WO2014104562A1 - Procédé de production d'au moins un composé de manganèse, de sulfate de potassium et d'engrais à partir d'une substance contenant du potassium et du manganèse de faible pureté - Google Patents

Procédé de production d'au moins un composé de manganèse, de sulfate de potassium et d'engrais à partir d'une substance contenant du potassium et du manganèse de faible pureté Download PDF

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WO2014104562A1
WO2014104562A1 PCT/KR2013/009872 KR2013009872W WO2014104562A1 WO 2014104562 A1 WO2014104562 A1 WO 2014104562A1 KR 2013009872 W KR2013009872 W KR 2013009872W WO 2014104562 A1 WO2014104562 A1 WO 2014104562A1
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manganese
potassium
sulfate
solid
leachate
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PCT/KR2013/009872
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Korean (ko)
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김명준
트람탐
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전남대학교산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C01D5/06—Preparation of sulfates by double decomposition
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C01D5/16—Purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
    • C01G1/12—Sulfides
    • 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; Hydroxides
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D1/00—Fertilisers containing potassium
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D1/00—Fertilisers containing potassium
    • C05D1/02—Manufacture from potassium chloride or sulfate or double or mixed salts thereof
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F7/00—Fertilisers from waste water, sewage sludge, sea slime, ooze or similar masses
    • C05F7/005—Waste water from industrial processing material neither of agricultural nor of animal origin

Definitions

  • the present invention is a high purity potassium sulfate (K 2 SO 4 ), high purity manganese compounds (manganese sulfate monohydrate (MnSO 4 H 2 O), trimanganese tetraoxide (Mn 3 O 4 ), EMM ( Electronic Managed Metal)) and at least one of manganese and potassium-containing fertilizers in a single process.
  • the secondary battery is composed of a negative electrode, a positive electrode, an electrolyte, and a separator, and manganese oxide is widely used in the manufacture of the positive electrode.
  • the demand for secondary batteries soars, the demand for materials required for manufacturing such secondary batteries is also increasing rapidly.
  • Trivalent manganese tetraoxide (Mn 3 O 4 ) and manganese oxide (III) (Mn 2 O 3 ) may be used as the positive electrode material of the secondary battery.
  • trimanganese tetraoxide (Mn 3 O 4 ) instead of manganese oxide (III) (Mn 2 O 3 ) but now, trivalent manganese tetraoxide (Mn 3 O 4 )
  • Mn 3 O 4 trimanganese tetraoxide
  • manganese sulfate monohydrate (MnSO 4 ⁇ H 2 O, manganese sulphate monohydrate) is the main material of the positive electrode active material used in secondary batteries.
  • manganese sulfate monohydrate used as an electrode material of a secondary battery has a problem that is almost dependent on imports like trimanganese tetraoxide (Mn 3 O 4 ).
  • Prior-A-10-2011-76109 discloses and discloses a method for manufacturing the same time the valuable metals and compounds of potassium sulfate from manganese nodules
  • -A-10-2012-93948 discloses a MnSO from MnO 2 of the medium and low quality ore 4
  • it discloses a method for producing a H 2 O
  • Laid-Open Patent Publication No. 10-2011-111057 discloses a manufacturing method of a crystalline sasanhwasam manganese, lithium-manganese oxide.
  • an object of the present invention is to economically obtain high purity potassium sulfate (K 2 SO 4 ), high purity manganese compounds (manganese sulfate monohydrate (MnSO 4 H 2 O), trimanganese tetraoxide (Mn 3 ) from low purity manganese and potassium content O 4 ), EMM (Electronic Managed Metal) and at least one of manganese and potassium-containing fertilizer in one process.
  • the above object is, according to the present invention, in the process for producing a high purity manganese compound, potassium sulfate and fertilizer from a low purity manganese and potassium content through one process, the first after adding water to the low purity manganese and potassium content Separating the first potassium leachate containing potassium hydroxide and the first solid by solid-liquid separation; Adding a sulfide to the first potassium leachate to remove the first impurity, and adding sulfuric acid or sodium sulfate to prepare high purity potassium sulfate; Obtaining a first manganese leachate by adding at least one of hydrochloric acid and sulfuric acid and a reducing agent to the first solid, and removing a second impurity using sulfide and potassium hydroxide to obtain a second manganese leachate; Preparing high purity trimanganese tetraoxide through pH adjustment using potassium hydroxide in the second manganese leachate; Removing a third impurity by using a s
  • the above object in the method for producing high purity potassium sulfate from low-purity manganese and potassium-containing, comprising adding potassium hydroxide through the first solid-liquid separation after adding water to the low-purity manganese and potassium-containing Separating the first potassium leach solution and the solid; Dissolving sulfide in the first potassium leachate by adding 2 to 5 times the total molar amount of impurities in water and then removing impurities; After obtaining the second potassium leaching solution from which the impurities have been removed through solid-liquid separation, high purity potassium sulfate is obtained by adding 0.1 to 3 times sulfuric acid or sodium sulfate of potassium molar ratio contained in the second potassium leaching solution and precipitating with potassium sulfate. It can be achieved by a method for preparing potassium sulfate from low purity manganese and potassium containing comprising the step of.
  • the above object in the production method of high purity trimanganese tetraoxide from low-purity manganese and potassium containing, containing potassium hydroxide through the first solid-liquid separation after the addition of water to the low-purity manganese and potassium containing Separating the first potassium leachate from the first solid; Hydrochloric acid diluted at a ratio of 2 to 4 times the molar content of manganese contained in the first solid and a reducing agent dissolved in water at a ratio of 0.5 to 2 times the molar content of manganese Obtaining a first manganese leachate and a second solid by separating solid solution; Removing iron by adjusting the pH of the first manganese leachate to pH3 or more using potassium hydroxide diluted to 1 M or more after obtaining the first manganese leachate; Removing impurities using sulfides and potassium hydroxide to obtain a second manganese leachate; It can be achieved by a high-
  • the above object in the method for producing high purity manganese sulfate monohydrate from low purity manganese and potassium containing, after adding water to the low purity manganese and potassium containing water through the first solid-liquid separation Separating the first potassium leachate and the first solid comprising;
  • a second solid solution by adding hydrochloric acid at a ratio of 2 to 4 times the molar content of manganese contained in the first solid and a reducing agent dissolved in water at a ratio of 0.5 to 2 times the molar content of manganese contained in the first solid Obtaining a first manganese leachate and a second solid through separation; Obtaining a third manganese leach solution by removing impurities using the sulfide in the first manganese leach solution;
  • the method of manufacturing a high purity manganese sulfate monohydrate from the low-purity manganese and potassium containing comprising the step of adjusting the pH of the third manganese leachate using potassium hydrox
  • the above object in the fertilizer manufacturing method from a low-purity manganese and potassium-containing material, after the addition of water to the low-purity manganese and potassium-containing material first containing potassium hydroxide through the first solid-liquid separation Separating the potassium leach solution and the first solid;
  • hydrochloric acid diluted at a ratio of 2 to 4 times the molar content of manganese contained in the first solid and a reducing agent dissolved in water at a ratio of 0.5 to 2 times the molar content of manganese to the first solid Separating the second solid through two-liquid separation;
  • Leaching lead by adding hydrochloric acid and an oxidizing agent diluted to 2M to 5M to the second solid; Separation of the third solid through the third solid-liquid separation, and drying the third solid to obtain a fertilizer containing potassium and manganese can be achieved by a fertilizer manufacturing method from low-purity manganese and potassium containing have.
  • the above object is, according to the present invention, in the method for producing high purity potassium sulfate and high purity trimanganese tetraoxide from low purity manganese and potassium containing, after the addition of water to the low purity manganese and potassium containing the first solid-liquid separation Separating the first potassium leachate containing potassium hydroxide and the first solid through; Dissolving sulfide in the first potassium leachate by adding 2 to 5 times the total molar amount of impurities in water and then removing impurities; After obtaining the second potassium leaching solution from which the impurities have been removed through solid-liquid separation, high purity potassium sulfate is obtained by adding 0.1 to 3 times sulfuric acid or sodium sulfate of potassium molar ratio contained in the second potassium leaching solution and precipitating with potassium sulfate.
  • the above object in the method for producing high-purity potassium sulfate and high-purity manganese sulfate monohydrate from low-purity manganese and potassium-containing, after the addition of water to the low-purity manganese and potassium-containing first liquid-liquid separation Separating the first potassium leachate containing potassium hydroxide from the first solid; Dissolving sulfide in the first potassium leachate by adding 2 to 5 times the total molar amount of impurities in water and then removing impurities; After obtaining the second potassium leaching solution from which the impurities have been removed through solid-liquid separation, high purity potassium sulfate is obtained by adding 0.1 to 3 times sulfuric acid or sodium sulfate of potassium molar ratio contained in the second potassium leaching solution and precipitating with potassium sulfate.
  • the above object in the production method of high purity potassium sulfate and fertilizer from low-purity manganese and potassium-containing, potassium hydroxide through the first solid-liquid separation after adding water to the low-purity manganese and potassium-containing Separating the first potassium leachate and the first solid comprising a; Dissolving sulfide in the first potassium leachate by adding 2 to 5 times the total molar amount of impurities in water and then removing impurities; After obtaining the second potassium leaching solution from which the impurities have been removed through solid-liquid separation, high purity potassium sulfate is obtained by adding 0.1 to 3 times sulfuric acid or sodium sulfate of potassium molar ratio contained in the second potassium leaching solution and precipitating with potassium sulfate.
  • the method for producing a high purity manganese compound and potassium sulfate from a low-purity manganese and potassium containing through the first solid-liquid separation after adding water to the low-purity manganese and potassium containing Separating the first potassium leachate and the first solid containing potassium; Adding a sulfide to the first potassium leachate to remove the first impurity, and adding sulfuric acid or sodium sulfate to prepare high purity potassium sulfate; Adding sulfuric acid to the first solid to be converted to manganese sulfate to remove the second impurity using at least one of calcium hydroxide and sulfide, and obtaining manganese leachate through second solid-liquid separation; It can be achieved by a method for producing a high purity manganese compound and potassium sulfate from a low purity manganese and potassium containing comprising the step of preparing a high purity manganese compound from the manganese leaching solution.
  • the above object in the method for producing manganese sulfate monohydrate from low-purity manganese and potassium containing, potassium is included through the solid-liquid separation after adding water to the low-purity manganese and potassium containing Separating the potassium leach solution and the solid; Converting the solid into manganese sulfate by roasting with the addition of sulfuric acid; Dissolving the manganese sulfate in water and then removing impurities using at least one of calcium hydroxide and sulfide to obtain a manganese leachate; Sequentially adding potassium hydroxide and sulfuric acid to the manganese leachate to obtain an aqueous manganese sulfate; It can be achieved by a method for preparing manganese sulfate monohydrate from a low purity manganese and potassium containing comprising drying the aqueous manganese sulfate solution to produce a high purity manganese sulfate monohydrate.
  • EMM Electronic Manganese Metal
  • potassium is added through solid-liquid separation after adding water to the low-purity manganese and potassium-containing Separating the potassium leach solution and the solid contained; Converting the solid into manganese sulfate by roasting with the addition of sulfuric acid; Dissolving the manganese sulfate in water and then removing impurities using at least one of calcium hydroxide and sulfide to obtain a manganese leachate; Sequentially adding potassium hydroxide and sulfuric acid to the manganese leachate to obtain an aqueous manganese sulfate;
  • the aqueous manganese sulfate solution may be achieved by a method of producing EMM (Electronic Manganese Metal) from low-purity manganese and potassium containing the step of producing an electronic manganese metal (EMM) using an electrolytic extraction method.
  • the above object in the method for producing trimanganese tetraoxide from a low-purity manganese and potassium-containing, potassium containing potassium through the solid-liquid separation after adding water to the low-purity manganese and potassium-containing Separating the leachate from the solid; Converting the solid into manganese sulfate by roasting with the addition of sulfuric acid; Dissolving the manganese sulfate in water and then removing impurities using at least one of calcium hydroxide and sulfide to obtain a manganese leachate; Precipitating manganese hydroxide using potassium hydroxide in the manganese leachate;
  • the manganese hydroxide may be achieved by a method of preparing trimanganese tetraoxide from low purity manganese and potassium containing the step of quenching the heat treatment in an oxidizing atmosphere to prepare trimanganese tetraoxide.
  • the above object in the production method of potassium sulfate and manganese sulfate monohydrate from low-purity manganese and potassium containing, adding water to the low-purity manganese and potassium containing potassium through solid-liquid separation Separating the first potassium leachate and the solid contained therein; Dissolving sulfide in the first potassium leachate by adding 2 to 5 times the total molar amount of impurities in water and then removing impurities; After obtaining the second potassium leaching solution from which the impurities have been removed through solid-liquid separation, high purity potassium sulfate is obtained by adding 0.1 to 3 times sulfuric acid or sodium sulfate of potassium molar ratio contained in the second potassium leaching solution and precipitating with potassium sulfate.
  • the above object is, according to the present invention, in the method for producing potassium sulfate and EMM (Electronic Manganese Metal) from low-purity manganese and potassium-containing, water is added to the low-purity manganese and potassium-containing after solid-liquid separation Separating the first potassium leachate and the solid containing potassium through the solid; Dissolving sulfide in the first potassium leachate by adding 2 to 5 times the total molar amount of impurities in water and then removing impurities; After obtaining the second potassium leaching solution from which the impurities have been removed through solid-liquid separation, high purity potassium sulfate is obtained by adding 0.1 to 3 times sulfuric acid or sodium sulfate of potassium molar ratio contained in the second potassium leaching solution and precipitating with potassium sulfate.
  • EMM Electro Manganese Metal
  • aqueous manganese sulfate solution may be achieved by a method of preparing potassium sulfate and EMM (Electronic Manganese Metal) from low purity manganese and potassium containing the step of producing an electronic manganese metal (EMM) using an electrolytic extraction method. .
  • EMM Electronic Manganese Metal
  • potassium is included through the solid-liquid separation after adding water to the low-purity manganese and potassium-containing Separating the first potassium leachate from the solid and the solid; Dissolving sulfide in the first potassium leachate by adding 2 to 5 times the total molar amount of impurities in water and then removing impurities; After obtaining the second potassium leaching solution from which the impurities have been removed through solid-liquid separation, high purity potassium sulfate is obtained by adding 0.1 to 3 times sulfuric acid or sodium sulfate of potassium molar ratio contained in the second potassium leaching solution and precipitating with potassium sulfate.
  • the manganese hydroxide may be achieved by a method of preparing potassium sulfate and trimanganese tetraoxide from low-purity manganese and potassium containing, including the step of quenching after heat treatment in an oxidizing atmosphere to prepare trimanganese tetraoxide.
  • a high-purity manganese compound manganese sulfate monohydrate, trimanganese tetraoxide and Electronic Manganese Metal (EMM), high-purity potassium sulfate and fertilizer economically from low-purity manganese and potassium content through one process
  • EMM Electronic Manganese Metal
  • FIG. 1 is a schematic flowchart of a method for preparing a manganese compound, potassium sulfate and fertilizer according to a first embodiment of the present invention
  • FIG. 2 is a flowchart of a method for preparing potassium sulfate in a manganese compound according to the first embodiment of the present invention
  • FIG. 3 is a flowchart of a method for preparing trimanganese tetraoxide in a manganese compound according to the first embodiment of the present invention
  • FIG. 4 is a flowchart of a method for preparing manganese sulfate monohydrate in a manganese compound according to the first embodiment of the present invention
  • FIG. 6 is a schematic flowchart of preparation of high purity manganese compound and high purity potassium sulfate according to the second embodiment of the present invention
  • FIG. 7 is a flowchart of a method for preparing high purity potassium sulfate according to a second embodiment of the present invention.
  • FIG. 8 is a flowchart of a method of manufacturing high purity manganese compound according to a second embodiment of the present invention.
  • FIGS. 6 to 8 illustrate a second embodiment of the present invention.
  • the present invention relates to a preparation method capable of simultaneously and / or respectively manufacturing a manganese compound and potassium sulfate.
  • the method for preparing potassium sulfate from low purity manganese and potassium content is the same.
  • the first and second embodiments differ in the method of preparing manganese compounds and / or fertilizers depending on the reagents added thereafter.
  • FIG. 1 is a schematic diagram of a method for preparing a manganese compound, potassium sulfate and fertilizer according to a first embodiment of the present invention.
  • the method for producing a manganese compound, potassium sulfate and fertilizer according to the present invention by adding water to the low-purity manganese and potassium containing water leaching potassium (S110), the first through the solid-liquid separation
  • the first potassium leaching solution containing potassium and the first solid is separated (S120).
  • Sulfide is added to the first potassium leachate separated through the first solid-liquid separation to remove the first impurity (S130), and sulfuric acid or sodium sulfate is added to precipitate with potassium sulfate to prepare high purity potassium sulfate (S140).
  • At least one of hydrochloric acid and sulfuric acid and a reducing agent are added to the first solid separated through the first solid-liquid separation in S120 to obtain a first manganese leachate (S210), and a second impurity is removed by using a sulfide. Obtaining two manganese leachate (S220).
  • the potassium hydroxide may use potassium hydroxide contained in the first potassium leachate separated in S120.
  • the potassium hydroxide may use potassium hydroxide contained in the first potassium leachate separated in S120.
  • the leaching of lead by adding hydrochloric acid and oxidation to the second solid remaining after the first manganese leachate is obtained through solid-liquid separation of S210 (S410), and then removing manganese and potassium to prepare a fertilizer containing manganese and potassium (S420). do.
  • the preparation of high purity potassium sulfate according to the first embodiment of the present invention will be described in more detail with reference to FIG. 2, and the preparation of the high purity trimanganese tetraoxide according to the first embodiment of the present invention will be described in more detail with reference to FIG. 3.
  • the manufacturing of the high purity manganese sulfate monohydrate according to the first embodiment of the present invention will be described in more detail with reference to FIG. 4, and the fertilizer manufacturing according to the first embodiment of the present invention will be described in more detail with reference to FIG. 5.
  • FIG 2 is a detailed view of a high purity potassium sulfate manufacturing method of the manganese compound according to the first embodiment of the present invention.
  • the low purity manganese and potassium inclusions include low purity manganese and potassium dust or low purity manganese and potassium ore.
  • potassium hydroxide is leached through a reaction as in Scheme 1 below.
  • the water is added in an amount that can be well stirred by adding about 2 to 4 times, preferably 2 to 3 times, and more preferably about 2.5 times by volume ratio of the low purity manganese and potassium containing.
  • the first solid solution separation is performed to separate the first potassium leachate containing the leached potassium hydroxide and the first solid (S120).
  • the first potassium leachate obtained through the first solid-liquid separation of S120 is used in the next step for the production of high purity potassium sulfate, or of the potassium hydroxide used for the production of high purity trimanganese tetraoxide or the production of high purity manganese sulfate monohydrate. It can be used as a material.
  • the first solid obtained through the first solid-liquid separation of S120 may be used as a material for the preparation of high purity trimanganese tetraoxide, or manganese sulfate monohydrate.
  • Sulfide is added to remove the first impurity in the first potassium leachate of S120 to precipitate the first impurity in the form of sulfide (S130).
  • the first impurity includes lead (Pb), nickel (Ni), zinc (Zn), cobalt (Co) or copper (Cu).
  • the sulfide includes at least one of sodium sulfide (Na 2 S), calcium sulfide (CaS) and hydrogen sulfide (H 2 S), and is added after dissolving 2 to 5 times the total molar amount of the first impurity in water. Due to the addition of these sulfides, the first impurity precipitates in the form of sulfides (NiS, PbS, ZnS, CoS, CuS).
  • the sulfide slurry is discarded through a second solid-liquid separation to obtain a second potassium leachate from which the first impurity is removed (S131).
  • the second potassium leachate from which the first impurity of S131 is removed is used as a next step for the production of high purity potassium sulfate, or as a material of potassium hydroxide used for the production of high purity trimanganese tetraoxide or the production of high purity manganese sulfate monohydrate. Can be used.
  • the second potassium leachate of S131 is used as a material of potassium hydroxide used for the production of high-purity trimanganese tetraoxide or a high-purity manganese sulfate monohydrate.
  • Potassium sulfate is precipitated by adding sulfuric acid or sodium sulfate to the second potassium leachate (S141).
  • the sulfuric acid or sodium sulfate is added 0.1 to 3 times, preferably 0.5 to 2 times the potassium molar ratio.
  • a third solid-liquid separation may be performed to prepare high purity (more than 99%) potassium sulfate (K 2 SO 4 ) as a solid.
  • FIG 3 is a detailed view of a method for producing trimanganese tetraoxide in the manganese compound according to the first embodiment of the present invention.
  • trimanganese tetraoxide may be manufactured using the first solid material separated at S120 during the preparation of potassium sulfate.
  • At least one of hydrochloric acid and sulfuric acid and a reducing agent are added to the first solid separated in S120 to perform a fourth solid-liquid separation to obtain a first manganese leachate and a second solid (S210).
  • the hydrochloric acid is dissolved in water at a ratio of 2 to 4 times the molar content of manganese contained in the first solid, preferably 2 to 4 times, and added to the first solid.
  • the reducing agent comprises a reagent, coke or sulfur dioxide (SO 2 gas) containing an oxalate group (C 2 O 4 2- ).
  • the reagent containing the oxalate group (C 2 O 4 2- ) includes oxalic acid (H 2 C 2 O 4 2H 2 O) or sodium oxalate (Na 2 C 2 O 4 ).
  • Iron is removed using potassium hydroxide in the first manganese leachate (S211).
  • the potassium hydroxide used may be potassium hydroxide contained in the first potassium leachate of S120 or the second potassium leachate of S131.
  • the potassium hydroxide may be removed by adding so that the pH of the first manganese leachate to pH 3 or more, preferably pH 3 to pH 5.5, the iron is removed in the form of Fe (OH) 3 or FeOOH This reaction is shown in Scheme 5 below.
  • solid-liquid separation may be performed to dispose of the slurry, thereby obtaining manganese leachate from which iron has been removed.
  • Sulfate and potassium hydroxide are added to the manganese leachate from which iron is removed to remove a second impurity to obtain a second manganese leachate (S220).
  • the manganese leaching solution from which iron is removed includes a second impurity such as nickel (Ni), lead (Pb), zinc (Zn), cobalt (Co), copper (Cu), and such impurities are added to sulfides to form sulfides. Can be removed by precipitation.
  • a second impurity such as nickel (Ni), lead (Pb), zinc (Zn), cobalt (Co), copper (Cu)
  • impurities are added to sulfides to form sulfides. Can be removed by precipitation.
  • the sulfide comprises at least one of sodium sulfide (Na 2 S), calcium sulfide (CaS) and hydrogen sulfide (H 2 S), wherein the sulfide is in a ratio of 10 to 50 times the total molar amount of the second impurity, preferably It is added at a ratio of 15 to 45 times, more preferably 30 to 35 times, and the pH of the added sulfide may be adjusted to pH 7 to pH 8, preferably pH 8.
  • the sulfide is added to react for about 10 to 100 minutes, preferably 20 to 80 minutes, more preferably 30 to 60 minutes.
  • potassium hydroxide was added for about 10 to 60 minutes, preferably 10 to 40 minutes, more preferably 20 to 30 minutes so that the pH of the iron-manganese leachate was pH5 to pH6.
  • nickel (Ni), lead (Pb), zinc (Zn), cobalt (Co), or copper (Cu) which are impurities other than the iron, are precipitated in the form of sulfides (NiS, PbS, ZnS, CoS, CuS). Can be.
  • the potassium hydroxide may be potassium hydroxide contained in the first potassium leachate of S120 or the second potassium leachate of S131.
  • the sulfide slurry is discarded through solid-liquid separation to obtain a second manganese leachate from which the second impurity is removed.
  • Manganese is precipitated by adjusting pH using potassium hydroxide in the second manganese leachate (S231).
  • the potassium hydroxide solution is diluted to 1 M or more and added to the second manganese leachate to pH 7 to pH 9 in a non-oxidizing atmosphere at a temperature of 60 to 70 to precipitate manganese.
  • the precipitated manganese form includes Mn (OH) 2 .
  • a fifth solid-liquid separation may be performed to obtain manganese oxide precipitated in S231, and the precipitated manganese oxide may further include washing with water in a non-oxidizing atmosphere at a temperature of 60 to 90 (S233). .
  • the washing has the effect of removing other impurities in the manganese oxide.
  • the remaining solution after separating the manganese oxide precipitated through the fifth solid-liquid separation may be used in place of water for potassium precipitation of S110 during the recovery step of the potassium sulfate.
  • Heat-treatment and quenching may be performed on the washed manganese oxide to prepare high purity trimanganese tetraoxide (S235).
  • the washed manganese oxide is dried using a drier and heat-treated at a temperature of 800 to 1100 after drying.
  • Heat treatment is performed using equipment such as rotary kiln incinerator, and the sample is mixed to allow sufficient reaction during the heat treatment. It also includes the step of quenching after the heat treatment.
  • Manganese from which impurities are removed by the heat treatment is reduced to Mn 2 O 3 , and rapidly cooled to oxidize it to Mn 3 O 4 manganese compound. After performing the heat treatment can be cooled to room temperature within a short time. Through this process, high purity trimanganese tetraoxide (Mn 3 O 4 ) that can be used in a secondary battery can be prepared, and the reaction is shown in Schemes 6 and 7.
  • FIG. 4 is a detailed view of a method of preparing manganese sulfate monohydrate in a manganese compound according to a first embodiment of the present invention.
  • manganese sulfate monohydrate may be prepared using the first manganese leachate obtained in S210 during the preparation of the high purity trimanganese tetraoxide. More preferably, manganese sulfate monohydrate can be prepared using the manganese leachate from which iron has been removed through step S211.
  • the third manganese leachate is obtained by removing the third impurity by using sulfide in the first manganese leachate (S310).
  • the third impurity is nickel (Ni), lead (Pb), zinc (Zn), and cobalt (Co). ), Copper (Cu), and the like, and these impurities can be removed by precipitation in the form of sulfides by addition of sulfides.
  • the sulfide includes at least one of sodium sulfide (Na 2 S), calcium sulfide (CaS) and hydrogen sulfide (H 2 S), and the sulfide is added after dissolving 2 to 5 times the total molar amount of the third impurity in water. do.
  • PH adjustment is performed using potassium hydroxide in the third manganese leachate to precipitate manganese (S321).
  • Manganese, magnesium, calcium, potassium and the like are dissolved in the third manganese leachate, and it is necessary to selectively precipitate manganese. Accordingly, the potassium hydroxide solution is diluted to 1 M or more and added to the third manganese leachate to pH 7 to pH 9 in a non-oxidizing atmosphere at a temperature of 60 to 70 to precipitate manganese. If the pH is lower than the appropriate pH, the recovery of manganese (Mn) is lowered. If the pH is higher than the pH, precipitation of impurities may occur, thereby lowering the purity of the final product.
  • potassium hydroxide contained in the first potassium leachate of S120 or the second potassium leachate of S131 may be used.
  • the precipitated manganese form includes Mn (OH) 2 .
  • the sixth solid-liquid separation is performed to obtain manganese oxide precipitated in S321 and then washed (S323).
  • the manganese oxide obtained after the sixth solid-liquid separation may further comprise the step of washing with water in a non-oxidizing atmosphere at a temperature of 60 to 90.
  • the washing has the effect of removing other impurities in the manganese oxide.
  • the remaining solution after separating the manganese oxide precipitated through the sixth solid-liquid separation may be used in place of water for potassium precipitation of S110 during the recovery step of the potassium sulfate.
  • the sulfuric acid is added to the manganese oxide obtained after the washing and redissolved (S325).
  • the amount of sulfuric acid added is added at a ratio of 0.5 to 1.5 times the molar content of manganese contained in the manganese oxide, and the reaction is shown in Scheme 8 below.
  • the method may further include neutralizing the solution redissolved by sulfuric acid.
  • Reagents for the neutralization reaction may be used manganese oxide of step S321, the manganese oxide of step S321 is neutralized so that the pH of the re-dissolution solution is pH4 to pH6.
  • the neutralizing solution performs a seventh solid-liquid separation to obtain a fourth manganese leachate (S327).
  • the obtained fourth manganese leachate is crystallized by performing vacuum evaporation to prepare a high purity manganese sulfate monohydrate (S329).
  • the appropriate saturated steam pressure for the vacuum evaporation is 0.57 ⁇ 0.7kgf / cm 2 , preferably 0.6 ⁇ 0.6.5kgf / cm 2 , the vacuum evaporation is carried out at a temperature of 85 to 90.
  • the evaporation point may be lower than 80, thereby producing manganese sulfate pentahydrate (MnSO 4 5H 2 0) instead of manganese sulfate monohydrate (MnSO 4 ⁇ H 2 O).
  • the temperature is higher than the above conditions, the energy efficiency may be lowered, resulting in lower economic efficiency.
  • Figure 5 is a detailed view of the manufacturing method of the fertilizer containing manganese and potassium according to the first embodiment of the present invention.
  • the hydrochloric acid is added by dilution in water at a concentration of 2M to 5M, preferably at a concentration of 2.5M to 3.5M, more preferably 3M.
  • the oxidant comprises hydrogen peroxide (H 2 O 2 ), the hydrogen peroxide is added in a molar ratio of 2 to 10 times with respect to the lead contained in the second solid, preferably 2 to 4 times molar ratio, more preferably Is added in three molar ratios.
  • H 2 O 2 hydrogen peroxide
  • a fertilizer containing potassium and manganese (S420).
  • the content of lead contained in the fertilizer is 0.03% or less and only a very small amount remains.
  • about 4% of manganese, more than 3% of potassium is contained. Because of this, it can be used as a fertilizer by itself or mixed with other fertilizers lacking manganese and / or potassium.
  • potassium hydroxide used in the preparation of high purity trimanganese tetraoxide or high purity manganese sulfate monohydrate is a hydroxide contained in the first potassium leaching liquid or the second potassium leaching liquid produced during the production of high purity potassium sulfate. Potassium can be used.
  • the potassium hydroxide is used to adjust the pH of the manganese leachate, sodium hydroxide (NaOH) may be used for pH control, the cost of sodium hydroxide (NaOH) is not economical because it is expensive.
  • potassium hydroxide used for pH control of manganese leachate may be separately purchased and used, but the hydroxide contained in the first potassium leachate or the second potassium leachate produced during the preparation of high purity potassium sulfate may be used.
  • the cost savings effect can be quite excellent.
  • FIG. 6 is a schematic flowchart of preparation of high purity manganese compound and high purity potassium sulfate according to the second embodiment of the present invention.
  • leaching potassium by adding water to the low-purity manganese and potassium containing (S1110), the first solid-liquid separation Separating the first potassium leaching solution and the first solid containing potassium hydroxide through (S1120).
  • Sulfide is added to the first potassium leachate separated through the first solid-liquid separation to remove the first impurity (S1130), and sulfuric acid or sodium sulfate is added to prepare high-purity potassium sulfate (S1140).
  • step S1210 Adding sulfuric acid to the first solid separated in step S1120 and roasting it to convert it into manganese sulfate (S1210), and adding a sulfide and potassium hydroxide to remove a second impurity to obtain a manganese leachate (S1220) and To obtain the manganese sulfate solution by sequentially adding potassium hydroxide and sulfuric acid to the manganese leachate (S1230), and drying the manganese sulfate solution to obtain a high purity manganese sulfate monohydrate (S1240).
  • the potassium hydroxide used in the steps S1220 and S1230 may be the first potassium leach solution of the step S1120.
  • the manganese sulfate aqueous solution obtained in step S1230 may be prepared by using an electrowinning method (Electrowinning) EMM (Electronic Manganese Metal) (S1310).
  • EMM Electro Manganese Metal
  • step S1410 the step of precipitating manganese hydroxide using potassium hydroxide in the manganese leachate obtained in step S1220 (S1410), and drying and quenching the manganese hydroxide to prepare a high-purity trimanganese tetraoxide (S1420).
  • the potassium hydroxide of step S1410 may also use the first potassium leach solution of step S1120.
  • the present invention provides a method for producing potassium sulfate, manganese sulfate monohydrate, EMM and trimanganese tetraoxide from low purity manganese and potassium content through one process.
  • FIG. 7 is a flowchart of preparation of high purity potassium sulfate according to a second embodiment of the present invention.
  • potassium is leached by adding water to low-purity manganese and potassium-containing materials (S1110).
  • the low-purity manganese and potassium-containing products leach potassium by adding water to low-purity manganese, potassium ore or by-product manganese, potassium dust.
  • potassium hydroxide is leached through a reaction as in Scheme 1 below.
  • the water is added in an amount that can be well stirred by adding about 2 to 4 times, preferably 2 to 3 times, more preferably about 2.5 times, by volume ratio of the low purity manganese and potassium containing.
  • the first solid solution is separated to separate the first potassium leachate containing the leached potassium hydroxide and the first solid (S1120).
  • the first potassium leachate obtained through the first solid-liquid separation of S1120 is used in the next step for the production of high purity potassium sulfate, or of the potassium hydroxide used for the production of high-purity trimanganese tetraoxide or the production of high-purity manganese sulfate monohydrate. It can be used as a material.
  • the first solid obtained through the first solid-liquid separation of S1120 may be used as a material for manufacturing high purity trimanganese tetraoxide, manganese sulfate monohydrate, and EMM which are manganese compounds.
  • a sulfide is added to precipitate the first impurity in the form of sulfide (S1130).
  • the first impurity includes heavy metals such as lead (Pb), nickel (Ni), zinc (Zn), cobalt (Co) or copper (Cu).
  • the sulfide includes at least one of sodium sulfide (Na 2 S), calcium sulfide (CaS) and hydrogen sulfide (H 2 S), and is added after dissolving 2 to 5 times the total molar amount of the first impurity in water. Due to the addition of these sulfides, the first impurity precipitates in the form of sulfides (NiS, PbS, ZnS, CoS, CuS).
  • the sulfide slurry is discarded to obtain a second potassium leachate from which the first impurity is removed (S1131).
  • the second potassium leachate from which the first impurity of S1131 is removed is used as a next step for the preparation of high purity potassium sulfate, or as a material of potassium hydroxide used for the production of high purity trimanganese tetraoxide or the preparation of high purity manganese sulfate monohydrate. Can be used.
  • the second potassium leachate of S1131 is used as a material of potassium hydroxide used for the production of high purity trimanganese tetraoxide or high purity manganese sulfate monohydrate. Do.
  • Potassium sulfate is precipitated by adding sulfuric acid or sodium sulfate to the second potassium leachate (S1141).
  • the sulfuric acid or sodium sulfate is added 0.1 to 3 times, preferably 0.5 to 2 times the potassium molar ratio.
  • a third solid-liquid separation may be performed to prepare high purity (more than 99%) potassium sulfate (K 2 SO 4 ) as a solid.
  • sulfuric acid is added and roasted to the first solid obtained in step S1120 of FIG. 7 to be converted into manganese sulfate (S1210).
  • the sulfuric acid to be added is preferably a diluted sulfuric acid, for example, the sulfuric acid in a ratio of 1 to 3 times the molar content of manganese contained in the first solid, preferably in a ratio of 1.5 to 3 times Dilute in water and add.
  • the roasting temperature is 300 to 1000, preferably 500 to 800 roasted to convert the first solid to manganese sulfate, the reaction scheme is as follows.
  • Manganese leachate is obtained by adding a sulfide and potassium hydroxide to manganese sulfate obtained in step S1210 to remove the second impurity (S1220). This step may include more detailed steps as follows.
  • the first manganese leachate is obtained by adding water to the manganese sulfate obtained in step S1210 (S1221).
  • a second manganese leachate from which iron is removed is obtained (S1223).
  • Calcium hydroxide may be added to remove the iron so that the pH of the first manganese leachate is at least pH3, preferably pH3 to pH5.5.
  • the iron is removed in the form of Fe (OH) 3 or FeOOH, the reaction is shown in the following scheme.
  • Sulfide is added to the second manganese leachate from which iron is removed to obtain a third manganese leachate from which impurities other than iron are removed (S1225).
  • the second manganese leachate from which the iron is removed may further include impurities such as nickel (Ni), lead (Pb), zinc (Zn), cobalt (Co), and copper (Cu) other than iron. Accordingly, sulfides may be added to the second manganese leachate to precipitate and remove impurities other than iron in the form of sulfides.
  • the sulfide comprises sodium sulfide (Na 2 S), calcium sulfide (CaS) and hydrogen sulfide (H 2 S) at least one, the sulfide is a ratio of 2 to 50 times the total molar amount of impurities other than iron, preferably 2 It may be added in a ratio of 10 to 10 times, more preferably in a ratio of 3 to 6 times.
  • the sulfide slurry may be discarded through solid-liquid separation to obtain a third manganese leachate from which impurities other than iron are removed.
  • Potassium hydroxide and sulfuric acid are sequentially added to the third manganese leachate from which the impurities are removed to obtain an aqueous manganese sulfate solution (S1230).
  • This step may include more detailed steps as follows.
  • Potassium hydroxide is added to the third manganese leachate to precipitate into manganese hydroxide (S1231).
  • Manganese leaching liquid obtained in step S1225 is dissolved manganese, magnesium, calcium, potassium, etc., it is necessary to selectively precipitate manganese. Accordingly, the potassium hydroxide solution is diluted to 1 M or more and added to the third manganese leachate to pH 6 to pH 9 at a temperature of 60 to 70 at a temperature of 60 to 70 so that manganese is precipitated in the form of manganese hydroxide (Mn (OH) 2 ). . If the pH is lower than the appropriate pH, the recovery rate of manganese (Mn) is lowered. If the pH is higher than the pH, impurities may be precipitated, which may lower the purity of the final product.
  • the manganese hydroxide may further comprise the step of washing with water in a non-oxidizing atmosphere at a temperature of 60 to 90 (not shown).
  • the washing may also have the effect of further removing other impurities in the manganese hydroxide.
  • Manganese hydroxide precipitated through the solid-liquid separation is obtained and used in the next step, and the solution remaining after obtaining manganese hydroxide may be used in place of water for potassium leaching in step S1110.
  • the method may further include neutralizing the solution redissolved with sulfuric acid (not shown).
  • the reagent for the neutralization reaction may use manganese hydroxide in step S1231, and the manganese hydroxide used for the neutralization reaction may be neutralized such that the pH of the re-dissolution solution is pH4 to pH6.
  • the obtained manganese sulfate aqueous solution may be dried to obtain a high purity manganese sulfate monohydrate (S1240).
  • the drying process may include preparing a high purity manganese sulfate monohydrate by crystallizing the aqueous manganese sulfate solution by performing vacuum evaporation.
  • the appropriate saturated steam pressure for the vacuum evaporation is 0.57 ⁇ 0.7kgf / cm 2 , preferably 0.6 ⁇ 0.6.5kgf / cm 2 , it can be carried out under a temperature of 85 to 90 vacuum evaporation.
  • the evaporation point is lower than 80, and thus, manganese sulfate pentahydrate (MnSO 4 ⁇ 5H 2 O) may be formed instead of the manganese sulfate monohydrate (MnSO 4 ⁇ H 2 O.) Its efficiency is low and economic efficiency can be lowered.
  • the manganese sulfate solution obtained in step S1233 can be used for the preparation of EMM.
  • the manganese sulfate aqueous solution obtained in step S1233 may be manufactured by using an electrowinning method (Electrowinning).
  • step S1231 using the manganese hydroxide obtained in the step S1231 can be produced in high purity trimanganese tetraoxide.
  • the manganese hydroxide obtained in step S1231 may be heat-treated at a temperature of 800 to 1100 after drying using a dryer. Heat treatment is performed by using equipment such as rotary kiln incinerator, and it is well stirred so that the sample can react sufficiently during heat treatment, so that the oxidizing atmosphere can be achieved. In addition, the quenching treatment is performed after the heat treatment. Manganese from which impurities are removed by the heat treatment is reduced to Mn 2 O 3 , and rapid cooling is performed to oxidize it to Mn 3 O 4 manganese compound. After performing the heat treatment can be cooled to room temperature within a short time. Through this, tri- manganese tetraoxide (Mn 3 O 4 ) that can be used in a secondary battery can be obtained with high purity, and the reaction is shown in the following reaction formula.
  • Mn 3 O 4 tri- manganese tetraoxide
  • the concentration of sulfide is as follows.
  • Sulfide is added at a rate of 10 to 50 times the total molar amount of impurities other than iron, preferably at a rate of 15 to 45 times, more preferably at a rate of 30 to 35 times, and the pH of the added sulfide is pH7 To pH8, preferably adjusted to pH8. After the sulfide is added, the reaction may be performed for about 10 to 100 minutes, preferably 20 to 80 minutes, more preferably 30 to 60 minutes.
  • potassium hydroxide is added so that the pH of the iron-containing manganese leachate is pH 5 to pH 6, about 10 minutes to 60 minutes, preferably 10 minutes to 40 minutes, more preferably Can react for 20 to 30 minutes. That is, when pH is adjusted by adding potassium hydroxide after addition of sulfide, impurities such as nickel, lead, zinc, cobalt, and copper, which are impurities other than iron, form sulfides (NiS, PbS, ZnS, CoS, CuS). It can help to settle, and thus be more effective in removing impurities in the form of sulfides.

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  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Manufacture And Refinement Of Metals (AREA)
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Abstract

La présente invention concerne un procédé dans lequel un processus unique est utilisé pour produire au moins du sulfate de potassium de haute pureté (K2SO4), un composé de manganèse de haute pureté (du sulfate de manganèse monohydraté (MnSO4·H2O), du tétraoxyde de trimanganèse (Mn3O4) ou de l'EMM (métal de manganèse électronique (EMM)) et un engrais à base de manganèse et de potassium à partir d'une substance contenant du potassium et du manganèse de faible pureté. La présente invention concerne un procédé qui permet de produire, respectivement, du sulfate de potassium de haute pureté, un composé de manganèse de haute pureté et du fumier à partir d'une substance contenant du potassium et du manganèse de faible pureté. L'invention concerne également un procédé dans lequel un processus unique est utilisé pour produire simultanément du sulfate de potassium de haute pureté et un composé de manganèse de haute pureté à partir d'une substance contenant du potassium et du manganèse de faible pureté. L'invention concerne également un procédé dans lequel un processus unique est utilisé pour produire simultanément du sulfate de potassium de haute pureté et un engrais à partir d'une substance contenant du potassium et du manganèse de faible pureté.
PCT/KR2013/009872 2012-12-24 2013-11-04 Procédé de production d'au moins un composé de manganèse, de sulfate de potassium et d'engrais à partir d'une substance contenant du potassium et du manganèse de faible pureté WO2014104562A1 (fr)

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KR20030028006A (ko) * 2001-09-27 2003-04-08 문상우 황산망간 제조방법
KR20120093948A (ko) * 2009-10-10 2012-08-23 구이쩌우 레드스타 디벨로핑 코포레이션 리미티드 중저품질의 ＮｎＯ2 광석을 사용한 배연탈황으로 ＭｎＳＯ4ㆍＨ2Ｏ를 제조하는 방법
KR20120099119A (ko) * 2010-03-31 2012-09-06 구이쩌우 레드스타 디벨로핑 코포레이션 리미티드 황산 망간 일수화물의 제조방법
KR20120120378A (ko) * 2010-03-29 2012-11-01 베이징 맥스퀸 테크놀로지 컴퍼니 리미티드 황산 망간 일수화물의 제조방법

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JPH05147948A (ja) * 1991-12-03 1993-06-15 Mitsui Toatsu Chem Inc 硫酸マンガンの製造方法
KR20030028006A (ko) * 2001-09-27 2003-04-08 문상우 황산망간 제조방법
KR20120093948A (ko) * 2009-10-10 2012-08-23 구이쩌우 레드스타 디벨로핑 코포레이션 리미티드 중저품질의 ＮｎＯ2 광석을 사용한 배연탈황으로 ＭｎＳＯ4ㆍＨ2Ｏ를 제조하는 방법
KR20120120378A (ko) * 2010-03-29 2012-11-01 베이징 맥스퀸 테크놀로지 컴퍼니 리미티드 황산 망간 일수화물의 제조방법
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