WO2022140805A1 - Procédé de production de zinc en tant qu'oxyde de zinc ou zinc métallique directement à partir de minerais sulfures - Google Patents

Procédé de production de zinc en tant qu'oxyde de zinc ou zinc métallique directement à partir de minerais sulfures Download PDF

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Publication number
WO2022140805A1
WO2022140805A1 PCT/VN2021/000025 VN2021000025W WO2022140805A1 WO 2022140805 A1 WO2022140805 A1 WO 2022140805A1 VN 2021000025 W VN2021000025 W VN 2021000025W WO 2022140805 A1 WO2022140805 A1 WO 2022140805A1
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zinc
ore
recovering
oxide
mixture
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PCT/VN2021/000025
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English (en)
Inventor
Trinh Hong TU
Trinh Duc ANH
Le Ngoc DIEP
Nguyen Xuan LONG
Le Thi Ngoc ANH
Tran Kim TUYEN
Trinh Tuan LINH
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Tu Trinh Hong
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Publication of WO2022140805A1 publication Critical patent/WO2022140805A1/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
    • C22B19/00—Obtaining zinc or zinc oxide
    • C22B19/04—Obtaining zinc by distilling
    • C22B19/16—Distilling vessels
    • 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
    • C22B17/00—Obtaining cadmium
    • C22B17/02—Obtaining cadmium by dry 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
    • C22B30/00—Obtaining antimony, arsenic or bismuth
    • C22B30/04—Obtaining arsenic
    • 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
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/02—Refining by liquating, filtering, centrifuging, distilling, or supersonic wave action including acoustic waves
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B47/00—Obtaining manganese
    • C22B47/0018—Treating ocean floor nodules
    • C22B47/0045—Treating ocean floor nodules by wet processes
    • C22B47/0081—Treatment or purification of solutions, e.g. obtained by leaching

Definitions

  • the present invention relates to non-ferrous metallurgy, more specifically the present invention relates to a process for tire production of zinc in the form of zinc oxide or zinc metal, and sulfur element directly from sulfide ores, including a source of zinc sulfide (ZnS) concentrate or zinc sulfide ore symbiotically with lead sulfide (PbS), copper sulfide (CuS), cadmium sulfide (CdS), iron sulfide (FeS), arsenic sulfide (AsS), etc.
  • ZnS zinc sulfide
  • CuS copper sulfide
  • CdS cadmium sulfide
  • FeS iron sulfide
  • AsS arsenic sulfide
  • the present process also allows to enrich valuable or precious combination of metals such as remaining Cu, Pb, Ag, Ba, Be, Bi, Cd, Co, Cr, Ga, Li, Ni, Sb, Sn, V, Zn, etc., and other rare elements such as La, Mo, Nb, Sc, Sr, Ta, W, Y, Ce, Ge, etc., present in the ores.
  • Zinc metal is produced by mining metallurgy. After crushing ores, foam flotation is used to separate minerals based on their different wettability. In this step, zinc accounts for approximately 50%, the rest is sulfur (approximately 32%), iron (approximately 13%), and S1O 2 (approximately 5%).
  • the pyrometallurgy reduces zinc oxide with carbon or carbon monoxide at 950°C to zinc metal in vapor form.
  • the zinc vapor is recovered in a condenser. This process is represented by the followings:
  • the electrowinning separates zinc from zinc oxide by sulfuric acid:
  • electrolytic method can be used to produce zinc metal
  • the process for the production of zinc above can only recover zinc, do not allow to recover zinc directly from sulfide ores due to requirement of intermediate stages.
  • two types of furnaces are usually used: old conventional fluidized bed furnace and new horizontal tube furnace, both of these technologies however yield a low content of zinc oxide powder, ranging from 55 to 90%.
  • Zinc components are also partially lost in each subsequent stage, resulting in low efficiency of zinc recovery of the above process in general
  • the present invention relates to a process for the production of zinc as zinc oxide or zinc metal directly from sulfide ores, the process including the steps of:
  • step (iv.1) recovering the zinc component in the form of zinc oxide by distillation in an open atmosphere: placing the milled mixture in step (iii) into the open-type distillation apparatus, raising temperature of the distillation apparatus gradually at a speed of 7- 9°C/minute to distillation temperature of 750-900°C, preferably 900°C to first recover a mixture of arsenic oxide (AS2O3) and cadmium oxide (CdO), and then 910-1050°C, preferably 1030°C, to recover zinc oxide (ZnO), when the above-mentioned distillation temperatures are reached, the temperature is kept until no more vapor is observed, and an exhaust fen system is used to first recover the vapor mixture of arsenic oxide and cadmium oxide and then the zinc oxide vapor at each of the above-mentioned distillation temperatures, respectively, finally when the zinc oxide vapor is no longer observed, supplying heat is stopped and the de-zincized residue is recovered;
  • AS2O3 arsenic oxide
  • step (iv.2) and/or recovering the zinc component in the form of zinc element and other metal elements with sublimation temperatures ⁇ 1000°C by distillation in a closed atmosphere placing the milled mixture in step (iii) into the close-type distillation apparatus, raising temperature of the distillation apparatus gradually at a rate of 3- 5°C/minute to reach up to 910-1050°C, preferably 1050°C, maintaining at the temperature until no more vapor is observed, fractionally condensing an evaporating mixture containing zinc element, cadmium element and arsenic element at condensing temperatures of 800- 900°C, 650-720°C and 520-570°C in three successive fractions to separate zinc element, cadmium element and finally arsenic element, respectively, and when the vapor is no longer observed, supplying heat is stopped and the de-zincized residue is recovered.
  • the process further including:
  • step (v) recovering iron from the de-zincized residue in step (iv) by magnetic extraction.
  • the process further including:
  • step (vi) recovering sulfur from the de-ironed residue in step (v) by reacting the residue with H 2 SO 4 35-40%, recovering evaporating H 2 S and reacting it with a moist Fe 2 O 3 adsorbent at room temperature, and blowing hot air of temparature between 115 and 125°C, preferably 119°C into the sulfur saturated adsorbent to yield sulfur element.
  • the process further including:
  • step (vii) separating the solid/liquid mixture in step (vi) by a filter, preferably a plate and frame filter press, to obtain a solid residue and a liquid solution mainly including MnSO 4 , FeSO 4 , ZnSO 4 .
  • a filter preferably a plate and frame filter press
  • the process further including:
  • step (viii) separating and enriching precious metals and rare elements from the solid residue obtained in step (vii): dissolving the solid residue into water and then pumping on a trough to collect the precious or valuable metals, which are located near the pump nozzle, such as remaining Cu, Pb, Ag, Ba, Be, Bi, Cd, Co, Cr, Ga, Li, Ni, Sb, Sn, V, Zn, and other rare elements such as La, Mo, Nb, Sc, Sr, Ta, W, Y, Ce, Ge which are heavier than other components in the residue and have an increase in content of the metals and rare elements compared to that of the original ore.
  • the process further including:
  • the process further including:
  • step (x) recovering Mn 2 O 3 from the resulting MnSO 4 solution for reuse in step (ii): adding Na 2 CO 3 solution 30% - 40%, preferably 30%, to the MnSO 4 solution until the pH is reached equal to 8 to precipitate MnCO 3 , washing the precipitate, then drying and calcining in air to a temperature of between 200 and 230°C to obtain Mn 2 O 3 , and reusing Mn 2 O 3 in step (ii) to reduce amount of the manganese ore to be used.
  • the manganese ore used is pyrolusite containing mainly MnO 2 .
  • the content of Mn metal in the manganese ore is more than 30%.
  • the carbon material is anthracite coal.
  • the mixture of arsenic oxide and cadmium oxide obtained in step (iv.l) is distilled at a temperature of between 130 and 140°C, preferably at 135°C, to sublimate the arsenic oxide from the cadmium oxide, thereby recovering each of the oxides separately.
  • the mixture of arsenic oxide and cadmium oxide obtained in step (iv.1) is mixed with the carbon material and heated at 300-630°C and 650- 800°C, respectively, to recover arsenic element and cadmium element, respectively.
  • ZnCO 3 obtained in step (ix) is decomposed to ZnO in 100°C water.
  • ZnO obtained is added to the mixture in step (iii) in case of recovering the zinc component in the form of zinc element in step (iv.2).
  • the present process differs at least from those known in that it uses manganese ores and carbon to bind sulfur in sulfide ores, such as source of zinc sulfide (ZnS) concentrate or zinc sulfide ores symbiotically with lead sulfide (PbS), copper sulfide (CuS), cadmium sulfide (CdS), iron sulfide (FeS), arsenic sulfide (AsS), etc., and to repel metals such as zinc, cadmium, arsenic, lead, copper, iron, etc., from their sulfide moiety.
  • ZnS zinc sulfide
  • PbS lead sulfide
  • CuS copper sulfide
  • CdS cadmium sulfide
  • FeS iron sulfide
  • AsS arsenic sulfide
  • the process of recovering zinc, cadmium, and arsenic metals with sublimation temperature below 1000°C ( ⁇ 1000°C) is easy, and the process of separating and enriching precious or valuable combination of metals such as remaining Cu, Pb, Ag, Ba, Be, Bi, Cd, Co, Cr, Ga, Li, Ni, Sb, Sn, V, Zn, etc., and other rare elements such as La, Mo, Nb, Sc, Sr, Ta, W, Y, Ce, Ge, etc., are favorable.
  • Figure 1 shows an open-type zinc oxide recovery-distillation apparatus.
  • Figure 2 shows a close-type distillation apparatus for recovery of zinc metal directly from zinc sulfide ores, wherein the distillation is accompanied with exhaust of generated gas during the distillation.
  • a process for the production of zinc as zinc oxide or zinc metal directly from sulfide ores includes the steps of:
  • Zinc sulfide ore used is a source of ore from which soil has been removed by selection such as source of zinc sulfide (ZnS) concentrate or zinc sulfide ores symbiotically with lead sulfide (PbS), copper sulfide (CuS), cadmium sulfide (CdS), iron sulfide (FeS), arsenic sulfide (AsS), etc.,
  • the above-mentioned manganese ore mainly containing MnO 2 is pyrolusite. Where Mn 2 O 3 or Mn 3 O4 ores are used, sintering is not necessary.
  • content of Mn metal in the manganese ore is more than 30%. If the content is below 30%, then there will be a large volume of the material during calcination at the step of recovering zinc below, thereby resulting in a considerable waste of heat energy and preventing metals in the zinc sulfide ore from sublimating.
  • step (iv.l) coverage of the manganese ore on particles of the zinc sulfide ore will be affected, or SO 2 will be released when recovering zinc components in the form of zinc oxide in an open environment (an open atmosphere) in step (iv.l) below, or other sulfide components mixed in the ore such as CdS, ZnS, AsS will be melt when recovering zinc components in the form of zinc metal in a closed environment (closed atmosphere) in step (iv.2) below.
  • the content of Mn content is higher than parts by weight, then bulk volume of the material will be increased, which results in a waste of the material and heat of calcination in the step of recovering zinc (iv) below.
  • the carbon material is anthracite coal.
  • the invention is not limited to this particular material, other carbon containing materials can also be used, for example, wood charcoal, coal dust
  • ratio of S:Mn:C is 1:
  • ratio of S:Mn:C is
  • the mixture is then blended and finely ground in a ball mill to a particle size of between 80 and 100 ⁇ m. If the particle size is smaller than 80 ⁇ m, the mixture is entrained in CO 2 when heated. If the particle size is large 100 ⁇ m, then coverage of the manganese ore on the sulfide ore particles is poor, resulting in an incomplete recovery of all sulfur.
  • the milled mixture in step (iii) is taken out and placed into an open-type distillation apparatus as shown in Figure 1 for distillation to recover zinc oxide as well as its sublimated components, including arsenic oxide (AS2O3) and cadmium oxide (CdO).
  • the apparatus includes an open body 1; a heating means 2 is located outside of the body, for example at the bottom as shown in Figure 1 (indirect heating) or inside of the body (direct heating - not shown in the figure); and an exhaust fan system 3 are arranged above the opening of the body 1 to recover zinc oxide vapor as well as a mixture of arsenic oxide and cadmium oxide vapor.
  • any heating means may be used, but the means preferably allows to control rate of gradual heating at a rate of 7-9°C/min to a distillation temperature of 750- 900°C, preferably 900°C to first recover the mixture of arsenic oxide and cadmium oxide, and then 910-1050°C, preferably 1030°C to recover zinc oxide. If the distillation temperature is higher than 1050°C, metals, for example, lead, silver, copper mixed in the sulfide ore easily form alloys with each other.
  • the heating means is a direct arc heating type (Direct arc furnaces).
  • Zn vapor rises and reacts with O 2 in air to form zinc oxide which is recovered by the exhaust fan system 3.
  • the mixture of arsenic oxide and cadmium oxide obtained in step (iv.l) is distilled at a temperature of between 130 and 140°C, preferably at 135°C, to sublimate arsenic oxide and the remainer is CdO, which can be recovered separately from the oxide.
  • the mixture of arsenic oxide and cadmium oxide obtained in step (iv.l) is mixed with the carbon material and heated at 300-630°C and 650-800°C, respectively, to recover arsenic element and cadmium element, respectively, according to chemical equations:
  • the content of C used in tins embodiment is preferably more than the reaction stoichiometry.
  • the close-type distillation apparatus includes: an apparatus body 10 for material storage, the body has an inlet port 11 for material, an outlet 12 for residue discharging, and a vapor observation window 13; a heating means 14 is located outside of the body 10, for example at the bottom as shown in Figure 2 (indirect heating) or inside of the body 10 (direct heating - not shown in the Figure); and a condenser 20 includes one end connected to the upper part of the body 10 and the other discharge end which is immersed in a water bath 30, wherein the condenser 20 consists of sections: the first section 21 for condensing and separating zinc element, the second 22 for condensing and separating cadmium element, and the third 23 for condensing and separating arsenic element, each of the sections includes
  • any heating means may be used, for example, a direct heating means of electric arc furnace type.
  • the means preferably allows to control rate of gradual heating at a rate of 3-5°C/min until the distillation temperature reaches up to 910-1050°C, preferably 1050°C. When the temperature within this range is reached, the temperature is kept constant (until no more vapor is observed). During distillation, several main reactions take place as follows:
  • Cd and Zn metals have low sublimation temperatures, they will then rise out of the distillation apparatus to form a vapor mixture.
  • Other metals such as Mn, Pb, Fe, Cu are in the residue, along with other oxides.
  • the vaporized mixture contains zinc element, cadmium element and arsenic element whose sublimation temperatures are lower than 1000°C ( ⁇ 1000°C).
  • zinc element, cadmium element and finally arsenic element are fractionally condensed and removed through the outlets 211, 222, and 233, respectively.
  • COi generated is discharged through the other discharge end of condenser 20 which is immersed in a water bath 30.
  • the present process further including:
  • step (v) recovering iron from the de-zincized residue in step (iv) by magnetic extraction.
  • the recovery is carried out using a magnetic separator which is well known to the person skilled in the art
  • the process further including:
  • A1(OH) 3 is present in the solid residue and, upon separation in step (viii) below, the precipitant will accompany remaining C in the residue.
  • H 2 S evaporated is recovered and reacted with a adsorbent Fe 3 O 3 moist, for example, the humidity is between 25 and 35%, at room temperature (28-30°C).
  • Sulfur element is then recovered by blowing hot air of temparature between 115 and 125°C, preferably 119°C, according to reaction equation below:
  • the process further including:
  • step (vii) separating the solid/liquid mixture in step (vi)
  • the solid/liquid mixture after reacting with H 2 SO 4 in step (vi) is passed through a filter, such as a rotary drum vacuum filter, a gravity filter, a plate and frame filter press, preferably a plate and frame filter press, to collect a solid residue and a liquid solution containing primary components which are MnSO 4 , FeSO 4 , ZnSO 4 (and possibly alkaline or alkaline earth metal salts such as K 2 SO 4 , Na 2 SO 4 , MgSO 4 in small concentrations).
  • a filter such as a rotary drum vacuum filter, a gravity filter, a plate and frame filter press, preferably a plate and frame filter press.
  • the process further including:
  • the sorted zinc sulfide also contains a variety of other elements in small or trace amounts, including precious or valuable combination of metals such as remaining Cu, Pb, Ag, Ba, Be, Bi, Cd, Co, Cr, Ga, Li, Ni, Sb, Sn, V, Zn, etc., and other rare elements such as La, Mo, Nb, Sc, Sr, Ta, W, Y, Ce, Ge, etc. These components remain in the residue.
  • gravity separation method can be applied. More specifically, dissolve the residue obtained in step (vii) in water, then pump to a trough, heavier precious or valuable metals and rare elements as above- mentioned will be located near the pump nozzle, wherein their contents have been already enriched (increased compared to that of the original ore), residual C with Al(OH) 3 are located farthest away, followed by commercially invaluable and harmless elements such as CaSO 4 , SiOz, coal slag, etc., which will be removed.
  • the mixture of residual C and A1(OH) 3 is burned to recover AbO 3 .
  • the mixture of residual C and Al(OH)j is reacted with H 2 SO 4 to recover Ab(SO 4 ) 3 .
  • the process further including:
  • step (ix) cleaning the liquid solution obtained in step (vii) to obtain manganese sulfate MnSO 4 .
  • the solution of step (vii) will be pumped to a storage tank, whose volume depends on the output
  • the solution contains main components MnSO 4 , FeSO 4 , ZnSO 4 (and possibly alkali or alkaline earth metal salts such as K 2 SO 4 , Na 2 SO 4 , MgSO 4 , these salts are however quite small in concentration that do not affect quality of the recovered MnSO 4 solution).
  • the resulting solution is filtered with a filter, for example a plate and frame filter press, to remove precipitants so as to obtain the MnSO 4 solution.
  • a filter for example a plate and frame filter press
  • ZnCO 3 is decomposed in 100°C water to recover ZnO.
  • the resulting ZnO is added to the mixture in step (iii) in case of recovering the zinc component as zinc element in step (iv.2).
  • the process further including:
  • step (x) recovering Mn 2 O 3 from the resulting MnSO 4 solution for reuse in step (ii).
  • Na 2 CO 3 solution 30% - 40%, preferably 30%, is added into the MnSO 4 solution obtained in step (ix) until the pH is reached equal to 8 to which MnCO 3 is completely
  • Mn 2 O 3 is reused in step (ii) to reduce amount of the manganese ore to be used.
  • Example 1 Recovery of zinc components in the form of zinc oxide (i) Preparation of zinc sulfide ore
  • Source of the zinc sulfide ore used in this example orginates from Cho Don mine, Bac Kan, Vietnam. Composition of the ore is shown in Table 1 below.
  • Source of the manganese ore used in the example is one from Cao Bang province, Vietnam (which is pyrolusite ore). Composition of the ore is shown in Table 2. A required amount of the manganese ore, as calculated below, will be calcined at a temperature of 530°C to completely convert MnO 2 m the ore into Mn 2 O 3 .
  • the Cao Bang manganese ore contains 37.57% Mn, so a required amount of the manganese ore is:
  • the mixture of the above ingredients is put into a ball mill to finely grind to a particle size of 80-100 ⁇ m.
  • step (iii) is placed into an open distillation apparatus as shown in Figure 1.
  • the apparatus is put on a brazier, temperature is slowly raised at 8°C/min to distillation temperature of 900°C to first recover a arsenic oxide and cadmium oxide mixture, and then 1050°C to recover zinc oxide.
  • distillation temperature 900°C
  • the temperature is kept (until no more vapor is observed) and an exhaust fen system is used to first recover the vapor mixture of arsenic oxide and cadmium oxide and then the zinc oxide vapor at each of the above-mentioned distillation temperatures, respectively.
  • the zinc oxide vapor is no longer observed, supplying heat is stopped and the residue obtained in Example 1 is taken out to further recover sulfur element, and to enrich precious metals and rare elements in accordance with steps in Example 3 below.
  • results of the zinc oxide recovery are shown in Table 3 below. From the Table 3, it can be seen that after sintering, elements recovered include zinc in the form of zinc oxide (after the recovery of zinc, remaining mass is 5.4 kg, so zinc it is all basically recovered in the form of zinc oxide with a recovery of 98.1%), the mixture of arsenic and cadmium oxides. Meanwhile, sulfur is mainly bound in the form of MnS and rare elements remain in the residue.
  • Source of the zinc sulfide used in this example originates from Tuyen Quang province, Vietnam.
  • the ore is further added with 3% ZnO.
  • Composition of the ore is shown in Table 4 below.
  • Natural manganese ore resource of battery company Van Dien (Vietnam) is used in this example: Amount of the manganese ore, as calculated below, is used and sintered at a temperature of 530°C to completely convert MnOi in the ore into Mn 2 O 3 .
  • the mixture is fed to a ball mill for fine grinding to a particle size of 80-100 ⁇ m.
  • the milled mixture is taken out to put in closed-type distillation apparatus as shown in Figure 2.
  • temperature of the apparatus body 10 will be raised slowly at a rate of 3-5°C/min until the temperature reaches up to 1050°C, the temperature is then kept constant to obtain a vapor mixture including zinc, cadmium and arsenic element.
  • zinc element, cadmium element and finally arsenic element are fractionally condensed, respectively, and removed through the metal outlets 211, 222, and 233, respectively.
  • Example 2 When it is observed that vapors are no longer escaped from the body 10, heat supplying is stopped, the residue obtained in Example 2 is taken out further recover sulfur element, and to enrich precious metals and rare elements in accordance with steps in example 3 below. Results of the zinc metal recovery are shown in Table 6 below.
  • the recovered elements include zinc in the form of zinc element (basically with a recovery of 94.74%), arsenic element, cadmium element. Meanwhile, sulfur is mainly bound in the form of MnS, heavy metals, rare elements remain intact in the residue.
  • step (v) Recovering iron from the de-zincized residue in step (iv) by magnetic extraction.
  • Al(OH) 3 is present in the solid residue and, upon separation in step (viii) below, the precipitant will accompany remaining C in the residue.
  • H 2 S evaporated is recovered and reacted with a adsorbent Fe 2 O 3 moist, for example, the humidity is 30% at room temperature 30°C.
  • step (vii) Separating the solid/liquid mixture in step (vi)
  • the solid/liquid mixture after reacting with H 2 SO 4 in step (vi) is passed through a plate and frame filter press to collect a solid residue and a liquid solution containing primary components which are MnSO 4 , FeSO 4 , ZnSO 4 (and possibly alkaline or alkaline earth metal salts such as K 2 SO 4 , Na 2 SO 4 MgSO 4 in small concentrations).
  • step (viii) Separating and enriching precious metals, rare elements from the solid residue obtained in step (vii) to increase content of the precious metals and rare elements.
  • the sorted zinc sulfide also contains a variety of other elements in small or trace amounts, including precious or valuable combination of metals such as remaining Cu, Pb, Ag, Ba, Be, Bi, Cd, Co, Cr, Ga, Li, Ni, Sb, Sn, V, Zn, etc., and other rare elements such as La, Mo, Nb; Sc, Sr, Ta, W, Y, Ce, Ge, etc. These components remain in the residue.
  • step (vii) The residue obtained in step (vii) is dissolved in water, then pumped to a trough of 2m in length, heavier precious or valuable metals and rare elements as above-mentioned are located near the pump nozzle, residual C with Al(OH) 3 are located farthest away, followed by commercially invaluable and harmless elements such as CaSO 4 , SiO 2 , coal slag, etc., which are removed.
  • step (ix) cleaning the liquid solution obtained in step (vii) to obtain manganese sulfate MnSO 4 .
  • the solution of step (vii) will be pumped to a storage tank.
  • the solution contains main components MnSO 4 , FeSO 4 , ZnSO 4 (and possibly alkali or alkaline earth metal salts such as K 2 SO 4 , Na 2 SO 4 , MgSO 4 , concentration of these salts is however quite small that do not affect quality of the recovered MnSO 4 solution).
  • the resulting solution is filtered with a plate and frame filter press to remove precipitants so as to obtain the MnSO 4 solution.
  • step (x) recovering Mn 2 O 3 from the resulting MnSO 4 solution for reuse in step (ii).
  • NazCO 3 solution 30% is added into the MnSO 4 solution obtained in step (ix) until the pH is reached equal to 8 to which MnCO 3 is completely precipitated as follows:
  • Mn 2 O 3 is reused in step (ii) to reduce amount of the manganese ore to be used.
  • the present process allows to enrich and recover valuable components in ores, and helps reduce waste which causes environmental pollution that the above known technologies cannot satisfy. This is demonstrated by following aspects: Thorough recovery of zinc (as zinc oxide or elemental zinc) and precious metals directly from zinc sulfide ores, the recovery rate of zinc components can reach 98%. Additionally, the present process also recovers precious metals and rare elements from manganese ores.
  • Enrichment of precious or valuable metal components such as residual Cu, Pb, Ag, Ba, Be, Bi, Cd, Co, Cr, Ga, Li, Ni, Sb, Sn, V, Zn, etc., and other rare elements such as La, Mo, Nb, Sc, Sr, Ta, W, Y, Ce, Ge, etc., present in sulfide ores, which are often mixed with ash and slag and discharged, insulting in matter waste, contamination of soil.

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Abstract

L'invention concerne un procédé de production de zinc en tant qu'oxyde de zinc ou zinc métallique directement à partir de minerais sulfures, le procédé comprenant les étapes consistant (i) à préparer un minerai de sulfure de zinc ; (ii) à préparer des minerais de manganèse ; (iii) à mélanger et broyer le minerai de sulfure de zinc avec un mélange du minerai de manganèse et de matière carbonée dans un broyeur à boulets ; (iv) à récupérer des composants à base de zinc sous la forme d'oxyde de zinc ou de zinc métallique. Le procédé comprend en outre séquentiellement l'une des étapes suivantes : (v) récupérer, par extraction magnétique, du fer à partir du résidu dézincifié à l'étape (iv) ; (vi) récupérer du soufre à partir du résidu déferré à l'étape (v) avec du H2SO4 ; (vii) séparer le mélange solide/liquide de l'étape (vi) au moyen d'un filtre-presse à plaques et à cadre ; (viii) séparer et enrichir des métaux précieux et des éléments rares du résidu solide obtenu à l'étape (vii) ; (ix) nettoyer la solution liquide obtenue à l'étape (vii) pour obtenir du sulfate de manganèse MnSO4 ; (x) récupérer du Mn2O3 à partir de la solution de MnSO 4 résultante, pour une réutilisation dans l'étape (ii).
PCT/VN2021/000025 2020-12-21 2021-12-20 Procédé de production de zinc en tant qu'oxyde de zinc ou zinc métallique directement à partir de minerais sulfures WO2022140805A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115612860A (zh) * 2022-10-26 2023-01-17 云南驰宏资源综合利用有限公司 一种高硅锌焙烧矿的浸出方法
CN115612860B (zh) * 2022-10-26 2023-09-19 云南驰宏资源综合利用有限公司 一种高硅锌焙烧矿的浸出方法

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