume of the mixture is kept constant during the gentle boil by the addition of water.
  • the pH of the first manganese solution 16 rises from about 1 to above 5.
  • the first manganese solution 16 is then filtered, and the filter cake is discarded.
  • the first manganese solution 16 has a manganese concentration of about 160 g/l to 180 g/l, and a heavy metal content including iron of below 5ppm.
  • the first manganese solution 16 is contacted with a source of bicarbonate, carbonate, or carbon dioxide 18 and a source of hydroxide 20 to obtain a precipitate of manganese carbonate 22.
  • the source of bicarbonate 18 is ammonium bicarbonate
  • the source of carbonate is sodium carbonate
  • the source of hydroxide 20 is preferably ammonium hydroxide.
  • the source of bicarbonate 18 is a stoichiometric amount of ammonium bicarbonate and the pH is controlled with the addition of ammonium hydroxide 20 to a pH of about 6 to about 7, preferably a pH of about 6.5.
  • Manganese is precipitated as manganese carbonate 22 with the purpose of rejecting magnesium from the solution. Magnesium carbonate is much more soluble than manganese carbonate 22 near neutral pH and can therefore be rejected, as it stays in solution while manganese carbonate 22 is precipitated. Magnesium rejection from the precipitate 22 will be above 99% and yield of manganese carbonate 22 from the dosed ammonium bicarbonate will be above 85%.
  • the amount of magnesium in the manganese carbonate 22 is less than about 50 ppm.
  • the manganese carbonate 22 is heated in the presence of air at a temperature of about 650°C to 950°C in a heating apparatus (manganese carbonate 22 is roasted oxidatively).
  • the heating apparatus is a furnace.
  • Manganese carbonate 22 is heated in order to convert all the carbonates to oxides, predominantly to MnaCU.
  • the manganese carbonate 22 is roasted in air for about 0.5-2 hours to convert the manganese carbonate 22 to manganese oxide 24. Emissions are released during the heating process, which includes carbon dioxide.
  • the manganese oxide 24 is allowed to cool to ambient temperature.
  • Manganese oxides in the (III) oxidation state is insoluble in water, while calcium and magnesium oxides are soluble.
  • the calcium (and any residual magnesium) oxides are not mixed in with manganese oxides, but exist as a separate phase that can be easily solubilised after the oxidative roast.
  • Calcium 28 is removed from manganese oxide 24, which is in the form of a powder, by washing the manganese oxide 24 with water 26.
  • the water 26 is deionised water with an initial pH of 7. Calcium oxide dissolves in the wash water. Two consecutive washes remove >90% of the calcium in the manganese oxides, as well as residual magnesium that may be present to produce a washed or purified MnO x 30.
  • the purified MnO x 30 is filtered and the filtrate discarded.
  • the purified MnO x 30 is added to a dilute sulphuric acid solution 34, containing a slight excess of sulphuric acid to react with the manganese.
  • An equimolar amount of hydrogen peroxide 32 is added to the mixture of purified MnOx 30 and dilute sulphuric acid solution 34 to react with the Mn(lll) in the MnOx (calculated as the amount in Mn 3 C>4).
  • Deionised water is also added to the mixture (not shown). The mixture is stirred until all the MnO x dissolves to produce a second manganese solution 36.
  • the resulting second manganese solution 36 is an ultra-pure manganese sulphate solution.
  • the ultra-pure manganese sulphate solution 36 has a calcium and magnesium content of less than 20 ppm, and the content of all other metals is less than 5 ppm.
  • the combination of sulphuric acid 34 and hydrogen peroxide 32 can also be substituted with SO2 addition in an acidic solution.
  • Manganese sulphate monohydrate is crystalized from the second manganese solution 36 by using the following steps:
  • step (ii) Evaporating the solution of step (i) under a vacuum to produce crystals 40;
  • step (iii) filtering the solution of step (ii) to remove moisture from a crystal slurry
  • step (ii) takes place at a temperature of about 80°C to 85°C under a vacuum until a specific gravity of about 1 .67 is achieved.
  • the crystals are dried at a temperature of about 105°C to 150 °C, even more preferably at a temperature of about 105°C to 120°C.
  • the purified crystals will conform to the following maximum impurity limits (PPm):
  • the manganese content is greater than 32% in the crystals.
  • the manganese carbonate 22 of step (c) is not heated.
  • the manganese carbonate 22 is redissolved in sulphuric acid (H2SO4), and the manganese solution is sent through a two-step crystallisation process. Calcium is removed through an intermediate calcium- seeded precipitation process, which may or may not include aeration.
  • a process for producing manganese sulphate monohydrate comprising the steps of: a) Providing an ore containing Mn 2+ ; b) Leaching the ore in sulphuric acid to produce a first manganese solution; c) Filtering the first manganese solution to produce a filtrate; d) Contacting the filtrate with a source of bicarbonate to precipitate manganese carbonate; e) Dissolving the manganese carbonate in sulphuric acid to provide a second manganese solution; f) Removing calcium from the second manganese solution; and g) Crystallising manganese sulphate monohydrate from the second manganese solution.
  • Steps (h), (I) and (J) are the same as steps of the first embodiment described above.
  • the manganese carbonate 22 of step (c) is repulped into a slurry using water.
  • the manganese carbonate 22, which is now in a form of a slurry, is redissolved by the addition of sulphuric acid (H2SO4) to obtain a solution with a concentration of about 120 g/kg Mn (as manganese sulphate).
  • H2SO4 sulphuric acid
  • the product solution is filtered to remove any insoluble components before feeding the manganese sulphate to a crystallizer. Crystallization is conducted under a slight vacuum at a temperature of about 80°C to 85°C. A combination of a small bleed and a calcium removal step (described below) will keep the calcium concentration in the mother liquor below 400 mg/kg.
  • centrate is seeded with calcium sulphate hemi-hydrate seed or alternatively calcium sulphate dihydrate seed, aerated for 12 hours, filtered, and returned to the crude crystallisation feed.
  • the resulting crystal slurry is centrifuged and washed to remove a portion of the entrained impurities, before it is air dried to produce the final high purity manganese sulphate monohydrate.
  • a pre-wetted, milled calcined ore 212 is fed to an oxidising leach container or tank B1 , typically an Oil Fired Kiln.
  • a dilute sulphuric acid (H2SO4) solution 214 is added to the ore 212 in the container B1 to produce a first manganese solution 216.
  • the first manganese solution 216 is initially at a pH of about 1 , and at a temperature of about 80°C.
  • the first manganese solution 216 is held at a gentle boil for about 1 to 2 hours during leaching, while adding air 213 to the container B1 .
  • the volume of the mixture or first manganese solution 216 is kept constant during the gentle boil by the addition of process water 215 and wash water 217.
  • the pH of the first manganese solution 216 rises to about 5-6 while the temperature drops to about 60°C in the leach container B1 after about 1 to 2 hours of leaching.
  • the first manganese solution 216 is filtered at a pressure of about 1800 KPa using a filtering apparatus B2 to produce a filter cake 219 and filtrate 219b.
  • the filter cake 219 is discarded.
  • Deionised water 223 is added to the filtering apparatus B2 during the filtration process.
  • MSMH ML Recycle 441 containing about 160 g/l of manganese is added to the filtered first manganese solution or filtrate 219b before the precipitation step (see Figure 4 for the composition of MSMH ML Recycle).
  • the filtrate or filtered first manganese solution 219b has a pH of about 5.5 and is at ambient temperature.
  • Ammonium bicarbonate, sodium carbonate or alternatively carbon dioxide gas 218 and ammonium hydroxide 220 are added to the first manganese solution 219b in order to precipitate manganese carbonate (MnCOs) 220.
  • MnCOs manganese carbonate
  • the pH of the mixture and of the precipitate rises to about 7.
  • Manganese carbonate 220 is filtered at atmospheric pressure and ambient temperature using a filtering apparatus C2 to produce a manganese carbonate (MnCOs) wet solids 220a and filtrate 221.
  • Deionised water 223 and recycled condensate 443 are added to the filtering apparatus C2 during filtration (see Figure 4 for the composition of the recycled condensate). A portion of the filtrate 221 is recycled back to the oxidising leach container B1 and the remainder is purged. The Manganese carbonate wet solids 220a proceeds to the heating stage.
  • manganese carbonate wet solids 220a is introduced to a heating or roasting apparatus D.
  • the manganese carbonate is heated to a temperature of about 650°C-950°C in the presence of air 323(air is added to the heating apparatus), and at atmospheric pressure.
  • the manganese carbonate 220a is preferably heated at 900 e C.
  • the carbonates are converted to oxides 324 and emissions are also produced, including carbon dioxide 325.
  • the oxides undergo a first wash E1 at a temperature of about 80°C and at atmospheric pressure.
  • the wash may be an ultrasonic wash.
  • Deionised water 326 is added to the oxides during the first wash.
  • sulphuric acid 327 may be added to oxides 324 during the wash thus lowering the pH of the mixture to about 1 .
  • the washed oxides 330 which are now at a temperature of greater than 60°C undergo a first filtration process E2.
  • the oxides are filtered at an atmospheric pressure using a filtering apparatus.
  • the wash water 217 from the filtration process is recycled back to the oxidising leach container of Figure 2.
  • the oxides are subjected to a second wash E3 and filtration process E4 using the same conditions as the first wash E1 and filtration process E2 to produce a purified Manganese Oxide (Mn x O y ) 331 .
  • the purified Mn x O y 331 undergoes a reductive leach in a leaching container F1 .
  • the purified Mn x O y 331 is added to a dilute sulphuric acid solution 334.
  • Sulphur dioxide (SO2) 333 and deionised water 326 are also added to the leaching container F1 .
  • Reductive leaching is conducted at a temperature of about 65°C, at a pH of about 1 and at atmospheric pressure in order to produce a leached solution.
  • the leached solution is filtered at a temperature of about 65°C, pH 2.5 and at atmospheric pressure in a filtration apparatus F2 to produce waste 343 and a filtered leached solution.
  • the filtered leach solution is then polished in F3 with hydrogen peroxide 335, air 337 and ammonium hydroxide 339 to produce a polished leached solution 336.
  • the Mn x O y 331 is contacted with hydrogen peroxide (H2O2) and sulphuric acid (lines not shown) in order to produce a leached solution.
  • This solution is then contacted with more hydrogen peroxide (H2O2) 335, air 337 and ammonium hydroxide 339 in order to produce a polished manganese sulphate solution 336.
  • This reaction takes place at a temperature of about 70°C, pH of about 4 to 5 and at atmospheric pressure.
  • the manganese sulphate solution 336 is filtered to produce a filtrate 336a and waster 341. Waste 341 (filter cake) discarded.
  • manganese sulphate solution (filtrate) 336a which is now at a pH of about 4.6 is subjected to a crystallisation process G1 at a temperature of about 80°C and pressure of about -46.7 KPa.
  • deionised water 438 is added to the manganese sulphate solution 336a, and the mixture consisting of deionised water 438 and manganese sulphate solution 336a is evaporated to produce manganese sulphate monohydrate crystals 440, MSMH ML recycle 441 , containing approximately 160 g/l manganese, and a condensate of pure water 443.
  • MSMH ML Recycle 441 is added to the filtered first manganese solution 219b or filtrate, in the example of Figure 2, before the precipitation step.
  • the manganese sulphate monohydrate crystals 440 are dried at about 150°C and at atmospheric pressure using a drying apparatus G2.
  • the purified crystals will conform to the following maximum impurity limits (PPm):
  • the manganese content is greater than 32% in the crystals.
  • manganese carbonate wet solids 220a is redissolved in sulphuric acid (H 2 SO 4 ) 514 using a leaching container H1.
  • Hydrogen Peroxide (H2O2) 516 and deionised water 518 are added to the leaching container H1 during leaching.
  • Leaching is conducted at a temperature of about 65°C, pH of 2 to 5.5 and at atmospheric pressure to produce a manganese sulphate solution 520.
  • the manganese sulphate solution 520 is polished and filtered using a filtering apparatus H2 to produce waste 522 and filtered solution 524.
  • the filtered solution 524 is treated with hydrogen peroxide 526, ammonium hydroxide 528 and air 530 in order to remove residual iron from the filtered solution.
  • the residual iron oxidation step H3 which is followed by filtration in a filtration apparatus H4 is conducted at a temperature of about 70°C, pH of about 4.5 to 5.5 and at atmospheric pressure to produce waste 534 and an even purer manganese sulphate solution 536.
  • the purer manganese sulphate solution 536 of Figure 5 undergoes a first crystallisation process J1 to produce manganese sulphate monohydrate 614.
  • Crystallisation is conducted under a slight vacuum at a temperature of about 80°C, pH of about 4.6 and at a pressure of about -46.66 KPa.
  • Deionised water 612 is also added to the vacuum during crystallisation.
  • a portion of the manganese sulphate monohydrate 614 is bled off, and sent to a calcium removal step in order to keep the concentration of calcium below 400 mg/kg in the mother liquor.
  • Calcium sulphate (CaSO4) 616 seed reacts with the manganese sulphate monohydrate 614 during the calcium removal step.
  • the more refined manganese sulphate monohydrate 618 is fed to the first crystallisation process in a continuous loop, until the target concentration of calcium is achieved in the manganese sulphate monohydrate 620 produced by crystallisation.
  • a calcium sulphate waste 617 is discarded.
  • the refined manganese sulphate monohydrate 620 undergoes dissolution J3 with deionised water 622 at a temperature of about 60°C, pH of 5.5. and at atmospheric pressure.
  • the product from dissolution 624 undergoes a pH adjustment stage J4 wherein sulphuric acid 626 and ammonium hydroxide 628 are added to the product of dissolution 624 to produce a product 630 which is at a lower pH of about 4.9.
  • the product 630 undergoes a second crystallisation and filtration process J2 at a temperature of about 80°C, pH of about 4.9 and pressure of about -46.66 KPa.
  • the resulting crystal slurry 632 is centrifuged and washed to remove a portion of the entrained impurities, and then dried at about 150°C in a drying apparatus J5 to produce a final high purity manganese sulphate monohydrate 636. A portion of the crystal slurry 638 is also sent back to the first crystallisation step J1 for further processing.
  • the purified crystals will conform to the following maximum impurity limits (PPm):
  • the manganese content is greater than 32% in the crystals.
  • Example 1 Preparing 2.5 litre of leach solution or first manganese solution
  • the leaching process was completed after about 1 to 2 hours when the pH of the leach solution was about 5 to 6;
  • the leached solution was filtered at a minimum of 5 bar and up to 18 bar to produce a filtrate and filter cake, the filtrate was retained for subsequent processes.
  • Example 2 Preparing 100g of manganese carbonate: 1 . A slurry consisting of 72g of food grade ammonium bicarbonate and 100 ml of deionised water was made;
  • step 3 Ammonium bicarbonate slurry of step 1 was added to the first manganese solution of step 2 while stirring the mixture;
  • the pH of the mixture was controlled with the addition of 25% ammonium hydroxide (approximately 40 mis) to a target pH of about 6.5, and with a band of 6 to 7; the ammonium hydroxide was added slowly, drop by drop; and
  • the manganese oxide was removed from the oven and allowed to cool to ambient conditions before the next step.
  • step 2 The solution of step 1 was heated to a temperature of about 80 to 85°C;
  • step 3 The mixture of step 3 was hot filtered after 45 minutes, the filter cake washed with deionised water and dried, and the filtrate was discarded;
  • step 2 The mixture of step 2 was stirred at 300 rpm, and drops of hydrogen peroxide were added to the mixture until the solution turned pink, showing that all the MnO x had dissolved and the resulting solution was a pure manganese sulphate solution.
  • Calcium level was at 134 mg/kg, and magnesium level was at 87 mg/kg.
  • the product from evaporation was 525 kg of manganese sulphate monohydrate crystals and 566 kg of entrained mother liquor.
  • the centrate had a maximum amount of 400 mg/kg of calcium.
  • the invention involves progressive removal of the “hard to remove” alkali earth metals, calcium and magnesium, first by carbonate precipitation and then by progressive partial crystallisation under vacuum and calcium precipitation;
  • the oxidative roasting and washing step has a high efficiency of removing calcium from the system
  • the crystallisation steps use calcium solubility limits to make sure that calcium does not precipitate together with manganese sulphate crystals, and the carbonate step uses ammonium hydroxide to maximise manganese carbonate yield;

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Abstract

L'invention concerne un procédé (10) de production de monohydrate de sulfate de manganèse (50). Le procédé comprend les étapes consistant à (B) lixivier un minerai (12) dans de l'acide sulfurique (14) pour produire une première solution de manganèse (16) ; (C) mettre en contact la solution (16) avec un bicarbonate (18) et un hydroxyde (20) pour précipiter le carbonate de manganèse (22) ; (D) chauffer le carbonate (22) pour produire un mélange d'oxyde de manganèse (24) ; (E) laver le mélange (24) pour éliminer le calcium (28) ; (F) mettre en contact le mélange lavé (30) avec du peroxyde d'hydrogène (32) et de l'acide sulfurique (34) pour convertir l'oxyde en une deuxième solution (36) ; (G) cristalliser le monohydrate de sulfate de manganèse (40) à partir de la solution (36) ; (H) dissoudre le monohydrate (40) dans de l'eau (42) pour produire une troisième solution (44) ; (I) éliminer le calcium (46) de la solution (44) pour produire une troisième solution de manganèse lavée (48) ; et (J) cristalliser le monohydrate de sulfate de manganèse (50) à partir de la solution (48).
PCT/IB2023/058530 2022-09-06 2023-08-29 Procédé de production de monohydrate de sulfate de manganèse Ceased WO2024052760A1 (fr)

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Application Number Priority Date Filing Date Title
GB2212989.4 2022-09-06
GBGB2212989.4A GB202212989D0 (en) 2022-09-06 2022-09-06 A process for producing manganese sulphate monohydrate

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Citations (12)

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US3106451A (en) * 1960-11-01 1963-10-08 United Internat Res Inc Method of producing manganese sulfate
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